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228.Журнал Сибирского федерального университета. Сер. Техника и технологии №5 2014

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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Журнал Сибирского федерального университета
2014
Journal of Siberian Federal University
7 (5)
Техника и технологии
Engineering & Technologies
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??.-????. ???, ?-? ???.-???. ????
?.?. ???????
??.-????. ???, ?-? ????. ????
?.?. ??????
??.-????. ???, ?-? ???.-???. ????
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??.-????. ???, ?-? ???.-???. ????
?.?. ????
Editorial Advisory Board
Chairman:
Eugene A. Vaganov
Members:
Josef J. Gitelzon
Vasily F. Shabanov
Andrey G. Degermendzhy
Valery L. Mironov
Gennady L. Pashkov
Vladimir V. Shaidurov
Vladimir V. Zuev
Editorial Board:
Editor-in-Chief:
Mikhail I. Gladyshev
Founding Editor:
Vladimir I. Kolmakov
Managing Editor:
Olga F. Alexandrova
Executive Editor for Engineering &
Technologies:
Vladimir A. Kulagin
CONTENTS
Sergei I. Andreev and Svetlana F. Babaeva
Mineral Resources of the Ocean: a Pragmatical Reality of the
Foreseeable Future or Geopolitical Phantom
? 501 ?
Alexander M. Barishnikov and Michael L. Gaft
The Application of Laser Element Online Analyzer MAYA for
Extraction of Mineral Raw Materials and For Stabilization of
Raw Mixtures in Nonferrous Metal Production
? 512 ?
Evgeniy V. Pustynnyh, Aleksey A. Nifontov,
Aleksey V. Perestoronin and Andrey V. Panov
Optimization of the Technology of Alumina Refinery of Branch
Ojsc &Sual[ &Uaz $ Sual[ in Processing of Bauxite STBR
? 525 ?
Peter V. Zaytsev, Yakov M. Shneerson,
Alexander Y. Lapin, Lev V. Chugaev,
Mikhail V. Klementiev, Mikhail A. Pleshkov,
Ilia V. Fomenko and Stepan S. Bakhvalov
Process Development for Refractory Gold Concentrates
Treatment on Pokrovsky POX Hub
? 533 ?
Natalya A. Grigorieva, Isaak Y. Fleitlikh,
Gennady L. Pashkov and Lidiya K. Nikiforova
Octyl Amine Influence on Redox Processes During Cobalt
Extraction with Bis(2,4,4-Trimethylpentyl)Dithiophosphinic
Acid
? 544 ?
Ilya I. Puzanov,
Andrey V. Zavadyak, Yaroslav A. Tretiyakov,
Mikhail M. Morozov, Anatoliy A. Gubin,
Vitaliy V. Platonov and Aleksandr V. Darkin
Electrical Resistance Preheating of High-Amperage Cells
? 552 ?
???????? ?.?. ?????? ????????? ?.?. ???????
???????????? ??????? ?.?. ?????????
????????? ? ?????? 27.08.2014 ?. ?????? 84x108/16. ???. ???. ?. 10,3.
??.-???. ?. 9,8. ?????? ???. ?????? ????????. ????? 1000 ???. ????? 2246.
?????????? ? ?? ??? ???. 660041, ??????????, ??. ?????????, 82a.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Editorial board for Engineering & Technologies:
Vladimir Kulagin ? Series Editor, Siberian Federal
University, Russia
Yury Alashkevich ? Siberian State Technological
University, Russia
Sereeter Batmцnkh ? Institute of Heat Engineering
and Industrial Ecology Mongolian Academy of
Sciences, Mongolia
Yuri Biba ? Dresser-Rand Company, USA
Carsten Drebenstedt ? Technische University
Bergakademie Freiberg, Germany
Yury Galerkin ? Saint Petersburg State Polytechnic
University, Russia
Gennady Gritsko ? Institute of Petroleum Geology and
Geophysics Russian Academy of Sciences, Siberian
Branch, Russia
Georg Guggenberger ? Institute of Soil Science Leibniz
University Hannover, Germany
Lev Endzhievsky ? Siberian Federal University, Russia
Feng-Chen Li ? School of Energy Science and
Engineering Harbin Institute of Technology, China
Vladimir Makarov ? Siberian Federal University, Russia
Aleksandr Mineev ? Siberian Federal University, Russia
Vladimir Moskvichev ? Special Designing and
Technological Bureau ?Nauka? Krasnoyarsk
Scientific Center of the Russian Academy of
Sciences, Siberian Branch, Russia
Bernard Nacke ? Institute of Electrotechnology Leibniz
University of Hannover, Germany
Oleksandr Nemchin ? CEO of the State Research
Institute of Innovative Technologies in Power
Energy and Energy Efficiency of the Fuel and
Energy Ministry of Ukraine, Ukraine
Valeriy Nikulin ? Kamsk Institute of Humanitarian and
Engineering Technologies, Russia
Oleg Ostrovski ? University of New South Wales,
Australia
Harald Oye ? Norwegian University of Science and
Technology, Norway
Vasili Panteleev ? Siberian Federal University, Russia
Petr Polyakov ? Siberian Federal University, Russia
Victor Timofeev ? Siberian Federal University, Russia
Ibragim Khisameev ? Kazan State Technological
University, Russia
Anatoly Shvidenko ? International Institute for Applied
Systems Analysis, Austria
Galina Chiganova ? Siberian Federal University, Russia
????????????? ? ??????????? ???
?? ? ??77-28-722 ?? 29.06.2007 ?.
????? ???????? ? «???????? ???????
????????????? ??????? ???????? ? ???????,
? ??????? ?????? ???? ????????????
???????? ??????? ?????????? ??????????? ??
????????? ?????? ??????? ??????? ? ?????????
????» (???????? 2010 ?.)
Olga Yu. Tkacheva, Alexander A. Red`kin,
Alexander. A. Dedyukhin, Alexey P. Apisarov,
Pavel E. Tin`gaev and Yurii P. Zaykov
Electrolytes Based on the Potassium Kriolit for LowTemperature Obtaining of Aluminium
? 561 ?
Juri A. Gorbunov
Main Characteristics and Future Development of
Aluminum Alloys with High Dispersion Ability of
Phase of Alloying Elements
? 570 ?
Vladimir A. Poluboyarov, Aleksandr A. Zhdanok,
Zoya A. Korotaeva and Victor A. Kuznetzov
Investigation of SHS Process IN W-TI-C System
for Production of Tungsten Carbides WC and
W2C. Application of Carbides Mixture for Cast Iron
Modification
? 579 ?
Viktor A. Berngardt, Tatiana N. Drozdova,
Tamara A. Orelkinа, Sergey B. Sidelnikov,
Olga V. Fedorova, Leonid P. Trifonenkov,
Viktor F. Frolov, and Aleksandr V. Salnikov
Development of Annealing Conditions wire Rod Alloy
of Al-Zr System to Reach Required Properties
? 587 ?
Andrey V. Zhuikov and Anatoliy I. Matyushenko
Decrease of Nitrogen Oxides in the Combustion
Process Kansk-Achinsk Coal
? 596 ?
Vladimir A. Kulagin, Ekaterina
S. Sapoghnikova, Olesya P. Stebeleva,
Ludmila V. Kashkina, Zhi-Ying Zheng,
Qian Li and Feng-Chen Li
Features of Influence of Cavitation Effects on
the Physicochemical Properties of Water and
Wastewater
? 605 ?
Nikolay D. Demidenko and Ludmila V. Kulagina
Numerical Analysis of Technological Systems
? 615 ?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
СОДЕРЖАНИЕ
С.И. Андреев, С.Ф. Бабаева
l,??!=???/? !??3!?/ l,!%"%?% %*?=?= $ C!=??=2,???*=
C!,?!=??/L ??%C%?,2,???*,L ?,!=?
!?=???%?2? %K%?!,?%?% K3?3???% ,?,
? 501 ?
Alexander M. Barishnikov and Michael L. Gaft
The Application of Laser Element Online Analyzer MAYA for Extraction of Mineral Raw Materials and For
Stabilization of Raw Mixtures in Nonferrous Metal Production
? 512 ?
Е.В. Пустынных, А.А. Нифонтов, А.В. Пересторонин, А.В. Панов
nC2,?,?=?, 2?.?%?%?,, ??,?%????%?% C!%,?"%??2"= ?= -,?,=?? n`n &q3=?[ &r`g $ qr`k[ C!,
C?!?!=K%2*? K%*?,2= q?ap
? 525 ?
Peter V. Zaytsev, Yakov M. Shneerson, Alexander Y. Lapin, Lev V. Chugaev,
Mikhail V. Klementiev, Mikhail A. Pleshkov, Ilia V. Fomenko and Stepan S. Bakhvalov
Process Development for Refractory Gold Concentrates Treatment on Pokrovsky POX Hub
? 533 ?
Н.А. Григорьева, И.Ю. Флейтлих, Г.Л. Пашков, Л.К. Никифорова
b?, ?,? %*2,?=?,?= ?= %*,??,2????%-"%??2=?%",2????/? C!%????/ C!, .*?2!=*?,, *%K=??2= K,?(2,4,42!,??2,?C??2,?)?,2,%-%?-,?%"%L *,??%2%L
? 544 ?
И.И. Пузанов, А.В. Завадяк, Я.А. Третьяков,
М.М. Морозов, А.А. Губин, В.В. Платонов, А.В Даркин
nK?,? "/?%*%=?C?!?/. .??*2!%?,??!%" C!, C%?%?, .??*2!%?%C!%2,"???,
? 552 ?
О.Ю. Ткачева, А.А. Редькин, А.А. Дедюхин,
А.П. Аписаров, П.Е. Тиньгаев, Ю.П. Зайков
}??*2!%?,2/ ?= %??%"? *=?,?"%?% *!,%?,2= ?? ?,?*%2??C?!=23!?%?% C%?3???, =???,?,
? 561 ?
Juri A. Gorbunov
Main Characteristics and Future Development of Aluminum Alloys with High Dispersion Ability of Phase of
Alloying Elements
? 570 ?
В.А. Полубояров, А.А. Жданок, З.А. Коротаева, В.А. Кузнецов
h?????%"=?,? C!%????= qbq " ?,?2??? W-TI-C ?? C%?3???, *=!K,?%" "%??-!=?= WC , W2C.
o!,?????,? ????, *=!K,?%" ?? ?%?,-,?,!%"=?, ?3?3?=
? 579 ?
В.А. Бернгардт, Т.Н. Дроздова, Т.А. Орелкина, С.Б. Сидельников,
О.В. Федорова, Л.П. Трифоненков, В.Ф. Фролов, А.В. Сальников
p=?!=K%2*= !??,?%" %2?,?= *=2=?*, ,? ?C?="%" ?,?2??/ Al-Zr ?? ?%?2,???, ?=?=??%?% *%?C??*?=
?"%L?2"
? 587 ?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
А.В. Жуйков, А.И. Матюшенко
C?,???,? %*?,?%" =?%2= " C!%????? ??,?=?, *=??*%-=?,??*,. 3???L
? 596 ?
В.А. Кулагин, Е.С. Сапожникова, О.П. Стебелева,
Л.В. Кашкина, Zhi-Ying Zheng, Qian Li and Feng-Chen Li
n?%K???%?2, "?, ?, .--?*2%" *=",2=?,, ?= -,?,*%-.,?,???*,? ?"%L?2"= "%?/ , ?2%*%"
? 605 ?
Н.Д. Демиденко, Л.В. Кулагина
),?????/L =?=?,? 2?C?%2?.?%?%?,???*,. ?,?2??
? 615 ?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 501-511
~~~
??? 551.214(265.53):553.32
Mineral Resources of the Ocean:
a Pragmatical Reality
of the Foreseeable Future
or Geopolitical Phantom
Sergei I. Andreev* and Svetlana F. Babaeva
FGUP VNIIOkeangeologi?
1 Angliysky prospect, St. Petersburg, 190121, Russia
Received 07.03.2014, received in revised form 12.04.2014, accepted 11.08.2014
The study is dedicated to the state of knowledge of the oceanic minerals (FMN, CMC, DSPS) and
estimation of their possible contribution to the raw materials base of the Country. The problem of
oceanic mineral resources may have not only geopolitical, but also practical value in the foreseeable
future.
Keywords: mineral resources of the ocean, ferromanganese nodules (FMN), cobaltmanganese crusts
(CMC), deep-see polymetallic sulfides (DSPS), prospecting, development perspectives.
???????????? ??????? ? ??????????? ???????? ?????? ?????? ? ??????????? ?? ?????????? ????? ?????? ?????????? ?????????. ?????? ????????????? ???????????? ??????? ???????? ?????????? (???) ? ????????????????? ????????? (???) ? ??????? ? ????? XIX ?.
? ???? ?????????? ??????? ?????????? ??????????? ???????????? ???????? ?? ??????? «??????????» ? 1872-1876 ??. ?????? ? ????????????? ??????????? ????? ??????????? ???????? ??????????? ??? ??????????? ? 1891 ?. [1]. ?????? ?????????? ???????? ? ??? ??? ?????????????? ????????? ??????????? ???????? ????? ???????, ? ???????? XX ????????, ? 1957 ?.,
????? ??????????? ? ??? ??????? ?????????? Ni ? Co (????? 1 %).
?????? ??????????? ???????? ??? ??? ?????? ? ?????????????????? ????? (???) ? ?????? ???????????? ? ???, ?? ??????? ? ???? ???????? ????? ???????, ? 70-? ??. XX ?., ?????
???????????? ? ??? ??????? ???????????? ?? (?? 0,8-1,0 %).
???????? ?????????? ????????????????? ??????????? (???) ?????? ? ????? ????????,
??? ??? ???????????? ????? ?????????? ??????????? ???? ? ???????????? Mn (25-30 %), Ni
(1,1-1,5 %), Cu (1,0-1,2 %), Co (?? 0,5-0,6 ?? 1 %), ??? ?????????? ????????????? ???????? ???????? ???????????: Mo (0,05-0,06 %) ? ??? (0,8-1,5 ??/?).
?????? ???????????? ??? ??? ?????? ? ????????????? ????????????????? ????????
(???), ?????? ? 1978 ?. ??? ?????, ? 1964-1966 ??., ? ??????? ???? ?????????? ??????????? ??
?????????? ??? ? ???????. ? ??????? ??? ???????????? Cu (5-10 %), Zn (10-20 %), Pb (2-5 %);
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: andreev@vniio.ru
# 501 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Sergei I. Andreev and Svetlana F. Babaeva. Mineral Resources of the Ocean: a Pragmatical Reality of the Foreseeable?
???????? Au (5-10 ?/? ? ????), Ag (????? ??????? ?? ????? ?? 10-11 ??/?); ?????? ? ??????????
????????: Cd, Sb, Ge, Se, Te, In, Bi ? ??.
?????????? ????????? ?????????? ???????? ?????????????? ????????, ???????????? ?
??? ??????: ??????????? ????? / ???? ?? Ni ? 3,7 ? ?????? ??????, ?? Co ????? ??? ? 25 ???, ??
???????? ? ? 1,3 ????, ?? ?? ? ? 1,9 ????. ???????????? ????????? Cu ?????????? 0,5 ????????
???????? ????? ??????? [2].
????????? ?????? ? ??????????? ? ???????? ???????????? ??? ???, ??? ? ??? ??
???????? ??? ???????? ????? ???????? ??????????. ??????? ?? ????????, ??????? ? ???????? ? ????????????? ?????? ?????? ???????? ????????????? ? 1982 ?. ? ???????????????? ?
1994 ?. ???????????? ?????????? ? ?????? ??? ????????????? ????????? ?? ???????? ?????. ?? ?????????? ???????????????? ? ?????????????? ????????????? ??????? ?? ????????
??? (????) ??? ???, ????-???????? ?. ????????, ??????.
?????? ? ???????? ??????????? ????????? ?? ???????? ?????, ????? ???????????????
?????????????????? ?????? (???) ?? ??? ? 1976 ?., ?? ??? ? 1985 ?., ?? ??? ? 1986-1987 ??. ?
1988 ?. ??? ???????? ??????????? ?????????????? ??????????? ?? ??????? ??? ? ???? ??????? ? ?????????? (????? ?????), ? ? 1992 ?. ????? ????????? ?? ???????? ????????? ??????
??????? ??????? ? ?????? ?? ??????? ??? ?? «????????????????» ? ??? ?? ???????.
? 2001 ?. ?????? ????????? 15-?????? ???????? ? ???? ?? ?????????? ??????????? ????? ?
???????? ??????????? ???????????? ?????? (???) ????????????? ??????? ??? ? ???? ??????? ? ?????????? (????? ?????).
? 2011 ?. ?????? ??????? ??????? ??? ? ???????? ????????????????? ???? ?????????????????????? ?????? (12є49ґ-20є54ґ?.?.), ? 2012 ?. ????????? ? ???? ???????? ?? ??? ???????? ?????? ?? 15 ???. ? ???? ?? ?????? ???????????? ?????? ?? ??????? ??? ? ????????????
????? (????? ?????), ??????????? ??????? ????????? ????? 2014 ?. ? ???? ?????? ????? ????????????, ??? ???????? ? ???? ?? ??? ???????? ????? ???????? ????? ????? 15 ???, ? 2029 ?.
????? ???????, ?????? ??????????? ?????? ? ??????? ???????? ??????????? ???????? ???????? ?????? ? ?????????????? ? ???? ? ?????? ????????? ?? ???????? ?????
? ??????? ????????? 35 ??? ???????? ?????????????? ????? ?? ???????? ? ???????????
???????? ???????????? ????????????? ???? ????? ???????????? ?????: ???, ??? ?
???. ??? ???? ???????, ??? ????????? ?????? ? ???? ?? ???????? ? ?????????? ?? ??????
??????????? XXI ?.
???????????? ?????? ? ????????????? ????? ???????? ?????? ?? ???????? ???-?? ?????????. ?? ??????? 1 ?? ????? ?????????? ????????? ???????? ?? ???, ??? ? ??? ? ??????? ?????? ???????? ??????????? ???????????? ?????????? ???????? ????????? ?????. ?????
??? 12 ???????? ??? ? ????? ?????? (???? ??????? ? ??????????) ?????????? ?? ???????,
????????, ???????, ??????, ?. ??????, ?????????, ?? «????????????????» (?????????? ?? ??????? ??????????????????? ????? + ??????), ?????, ?????, ???????????????, ???????? ? ????????, ?????????? ?????? ?? ?????????. ????? ???????? ?????-?????????? ??????
??????????????? ??????? ? ???? ??????? ? ?????????? ??????????????? ?? ?????????????? ?????????????: ???, ???, ????, KCON, ??????????? ?????? ?? ????????????? ??????????? ???????? «???????? ????????». ???? ??????? ??? ? ????????? ?????? ?????????
?? ??????.
# 502 #
???. 1
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Sergei I. Andreev and Svetlana F. Babaeva. Mineral Resources of the Ocean: a Pragmatical Reality of the Foreseeable?
?? ????? ??? ???????? ?????? ???????: ??? ? ????????????? ?????? (?????? ? ???????),
??? ? ????????? ?????? (????? ? ?. ?????), ????? ?? ?????????? ?????? ?? ?????. ????????
?????????? ????????? ?????? ?? ??? ? ????? ???????????? ?????????? ????? ????? ? ?????
??????, ?????, ?????????????? ????????? ?????????? ????????? ? ??????????. ?? ?????????? ???? ????????, ? ?????? ????????, ?????-?????? ????????? «???????? ????????» ?????????? ?????????? ?????? ???????? (??????? 1) ? ???????????? ?????? ???, ??????????????
?????????? ????????? ???????? ? ??????????? ??? ? ???????? ???????? ??????? ????????? ??
????????????? ????? ? ????????? ????.
?? ????? ??? ???????? ??? ??????? (?????? ? ?????) ? ???????????? ????? (?????
?????), ??? ?? ?????????? ?????? ??????? ?? ??????.
????? ????????? ????????? ????????? ??? ???????: ??? ? 56,6 ???? ? ????? ??????
?????; ??? ? 43,1 billion ton; ??? ? 223 million ton [2, 3].
??? ???????????? ????? ???????? ?????????, ?????????? ? ???????? ?? ???????????
??? ? ??????????? ??????????, ?? ???????? ?? 4200-5500 ?, ?????? ?????????? ??? 2/3 ???????????? ? ?????? ??????. ??????? ???????? ?? 2 ?? 12 ??.
??? ???????? ?? ???????? ???????? ?????????, ???????????, ?????????? ???????????
? ??????????? ?? ??????? ? ???????? ????????? ??? ? ??????? ?? ???????? ?? 500 ?? 3500 ?.
???????? ????? ?? 2 ?? 23 ??.
??? ?????????? ? ????? ???????-????????????? ??????????, ?????????????? ? ??????
???????? ?????????? ????????-???????????? ???????, ? ????????? ? ?????????? ??????
????????? ???. ???????? ??????? ?????? ? ????????????? ?????? ????, ?? ??????????? ??????? ???????????? ?????????????? ??????????? ??????????? ????? ? ?????? ? ???????
????????????. ??????? ????????? ?? 850 ?? 4200 ?.
?????????? ??????????? ????? ??? («??? ? ???») ????????????? ? ?????? ????
??????? ? ??????????, ? ??????????? ????? ??????-????????? ????????? ?????? ??????, ??????? ??????? 4800 ?. ?????????? ?? ?. ??????? 10 500 ??, ?? ????????????????????????? 8500 ??. ?????? ??? ????????????, ?????? ?????? 100-200 ?. ?????? ????????? ? ???????? ?? 2 ?? 10-15 ??. ??????? ??????? ????????? ????????? 14 ??/? 2. ??????
????????????? ??? ? ???????? «??? ? «???»: Mn ? 30,16 %, Ni ? 1,41 %, Cu ? 1,13 %,
Co ? 0,23 %, Mo ? 0,04-0,05 %. ??????? ?????? ????? 580 ??? ?. ?????????? ??????? ???????? ????????? ?2 ? ?1: Mn ? 120,5 ??? ?; Ni ? 5,68 ??? ?; Cu ? 4,54 ??? ?; ?o ? 1,33 ??? ?.
???????????-????????? ?????????? ??????? ?? «????????????????» ????????????? ?? ?????????? ?? «??? ? ???». ??? ?????? ? ??? ????????? ????????? 20-??????????
????????????? ?????. ????? ??????????? ??????????? ????? ?????????? ?????? ???????? ? ???????? ??????????? ???????, ?.?. ??????????? ? 2016 ?. ?? ???????-?????????????
??????? [4] ????????? ????????????? ??? ???????????? ????? ??????????? ?????? ??????: ?? ?????????? Mn ? ??????? (????? 25 %), ?? ???????? ??????? (????? 100 ??? ?);
?? ?????????? Ni ? ??????? (????? 1,3 %), ?? ???????? ? ?????? ??????? (????? 1 ??? ?);
?? ?????????? Cu ????????? ? ???????, ?? ???????? ? ? ???????, ?? ?????????? Co ? ?
???????, ?? ???????? ? ? ????? ??????? (??????????). ???????? ?? ?? ??????????
????????? ? ????????? ???????, ?? ???????? ? ? ??????? (260 ??? ?) ????????. ???????
?????, ??? ??? ???????? ?????????????? ????????? ?????? ?? ????????. ??? ???????# 504 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Sergei I. Andreev and Svetlana F. Babaeva. Mineral Resources of the Ocean: a Pragmatical Reality of the Foreseeable?
?????????????? ?????????? ?????????? ???????? ?????????? ?? Cu ? 89-90 %; Ni ? Co ? 9394 %; Mn ? 97-98 % [4].
?????????? ?????????? ??????? ??? ????????????? ? ???????????? ????? (????? ?????), ?????????? ?? ?. ??????? ? 3600 ??, ?? ??????????????-??????????? ? 4450 ??, ???????
1400-3500 ?. ?????? ??? ????????????? ?? ????????? ???????, ?? ????????? ??????? ????????? ???????????. ??????? ??????? ????????? ????????? 70-80 ??/?2 ??? ??????? ?????
6-8 ??. ?????? ???????? ???: Mn ? 20-22 %; Co ? 0,55-0,60 %; Ni ? 0,43-0,47 %; Mo ? 0,04-0,05 %.
??????? ?????? ????? ? 350 ??? ?, ??????? ???????? ? Mn ? 70,0 ??? ?; Co ? 1,87 ??? ?; Ni ?
1,46 ??? ?; Mo ? 0,15 ??? ?.
?? ???????-????????????? ??????? [5] ?????? ??? ???????????. ?? ?????????? Mn
???????, ?? ??? ???????? ? ???????; ?? ?????????? Co ????? ??????? (????? 0,3 %), ?? ???????? ????? ??????? (????? 100 ??? ?); ?? ?????????? Ni ??????, ?? ???????? ???????; ?? ?????????? Mo ???????, ?? ???????? ???????. ?????????????? ????????? ????????????? ???
?????????? ?? ??????? ?????????? ????????, ??????? ?? ???????? ?????????? ??. ?????????
???????? ?????????? (Mn, Ni) ??? ???????? ????????????? ??? ????? ????????? ????????
????????, ???????????? ? ???. ??? ????????????????????? ?????????? ?????????? ???????? ?????????? ?? Co ? 93 %, Ni ? 88 %, Mn ? 93 % [4].
?????????? ??????????? ????? ??? ????????????? ? ?????? ???????? ???? ?????????????????????? ??????. ?????????? ?? ?????-?????????? ? 8000 ??, ?? ?????????? ? 8600 ??,
?? ????????? ?????? ?????? ????????? (?-? ????????) ? 1600 ??, ???-??????? (???? ???????, ???????) ? 3150 ??. ? ????????? ??????? ????? ???????? 10 000 ?? 2 ????? 7 ??????
???????? (????. 1), ??????????? ??? ????? ??????????? ?????????? ?????? ????? ?????? ????????? ??????????? ??? (?????? ???? ??????????, ????????? ? ???????) (???. 2). ? ???????????? ? ???????? ????????? [5] ??? ??????? ??? ??????? ??????, ????????? ????????
?? ?????????? Cu (????? 10 %). ??? ?????? ???? ?????? ? ???????. ??? ??????? ???????????? ?????? ???????? (????? 3,0 %) ??????: ?????? ???? ???-??-????? ? ?????????????;
???? ???????? ?????? (????? 2,0 %) ? ?????? ???? ??????? ? ???? ???????? ?????? (?????
1,0 %) ? ?????? ???? ?????-????????. ???? ?????? ? ?????? ???? ??????? ? ??????? ??????? ???????????? ?????? (Cu ????? 1 %), ????? ??????? ??????????? ??????? ? ????????
??????? 1. ?????? ? ?????????? ??????? ??? ? ???????? «??? ? ???» (???)
???????????? ??????? ???
(????????????? ?????????????)
?????? ?????? ?????
Cu, %
Zn, %
Pb, %
Au, ?/?
Ag, ?/?
???????,
??? ?
???-??-????? (Cu-Zn)
7,42
2,51
0,04
0,50
36,0
11,89
?????-???????? (Cu-???????????)
1,86
0,63
0,02
0,20
17,7
15,18
????????????? (Cu-???????????)
7,73
0,16
-
0,48
16,1
2,90
??????? (???????????)
0,37
0,36
0,18
0,50
8,3
12,79
??????? (Cu-Zn, ????????)
32,71
3,85
-
17,6
46,7
1,87
??????? (Cu-???????????)
2,64
0,12
0,03
0,80
13,4
38,97
?????? (Cu-???????????)
12,43
1,15
-
5,4
15,7
5,23
?88,83
# 505 #
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Sergei I. Andreev and Svetlana F. Babaeva. Mineral Resources of the Ocean: a Pragmatical Reality of the Foreseeable?
? ???????? ??????????????? ??????.
?? ?????????? ??????, ? ???????? «??? ?
???» ?? ?????? ??????????? ????? ????????? ?????? ????????? ??????????
????? 90 ??? ?, ????? ???????? ???????
??? ? ??????????? Cu ????? 10 % ?????
????????? 30,0 ??? ? ????? ?????? ?????,
??? ????????????? 3 ??? ? ???????, ?.?.
???????? ???????? ????????????? ????
?? ???? [5].
????? ???????? ???????? ??????????? ???????? ??????? Au, ??????????
??????? ???????? ? ???????? ????? ?????????? ?????? ??????????? ? 100 ?. ?????????? ?????????? ?????????? Ag (??
50-60 ?/?). ????? ?????? ? ?????????? ????????? ????? ???????????? ??????? Se, In,
Ge, Bi, ???????? ? ?????? ???????. ??????? ??????????????? ??????????? ??? ??
?????? ???????????????? ???????? ????????????? ????????? ?? ????????? ???????? ? ??????? ??????????? ? ?????????
96,3 % ????, 94,7 % ??????, ?? ?????????
??????????? ? ?? 94,7 % ????? [6].
?? ????????? ??????????? ?????????????? (???? 2008-2012 ??.) ??????????? ???????????? ????????????? ???,
???. 2
??? ? ??? (???. 3) ?????????? ? ??????? ??????????? ??????? ???????? ????????????? ????????????? ????, ????????
?????????? (?????????? ??????), ??????? ??????????? Cu-Zn (????), ?????? ? ???????? ????????? (??????????) (???. 3).
???????? ???? ????? 40-?????? ?????????? ???????????????? ??? ? ??????? ??????:
? ??????? ? ????????? ? ?????? ?????????? ??????????? ????? (????????? ? 2016 ?.) ?????????? ??????????? ????????????? ??? (Mn, Ni, Cu, Mo) ? ????? ??????. ? ??? ??
???????, ?? ??? ?? ?????? ??? ????????? ????????????? ??? ?? «????????????????», ? ???????? ???????? ?????? ????????? ??????? ??????? (20 %);
? ??????? ??????? ??? ? ???????????? ????? (????? ?????), ?? ?????????? ?????? ?????????????? ????? ??????????? (Co, Mn, Ni, Mo) ??????, ? ?????? ??????? ??????? ??
(0,55-0,60 %), ?? ???????? ???????????? ? ????? ??????? ???????? ??????????????
????? ???????. ?????????? ??????????? ??????????? ????? ?? ??????? ??? ?????????
? 2029 ?.
# 506 #
???. 3
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Sergei I. Andreev and Svetlana F. Babaeva. Mineral Resources of the Ocean: a Pragmatical Reality of the Foreseeable?
? ?????? ???????? ??????????? ?????????????? ???? ?? ???????? ? ??????????? ???????? ??????? ??? ? ????????-????????????? ??????. ?????? ??????????? ?????? ???????? (???? 3,0 %) ? ????????? ???????? (????? 10 %) ??????????????? ??????,
?? ?????????? ?????????? ??????????? ???????? ????????????? ?? ???? (?????
3 ??? ? ???????). ????????? ??????????? ??????????? ????? ? 2027 ?.
?? ?????????? ???????, ??? ? ??????? ??????????? XXI ?. ?????? ????? ?????????
????? ???????? ?????? ????????????? ???????? ??????????? ???????? ???????? ??????:
????????????? ??? (2016-2020 ??.), ????????????? ??? (2029-2030 ??.) ? ?????????????
??? (2027-2030 ??.). ? ???????????????? ????? ???? ???????, ? ????? ???????, ???????????
???? ???????-????????????? ??????, ? ?????? ? ????? ????????????? ???????????.
??? ????????, ?????? ?????????? ?????? ??????? ? ????????. ?????????? ??????
Mn ? 232,1 ??? ? [7]. ? ??? ?????? ?????????? ??????? ? 9,1-32,8 %. ???? ???????????????
???????????????? ??????????? ??? ?????????? ?? ????? ????????????. ????? ???????
????????? (31,3-32,8 %) ?????????? ????????????? ????????? ? ???? 1,7 % ?????????? ???????
??????. ??????? ?????? ? 60 ???. ? ???????, ?????? ? 2012 ?. ? 1088,6 ? ??????? ??? ????????? ?
?????????? ????? ??????????. ????????? Fe-Mn-???? ????????????? ? ???????? ??? ???????
?????????? Mn ???? 30 % ? ??? ? 20-22 % ? ???. ??????? ?????? (?2+?1) ? 120,5 ??? ?,
?????? ? 70,0 ??? ?.
????????? ??????? Mn ? ??? ? ??? ? 190,5 ??? ?, ?.?. ?????????? ? ????? ???????????
?????? ?? ????? ???????. ??? ????????? ?????? 3 ??? ? ??? ? 1 ??? ? ??? ????? ????
????????? ?? 1,100-1,150 ??? ? ???????, ??? ????????????? ??????? ??????????? ?????? ? ????
?????????????? ?????.
?????? ? ???????? ?????????? ??????. ???????? ????????? ? «?????????? ??????».
????????????? ??????????????? ? 1946 ?. ?????????? ??????? ? ??????? ????? 3,69 %
? ???????? ?????? ????? ??????? ?????????? Ni ? ?????????????? «???????????» ?
«??????????» 0,69-0,82 % [7]. ??????? ??????????? ?????? ?? ????????? ??????? ??? ?
?????? ????????? ?????????????? ???????????? ????????????? ?? ???????? ??????, ??
?????? ????????????? ????. ??????? ?????????? Ni ? ??? ? 1,41 %, ? ??? ? 0,43-0,47 %.
?????????? ??????? Ni ? ????????????? ??? ? 5,68 ??? ?, ? ??? ? 1,46 ??? ?; ????? ?
7,14 ??? ?. ????? ?????????? ??????? (?1) Ni ? ?????? 1,2 ??? ?. ??????? ?????? ? 371 ???. ?.
??? ????????? ????????????? ??? (??????? ?????????????????? 3 ??? ?) ? ??? (1 ??? ?)
+ 20 % ?? ??????? ?? «????????????????» ??????? ????? ???????????? Ni ?????
????????? 55-60 ???. ?, ?.?. ????????? ??????? 15-16 % ???????????? ?????? ??????? ? ???
????? ?????????? ???????????? ?????????? ?????? ??????.
Cu ?? ???????? ??????? ? ????????? ???????? ??? ? ??? ????? ???, ??? ??? ?????? ?????????? 0,12 %. ?? ??????? (?2+?1) ? 4,54 ??? ?. ??????? ?????? (?1) ? 12,0 ??? ? [7]. ?????? ?
????????? ? ????????? ??????????????? ??????????????? ??????????? ??? ???? ??????
?????, ?????? ??? «???????» (4,6 ??? ? ??? ??????????? 1,3 %), ?????????????? ??????????
????????????? ??? ?????????????? ???????????? ??????????.
???????? ??? ? ??? ????????, ??? ?? ???????? «????????????» ????????. ?? ????????? ???????????? ? ??? (0,22-0,23 %) ? ??? (0,55-0,60, ?????? ?? 0,8-1,0 % ? ????). ????????? ???????????? ??????? ?? ? ????????????? ??? (1,33 ??? ?), ??? (1,87 ??? ?) ??????? ?
# 508 #
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Sergei I. Andreev and Svetlana F. Babaeva. Mineral Resources of the Ocean: a Pragmatical Reality of the Foreseeable?
3,2 ??? ?. ? ???????? ?????????????? ?????? ?????????? ??????? ?? 0,65 ??? ? [8]. ???, ???
????? ????????? ???????????? ????????????? ??? ? ???, ????? ????? ??????? ?? ????????
????? ??????? ? ????.
?? ??????????????? ? ??????? ??? ? ??? ??? ????????. ?????? ??? ??????? ???????
??????????? ??????? ???????? ?????????? ??? ??????. ??? «?????????????» ?? ????? ???????? ??? ????????????? ????????: ???????????? ?????????? 0,04-0,05 % ? ???????? ?????????? ? ??????? ?? ?????????????? ? ?????? ????? ???????? ??? ????????? ?? ????????????
?????? ???.
????????????? ??????????? ?? ????? ??? ???????? ? ????????????? ??????? (7,42 %) ?
????? ??????? (12,43-32,71 %) ?????????? Cu ? ????????? ? ?????????: ??????????? ? 1,67 %;
?????????? ? 1,11 %; ????????? (????????????) ? 1,71 %; ???????? (???????) ? 0,83 %. ?????????????????? ?????? ? ???????? ?????????? ??????? ??? (???) ????????? ????????? ??
???????????? ?????????? ????????? ???? ? 90 ??? ? ? 1,5-2,0 ???? ?? ???? ????????? ????? ?
???????? ????? ???????? ?????????? ? ??????????? ?????????????? ???????. ????????????
????? ???????? ? ????? ??????? ? ????? ??????? ???, ??? ????????? ?????? ??? ? ?????????? Cu-?????????? ????????????? ? ???????? ???????, ? ???????? ? ???????? (?? 40-50 ?/?).
?????? ? ???????????? ?????????? ?????? ? ?????????? ????????? ????? ????? ???????????
???? ???????? ???????????? ? ????????? Se, Ge, In, Bi, ???????? Co ? Ni.
?? ???????????? ????????? ??????????? ???, ??? ? ??? ???????, ??? ????????????
????? ???????? ??????? ???????, ? ?????? ??????? ?? ????? ???????? ????????????? ???
? ????? ??????. ??????????? ?????? ?? ??? ? ??? ???? ????????? ? ????????? ??????. ??????? ?????????????? ????????? ?? ???????? ??? ??????? ??????????? ? ?????????? ???????
??????, ?????????? ??????????????? ????? ??????????? ????????????? ????, ?????? ??????????????? ?????????? ???? ? ?????????, ?????????? ?????? ??? ?????-?????????; ????????????? ? ??????????????? ??????????? ????? ?????-????????????????? ?????????. ???????? ????????? ????????????? ???, ? ? ??????????? ? ???, ?????-????????????????
?????????????? ????????????? ?????????? ?? ????????? ? ???????? ? ??????? ?? ?????????????? ?????????? ? ???????? ???????????? ????????????? ?? ???? ????????, ???? ???????????? ????????.
???????? ???????? ???????????? ??? ???????????? ????? ???????? ??????, ???, ????? ????? ? ???? ????????-??????????? ?????, ??????? ???????? ?? «????????????????». ? ??? ????????? ?? ???????? ????????? ? ?? ?? ?????, ? 2016 ?., ? ??????? ???????
??? ?? ?????, ?? ? ???????? ????? ????????????? ???????????????? ???????????? ? ???????
???????? ?????????????? ????????. ??? ?????????????? ??????? ?? ????? ? ?????????????
?????????? ?????, ???????????? ??????????? ????? ??? ????????????? ???????????? ?????
??? ??????? ?? ????????? ???????? ?????? ????????? ?????????? ???????????, ???????????????? ??????????? ? ?????? ????????????? ???????????? ????? ? ????????? ?????????
? ????????????? ?????????. ???????, ??? ?? ??????? ????????? ???? ???? ?? ?? ??????????
???????? ????? ???? ???????, ????? 3-5 ???. ????? ?????-???????????????? ????? ?? ???????
??????? ????? ?????????????? ???????????????? ????? ????. ?? ?????? ?????????????????
???????? ????????????, ??? ??????? ????????????? ????????. ? ?????? ????? ????????????
??????????? ?? ?????? ??????, ?? ? ?????, ???????? ? ???? ??????. ????? ??????? ?????????
# 509 #
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Sergei I. Andreev and Svetlana F. Babaeva. Mineral Resources of the Ocean: a Pragmatical Reality of the Foreseeable?
? ???????? ?????? ? ????????? ??????? ?? ??????????? ? ????????? ???????????, ? ????????
? ????????? ???? ????????????? ???????????? ????? ? ??? ? ? ????????? ????????? ?????
?????????? ??????? ????????????? ????? ??????-????????? ???????? ?????????????? ???????.
???????? ??????, ??????????? ??? ?? ????? ?????????? ??????? ???????? ???????????
???????? ??? ???????? ??????, ??????? ???????? ??????????? ???? ? ??????? ????? ? ??????????? ????? ? ????????????? ??????? ????? ??????. ?? ??????? ? ???????? ??????? ?????????
?????????? ? ????????????? ???????? ???????????? ??? ????? ???? ???????? ????????????
?????-?????? ????????, ??????? ????????? ?? ?????????? ????????.
1. ??????????? ?????? ? ????????? ????????? ???????? ????????????? ????????????
????, ?? ????????? ?????????????, ??????? ? ?????????????.
2. ??????? ????????? ????? ??????? ? ????, ? ????????????? ??????????? ??????, ???????????? ? ?????????? ?????????? ???????, ????????? ? ????.
3. ??????? ??????????? ????????????? ????? ?????? ???????? ?????????????? ??????,
???????? ?? ???????????? ??????? ?????????? (??????? ????????? ?????, ????????, ??????
??????? ???????? ? ?????????? ???????????).
4. ?????????? ??? ??????? ?? ??? ? ??? ????????????? ????????? ?????. ????? ?
????????? ????? ?? ??????????? ???. ??? ???, ?????? ?????, ????? ?????? ?????????????
?????????????? ?????? ????.
5. ?????? ????? ?????? ? ????????? ???????? ??????????-????????? ????? ????????????? ??????????. ??? ?? ??????, ??? ?? ?? ????? ???????? ?? ??????? ??????????? ???????????. ?????? ????? ???????? ????????? ???????????, ??????? ?????????? ???????????
????? ?? ?????? ?????????? ?????, ???? ?? ???? ?? ???????????.
6. ????????????? ?????? ??????? ?????, ?? ????????? ?????????????? ??????????????
? ?????????? ?????? ??? ???????? ?????????? ??????? ????? ? ????? (??????????? 22-26 є?)
? ????????? ? ????? ???????? ????, ??? ????????? ???????? ??????.
???????? ???? ???????? ???????????? ????? ?????? (???, ???) ? ??????????? ????????, ?? ?????? ????????, ??? ???????????????? ??? ???????? ? ?????? ??????????????? ???????????? ???????????? ????? ????????? ?? ?????? ????? ??????? ? ?????? ???????????
?????? ????. ???????? ????????????? ??????????? ???????? ???? ????? ????? ? 20-30-? ??.
XXI ???????? ? ???? ????????? ???????, ????? ???????? ??????????? ???????? ????????
?????? ???????? ?? ??????????????? ???? ? ?????? ????????????? ????????? ?????? ? ????????? ??????.
?????? ??????????
[1] Murray J., Renard A.F. Report on deep-sea deposits based on the speciments collected during
the voyage of the H.M.S. Challenger Reports. London: Government printer, 1891.
[2] ??????????? ??????? ???????? ??????. ????????? ???????? ? ???????? (?? ??????
?? 2020 ?.) / ??. ???. ?.?. ???????. ???.: ?????????????????, 2007. 97 ?.
[3] ???????????? ??????????????? ??? ???????? ?????? / ??. ???. ?.?. ???????. ???.:
?????????????????, 2013. 207 ?.
[4] ??????????-????????????? ?????? ???????? ????????????????? ??? ???????? ??????. ?.: ????, 2009. 323 ?.
# 510 #
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Sergei I. Andreev and Svetlana F. Babaeva. Mineral Resources of the Ocean: a Pragmatical Reality of the Foreseeable?
[5] ??????????? ?????. ??????????. ?.: ??? ?????????????, 1999. 302 ?.
[6] ??????????? ?????? ???????? ????????????? ??????? ????????????? ????????????????? ????????? ???????? ??????. ?.: ????. 2013. 377 ?.
[7] ??????????????? ?????? ? ????????? ? ????????????? ??????????-???????? ???????? ?????????? ????????? ? 2011 ?. / ??. ???. ?.?. ??????. ?.: ???????, 2012. 332 ?.
[8] ??????? ?.?., ???????? ?.?., ??????? ?.?., ???????? ?.?. // ?????? ??????. 2013. ? 11.
?. 65-72.
??????????? ??????? ???????? ?????? ?
?????????????? ?????????? ?????????? ????????
??? ?????????? ??????????????? ?????
?.?. ???????, ?.?. ???????
???? «????????????????? ??. ?.?. ?????????,
??????, 190121, ?????-?????????, ??. ??????????, 1
???????? ????????? ??????????? ??????? ???????? ?????????? ???????? ??????
(???, ???, ???), ???? ?????? ?????????? ?????? ? ??????????-???????? ???? ??????.
??????????, ??? ???????? ??????????? ???????? ?????? ??? ? ????????? ??????? ?????
????? ?? ?????? ???????????????, ?? ? ???????? ???????????? ????????.
???????? ?????: ??????????? ??????? ???????? ??????, ????????????????? ?????????
(???), ?????????????????? ????? (???), ????????????? ????????????????? ????????
(???), ????????, ??????????? ????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 512-524
~~~
??? 669.2/8:621.317.757
The Application of Laser Element Online Analyzer MAYA
for Extraction of Mineral Raw Materials
and For Stabilization of Raw Mixtures
in Nonferrous Metal Production
Alexander M. Barishnikova* and Michael L. Gaftb
a
Icon Steel,
USA
b
Laser Distance Spectrometry
9 Mota Gur St., Petach Tikva, 49514, Israel
Received 12.02.2014, received in revised form 07.07.2014, accepted 14.08.2014
The laser analyzers MAYA are successfully applied in industry in order to solve the tasks of crushed ore
sorting and stabilization of the composition if raw material mixtures in metallurgy and in production of
fireproof materials. The tests of non-ferrous ores such as Cu, Mo, Zn, Pb, Sn, Ti, Be, Sr and Ba confirm
that the laser analyzers could be applied in this branch at different stages of the technological process:
extraction of raw material, preparation of raw material mixture, check of technical composition,
operative check of the finished products? quality.
Keywords: LIBS, online, industry, minerals, metals.
Introduction
During the process of mineral raw material extraction it is necessary to separate the raw materials
by grades. Nowadays in most branches of industry dealing with extraction, processing of mineral raw
materials and production of the most part of industrial materials including ferrous and nonferrous
metal industry, production of fireproof and constructional materials, fertilizers, solid fuel the crude ore
comes for processing with significant variations of chemical and mineralogical composition appearing
just after extraction from open cast or mine and after storage as well. This decreases the stability of
technological processes of concentration, processing, worsens the quality of finished products, and
decreases in whole the efficiency of production. Therefore it is necessary to guarantee the stability of
the raw material quality during realization of the specified technology for receiving the products with
pre-assigned qualitative factors.
It is possible to solve these problems by separating the raw materials by grades including the
rejection of the portions of material unsuitable for specific purpose application and by well-grounded
regulation of the parameters of its processing based on operative information on chemical composition
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: alex@iconsteel.net
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Alexander M. Barishnikov and Michael L. Gaft. The Application of Laser Element Online Analyzer MAYA for Extraction?
of raw material. This regulation could be applied at all the stages of production ? from minerals survey,
their extraction and concentration and up to preparation of raw mixtures with the specified composition
and operative automatic regulation of the parameters of technological processes.
In most cases the information on chemical composition of raw material being extracted in open
cast and moved along conveyers, on raw mixtures and their components becomes accessible for
technologists who perform the control of processes of extraction, generation of averaging storages,
batching of components of raw mixtures only in some hours after sampling. In case of large-tonnage
production this information delays significantly not permitting to use it for the tasks of controlling these
processes. Besides, the validity of the information received is also often rather low due to complexity
of providing the representativeness of the samples taken and of preparing the samples for laboratory
analyses.
The specified reasons stimulated the development of different flow element analyzers at the 20
century end. Their application permits to receive information on raw material composition in realtime mode directly at conveyers or in flow without sampling and gives a possibility to control the
technological processes operatively, increases the degree of correspondence of analytical information
to real composition of raw material moved [1-4]. But the majority of analyzers are based on activity of
different sources of ionizing radiation ? Roentgen, neutron or gamma ? being rather dangerous for the
personnel and for the environment pollution. Besides, their application requires to receive the permits
from different state bodies dealing with radiation monitoring, is rather complicated from technological
point of view and cost-based, all these reasons limit their application rather often.
For solving the same tasks of stabilizing the composition of ores, ore mixtures and quality of
finished products in real-time mode by fully unsafe method, the Israeli firm Laser Distance Spectrometry
(LDS) has developed the laser optic-emission element analyzer MAYA.
The operating principle of the analyzer MAYA is based on the method of laser optic-emission
spectrometry (Laser Induced Breakdown Spectrometry, LIBS), where the solid-state pulsed Nd:YAG
laser serves as an excitation source of the substance studied. The laser beam with a rate from 1 to 20
times per second is focused at the surface of material being analyzed where the temperature of more
than 30000є? is achieved immediately, and small amount of the substance turns into plasma state.
The plasma is practically electric neutral but heavily ionized gas containg the molecules, atoms and
ions of the chemical elements being in the material and the free electrons as well. The processes
of recombination of positively and negatively charged particles begin in the plasma immediately
and are accompanied by emission of photons ? «glow» of the plasma occurs. The atom of every
chemical element emits the photons with strictly defi ned wavelengths, and the lumonous intensity
is connected in general case with the concentration of this element in the material analyzed (Fig. 1).
Thus, the spectra received are the characteristics of the material analyzed, figuratively speaking
their «fi ngerprints» [5-7].
The optical radiation of the plasma within wide optical range from 190 to 1000 nm is fixed by
special spectrometers transferring the digital information on the spectrum composition to the analyzer
computer (Fig. 2).
In result of statistical processing of a set of spectra for the period of time required for technologist
in order to solve his task (usually from 20 s to several minutes) the concentrations of the elements
being the components of the material analyzed are calculated [8]. The main advantages of the method
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Alexander M. Barishnikov and Michael L. Gaft. The Application of Laser Element Online Analyzer MAYA for Extraction?
Fig. 1. Typical spectrum of limestone obtained by means of MAYA
SCADA and ERP systems
(operational process and factory
management automatic control
systems)
Administrative
Computer
Detecting
spectrometer
Laser system
Guiding and/or
focusing optics
Collecting
optics
Optical emission (plasma,
luminescence, Raman
scattering effect)
Sampling material
Fig. 2. Principal diagram of the laser analyzer MAYA operation
of laser-emission spectrometry in comparison with other analytical methods applied for analysis of the
element composition in real-time mode are as follows:
? high sensitivity, low detection limits and high accuracy due to clear spectral lines of magority
of the elements within wide optical range and to practical absence of thier interferences;
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Alexander M. Barishnikov and Michael L. Gaft. The Application of Laser Element Online Analyzer MAYA for Extraction?
? ability to analyze simultaneously all required elements including light (C, Si, Mg, Al);
? absence of any types of ionizing radiation (neutron, gamma and Roentgen), absolute unsafety
for the personnel, absence of necessity to get permits and permanent inspection of the state
bodies dealing with atomic monitoring;
? independence of the analyses results from quality of the matrial surface, size of lumps an
height of the matrial layer on conveyer;
? stability of calibration during long period of time;
? simplicity and safety of the analyzer?s operation and maintenance.
A potential advantage of PGNAA in comparison with XRF and LIBS is its ability to measure
the volume and not only the surface. The penetration depth of a laser beam is very shallow, so on a
moving belt conveyer only the surface of the material is analyzed while we need to know the impurity
concentrations of the volume. Moreover, only tiny spots on the particles? surface are analyzed. Thus
the greatest challenge was to prove in ambient conditions of material transported on a conveyor that
it is possible to transform LIBS data to quantitative elemental content evaluations, and that highfrequency sampling of surface chemistry is commensurate with the average of the total cross-section
and length. It is clear that the LIBS analyzer has to be employed on a surface which statistically
represents the whole volume of the material. For industrial control, you need the data for certain time
periods, from 30 s to 5 min (approximately 60 to 600 m of conveyer belt run). For such large quantities
of sample, the surface in most cases is statistically relevant, since bulk materials typically get to the
conveyer belt after explosive/crushing processes that are random in nature. Its efficacy has been proven
by many industrial installations of XRF, which is also of the surface analyzer type, and by our LIBS
installations. According to our accumulated experience, to get the surface representative of the volume
you need the following: get material to the conveyer belt via averaging storage; chose the installation
point after the mixing drums; mix the material by inexpensive mechanical tools. The applicability of
LIBS surface analysis has been practically confirmed by all current industrial installations.
Examples of industrial applications
Similarly to other existing today methods of online analysis, the applications of the laser analyzer
MAYA in extraction, concentration and processing of the mineral raw materials could be divided
into two basic groups ? automatic sorting of the ore being extracted or crushed (Fig. 3) and automatic
batching of components of the raw material mixtures for stabilizing the composition of the raw material
mixtures.
For sorting of the crushed ore with fractions of up to 150 mm the analyzer MAYA is used, for
example, at crushing-concentration factory of Magnesite Complex [9] (Fig. 4). Depending on the
content of CaO and SiO2 in portion of the material, passing along the conveyer during 60 s, the system
SCADA, performing the control of automatic gate, determines a bunker where this portion of the
material is to be directed on the basis of the operator?s task and the data received from MAYA.
The accuracy and reliability of the analyzer?s readings are well confi rmed by the following
example: : at setting as a task the threshold value of silicon oxide content equal to 1.45 % (at losses
during burning for raw magnesite of about 50.6 % this corresponds to approximately 2.9 % of silicon
dioxide in terms of the content in the material after burning) the raw magnesite was sorted into
bunker, and burning of this raw magnesite gave a batch of fi red periclase ? fi reproof powder with
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Alexander M. Barishnikov and Michael L. Gaft. The Application of Laser Element Online Analyzer MAYA for Extraction?
Primary extraction (separation)
Information about chemical
composition in real-time mode
Separated material (C > Cmax)
Automatic sorting
unit
Starting material (C)
Standard product (Cmin < C < Cmax)
Depleted material (C > Cmin)
(debris)
Fig. 3. Principal diagram of automatic sorting of crushed ore on the basis of data on its chemical composition
coming in real-time mode
Fig. 4. The analyzer MAYA at crushing-concentration factory of Magnesite Complex
fraction of 0-150 mm with a level of silicon oxide of less than 3 %. Thus the relative deviation of
the analyzer?s readings from the laboratory data is less than 5 % (Fig. 5), this is not worse than the
reproducibility of the laboratory analyses. In the result of MAYA implementation the capability to
reject the material with non-corresponding parameters (up to 10-15 %) from the flow of qualitative
raw magnesite and to extract additional volume of high-quality raw material (10-30 %) from the flow
of the medium grade crushed magnesite was realized. The estimated period of the cost recovery for
the project was equal to not more than one year from the commissioning due to separation of more
expensive high-quality products without damage to the mass production being realized and due
to timely correction of quality of the fi red magnesite used at subsequent production stages and for
shipment to the consumers.
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Alexander M. Barishnikov and Michael L. Gaft. The Application of Laser Element Online Analyzer MAYA for Extraction?
Fig. 5. Comparison of laboratory data and the analyzer MAYA data for SiO2
Chemical composition data in real-time mode
Material 3
Material 2
Material 1
APCS
APCS
Dosage
adjustment
Incoming material
control
Corrective
additives
Dosage
control
Fig. 6. Principal diagram of automatic batching of the raw material mixture components on the basis of information on its chemical composition coming in real-time mode
The operating experience of the analyzers demonstrates that they could be also used in the
composition of crushing and sorting complexes directly at places of the ore extraction and the primary
crushing of the ore materials and for technological operative inspection of the finished products quality
as well.
For stabilization of composition of the raw material mixture the analyzer MAYA is used, for
exampleat public corporation «Novolipetsk metallurgical complex» [10-11] (Fig. 6).
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Alexander M. Barishnikov and Michael L. Gaft. The Application of Laser Element Online Analyzer MAYA for Extraction?
The chemical composition of the iron-ore materials used in the agglomeration production of ferrous
metallurgy is significantly varied, first of all by content of such elements as Fe, Ca, Si, Mg. The content
of CaO and SiO2 in the iron-ore mixture has significant variations connected with bad averaging and
segregation of the materials in pile. The addition of lime into the iron-ore pile for moisture fixation
causes considerable influence on variations. This is one of the main problems connected with obtaining
of agglomerate being stable by content of Fe and by basicity factor (CaO/SiO2). It is known that the
quality of the iron-ore materials (agglomerate and pellet) has strong influence on efficiency of operation
of blast furnaces. The stability of the chemical composition of agglomerate and its basicity is also such
an important characteristic of the quality as reducibility, reactivity index and strength after reaction.
The decrease of the agglomerate basicity variation permits to reduce the output of slag per ton of cast
iron and to decrease the coke rate in blast furnaces.
The analyzer MAYA was installed at combined conveyer of aggloburden coming to agglomachine
No.1 before place of flux batching. The system is based on receipt of information on content of Fe,
CaO and SiO2 in iron-ore mixture from the analyzer MAYA and performs the automatic continuous
correction of the flux flow rate at subsequent batching, decreasing the agglomerate basicity variations.
(Fig. 7, 8). Starting from February 2011 the laser analyzer MAYA, installed at agglomachine No.1
of Novolipetsk metallurgical complex, has been operated round-the-clock without failures in rigid
conditions of high dust level, ?vibrations and temperature variations from -10 to +40 ??.
In one year after the start of the analyzer?s operation the check of the current calibration (correctness
of its readings) was carried out, and it confirmed the stability of the analyzer?s calibration during
that period. The comparison of the analyzer?s data for the content of Fe and ?aO in iron-ore and the
results of the laboratory analyses are given in Fig. 9. This compatibility of the data is the result of high
stability of the laser radiation parameters and of the optical schemes used, and application of effective
means of the analyzer?s protection from industrial factors (dust, vibration, variations of temperature
and humidity) during continuous operation.
In the result of this system implementation the portion of agglomerate, which basicity deviated
from the value specified by the blast furnace shop by more than 0.05 was decreased by more than
twice ? from 8-10 % to 3-4 %, the saving of flux in the blast furnace shop was reduced by more than
Fig. 7. The interface of automatic flux batching system to agglomerate furnace charge
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Alexander M. Barishnikov and Michael L. Gaft. The Application of Laser Element Online Analyzer MAYA for Extraction?
CaO tracking lines
8
7
6
Lab CaO %
M2010 CaO %
CaO %
5
4
3
2
0
10
20
30
40
50
60
70
80
Sample number
Fig. 8. Comparison of laboratory data and MAYA data
Fig. 9. Comparison of the analyzer?s data and laboratory data for the content of Fe and CaO
0.6-0.8 kg per ton of cast iron; the period of cost recovery for the project was equal to less than 6
months.
Applications proven feasible by laboratory scale LIBS analyzer Cu and Ni
Copper ores quality control is usually needed for several tasks, for example online control of
Cu, S, Ca and Si and laboratory scale tests gave very satisfactory correlations for all these elements
(Fig. 10). Another important task is online control of Mo impurity in copper-bearing ore. Molybdenum
impurities are confidently detected even with Mo concentrations in the hundreds of ppm range and
correlation with laboratory data of Cu, Mo and Fe are quite satisfactory (Fig. 11), promising good
results in industrial online LIBS application.
Nickel- and copper-bearing ore requires online control of both elements? contents. Correlation
between laboratory data on Cu and Ni and laboratory-scale LIBS tests for two different fractions are
quite satisfactory (Fig. 12), promising good results in an industrial online LIBS application. In another
task, Fe/Ni concentration ratio and MgO content were the aims of online analyses, and the correlation
between laboratory data and laboratory-scale LIBS conveyer tests was very satisfactory (Fig. 13).
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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Fig. 10. Correlation between online LIBS and traditional laboratory data on Cu (a), CaO (b), SiO2 (c) and S (d)
for copper bearing ore
Fig. 11. Correlation between online LIBS and traditional laboratory data on Cu (a), Mo (b), and Fe (c) for copper
bearing ore
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Fig. 12. Correlation between online LIBS and traditional laboratory data on Cu (a, b) and Ni (c, d) for different
batches of Ni bearing ore
Fig. 13. Correlation between online LIBS and traditional laboratory data on Fe/Ni ratio (a) and MgO (b) for Ni
bearing ore
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander M. Barishnikov and Michael L. Gaft. The Application of Laser Element Online Analyzer MAYA for Extraction?
Good analytical results have been received also for Zn-, Pb-, Sn-, Ti-, Be-, Sr- and Ba-bearing
ores.
Potential for bauxite, alumina and aluminum industry
As the Al industry continues to grow the concentrations of impurities in raw materials are
increasing with significant implications to meet customer chemical specifications. The mostly important
impurities are Cr, Ti, Ni and V of the coke and Fe, Si, Ga, Zn of the alumina. These impurities must be
removed in order to get good quality aluminum, because they make it brittle and liable to corrosion.
In some smelters the concentration of these impurities is beginning to exceed customer cast product
specifications. Rapid and automatic analysis allows industrial minerals producers to promptly detect
changes in incoming raw materials, allowing them to take appropriate action in the process streams.
Specifically in Russia, the absence of high quality local bauxites, with silicon module (A/S) up to
10 with corresponding 50 % Al2O3 content, and strategic reasons led to creation of unique technologies
to process domestic low grade bauxites with A/S in 3-6 range [12]. The term bauxite is used for
naturally occurring mixtures of aluminum monohydrate (boehmite or diaspore) and trihydrate gibbsite
Al(OH)3, including impurities which are typically clay minerals, free silica, iron hydroxides and titania.
Thus online bauxite control enables to detect bauxite parts with low aluminum contents and to remove
them from the following beneficiation process. It may be done by the way used for crushed magnesite
ore mechanical sorting.
The applicability of radiometric sorting by XRF technique of Russia bauxite rocks has been
extensively studied [13]. It was proved that for -100+50 and -50+25 fractions of North Ural deposit it
is possible to remove carbonate from bauxite using intensity lines of Ca and Fe. As a result, the CO2
content was lowered from 18.0 to 4.1 %, while the A/S was increased from 10.2 to 14.1 %. For Timanskoe
deposit, the main task was to improve the A/S of the low grade hematite-boehmite bauxite. It may be
done by separation of minerals with high Fe and Si contents, mainly chlorites, using characteristic Fe
emission. It was proved that A/S may be raised by 1.6.
Another source is non-bauxitic raw materials such as nepheline Na3K(AlSiO4)4 and alunite
KAl3(SO4)2(OH)6. At the moment 4 major bauxite mines and 2 nepheline sources/mines are in operation
in Russia. The Al2O3 content is substantially lower than in bauxite ores and in order to produce 1 t of
Al, usually 3-4 t of bauxite is enough, while 7-8 t of nepheline and alunite are needed. Nevertheless,
nepheline ore is a part of apatite-nepheline, nepheline sienite and urtite deposits. It enables complex
process with nepheline concentrate used for alumina and apatite concentrate for fertilizers production.
Alunite is also complex source, containing alumina, sulfur anhydrite and alkali Na and K metals [14].
Once again, all those elements may be definitely detected and controlled by online LIBS technique.
The applicability of XRF sorting of nepheline was studied on non-conditional rocks with the following
composition: Al2O3 ? 22 %; SiO2 ? 40,1 %; CaO ? 11 %; MgO ? 2,2 %; Fe2O3 ? 5,6 %; Na2O ? 9,0 %;
K 2O ? 2,3 %. It was proved that 10-40 % of the rocks may be separated as tail while the remaining
part is a suitable for further technological treatment. Good XRF radiometric sorting results prove that
the corresponding rocks are very contrast and online process control may be very effective. The main
potential advantages of LIBS technique compared with XRF are the following. XRF is not suitable for
the light elements detection, usually with atomic number less than 20. If the energy of characteristic
emission is less than 5 keV, the interference is very strong because of air absorption and water on the
# 522 #
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Alexander M. Barishnikov and Michael L. Gaft. The Application of Laser Element Online Analyzer MAYA for Extraction?
minerals surface [1]. Thus very relevant elements, such as Al and Si, may not be detected directly and
all control may be accomplished using accessory elements analysis, such as Ca and Fe. LIBS can detect
all elements relevant for online control, including Al, Si, Ca, Fe and Ti.
References
[1] Mokrousov V., Lileev V. Radiometric concentration of nonradioactive ores. Moscow: Nedra,
1979.
[2] Salter J., Wyatt N. Sorting in the minerals industry: past, present and future. Minerals
Engineering, V. 4, N 7-11, p 779-796, 1991.
[3] Cutmore N., Eberhard M. www.min-eng.com/protected/me02ex.
[4] Gaft M., Reisfeld R. and Panczer G. Modern luminescence spectroscopy of minerals and
materials. Springer-Verlag GmbH&Co.KG, 2005.
[5] Cremers D., Radziemski L. Handbook of Laser-Induced Breakdown Spectroscopy, WILEY,
2006.
[6] Laser-Induced Breakdown Spectroscopy. Fundamentals and Applications. Edited by A.
Miziolek, V. Palleschi, I. Schechter: CAMBRIDGE, 2006.
[7] Gaft M., Nagli L., Groisman Y., Barishnikov A. Industrial online raw materials analyzer based
on Laser-Induced Breakdown Spectroscopy, Applied Spectroscopy, 2014 (In press).
[8} Gaft M. and Nagli L. Mineral Detection and Content Evaluation Method. ? US Patent 6,753,957
B1, 2004.
[9] Akselrod L., Zaitsev V., Sharov M., Savchenko A., Barishnikov A. The system of raw
magnesite sorting at crushing-concentration factory of Magnesite Complex with application of flow
laser analyzer MAYA 6060 M-2010, Novye ogneupory, No. 11, 2012.
[10] Tikhonov D., Mansurova N., Barishnikov A., Isaenko G., Titov N., Istomin V., Semenov
O. Th experience of stabilizing the chemical composition of agglomerate by means of flow online
analyzer MAYA», Journal Metallurg, No. 2, 2013.
[11] Barishnikov A., Gaft M., Isaenko G., Mansurova N., Tikhonov D. Stabilizing material?s
chemistry by implementation of real time elemental laserinduced breakdown spectroscopy (LIBS)
analysis, ICSTI ? 6th International Congress of the Science and Technology of Ironmaking, Brazil,
2012.
[12] http://www.mining-media.ru/ru/article/ekonomic/519-sostoyanie-syrevoj-bazy-alyuminievojpromyshlennosti-rossii
[13] http://technoros-kras.ru/index.php?&block=14&page=list.
[14] http://library.krasu.ru/ft/ft/b72/0227142/pdf/16/101.pdf
[15] Gaft M., Stana R. Remote real-time analyses of phosphate rock, Final FIPR Report. 2011.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander M. Barishnikov and Michael L. Gaft. The Application of Laser Element Online Analyzer MAYA for Extraction?
?????????? ????????? ???????????
??? ?????????? ???????????? ?????
? ???????????? ???????? ??????
? ?????? ????????? ???????
? ???????????? ??????? ????????
?.?. ??????????a, ?.?. ?????
a
Icon Steel,
USA
?
Laser Distance Spectrometry
9 Mota Gur St., Petach Tikva, 49514, Israel
???????? ??????????? MAYA ??????? ??????????? ? ?????????????? ??? ??????? ?????
?????????? ????????? ???? ? ???????????? ??????? ???????? ?????? ? ??????????? ?
???????????? ??????????? ??????????. ????????? ??? ??????? ????????, ????? ??? Cu, Mo,
Zn, Pb, Sn, Ti, Be, Sr ? Ba, ??????????????? ? ???, ??? ? ?????? ??????? ???????? ???????????
????? ???? ????????? ?? ????? ?????? ??????? ???????????????? ????????: ?????? ?????,
?????????? ???????? ?????, ???????? ???????????? ???????, ??????????? ???????? ????????
??????? ?????????.
???????? ?????: LIBS, online, ??????????????, ????????, ???????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 525-532
~~~
??? 66.011
Optimization of the Technology of Alumina Refinery
of Branch Ojsc «Sual» «Uaz ? Sual»
in Processing of Bauxite STBR
Evgeniy V. Pustynnyha*, Aleksey A. Nifontova,
Aleksey V. Perestoroninb and Andrey V. Panovb
a
OJSC «SUAL» «UAZ ? SUAL»
4 Zavodskaya Str., Kamensk-Uralskiy,
Sverdlovsk region, 623406, Russia
b
Separate division
OLLC «RUSAL ETC» St.Peterburg
86 Sredniy, St. Petersburg, 199106, Russia
Received 30.01.2014, received in revised form 24.03.2014, accepted 16.07.2014
Presents data on the processing of bauxite ???? in alumina refinery Branch of OJSC «SUAL» «UAZ ?
SUAL». There are the results of trials of the stages: grinding, autoclave digestion, thickening and
washing of red mud, when the basket bauxite is change. Presents final date the results of trials in the
alumina refinery.
Keywords: alumina refinery, bauxite STBR, grinding, removed soda, crystal soda, autoclave
digestion.
????????
? ???????????? ???????? ? ??????? ??? «????» «???-????» ??????? ??????????????? ?????? (????) ?????? ?????????????? ? 1998 ?. ??? ????????????? ????? ? ???????????? ? ???????? ??????-?????????? ??????????? ??????? (????). ??? ??????????? ????????????? ? ????????? ?????????? ??????????? ?????? ????? ????????????? ? ????????
«????» ? ???????? 1995 ?. ?? ????? ???? ?????????? ??????? ?????? ??????? ? ??????????
12 ???. ?, ?? ??????? ????????? ???????????? ????????? 9?23 ??????? 1995 ?. ? 1998 ?. ?????? ??? «????» «???-????» ?????????????? ?????? ???? ? ???????????? ???????? ?
??????????? ??????????? ??? ???? ? ???????? ??????? ???????????, ? ? ???? 2012 ?. ???
??????????? ??????? ?? ??????????? 100 % ??????? ????.
??????????? ???????????
??????? ?????-????????????? ?????????????, ? ????????? ????? ???????????????? ?? «????», ????????? ? ?????-???????-???????????? ???? ? ????????? ???????? ??*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: Evgeniy.Pustynnykh@rusal.com
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Evgeniy V. Pustynnyh, Aleksey A. Nifontov? Optimization of the Technology of Alumina Refi nery of Branch Ojsc?
??????? 1. ?????? ????????? ?????? ???????? ????
?????????? ??????, % ????.
4,54
6,52
8,34
12,62
17,47
Al2O3
SiO2
FeO
Fe2O3
?Si, ??.
44,60
10,21
9,85
27,79
48,80
7,48
3,39
27,50
47,62
5,71
4,21
30,29
51,82
4,10
1,58
26,43
52,47
3,02
0,86
26,64
?????
???????
???????
????????
???????
?????
38,0
1,0
36,0
14,0
6,0
54,0
2,0
6,0
20,0
5,0
57,0
1,0
3,0
22,0
4,0
???????????????? ??????, %
44,0
4,0
13,0
8,0
17,0
8,0
48,0
1,0
16,0
22,0
5,0
??????. ?????? ??????? ????????? ? ???? ???????? ????????, ????????? ?????? ???????
????? 6ч7 ??????, ? ??????????????? ?????????? ??????????? ?????? ?????? ? ??????
??????.
??????? ?????????????????? ????????? ???????? ???? ???????? ?????, ????? ????????? ???????? ????? ?????????? ???????? ?? ????????? ? ????????? ???????? ????? (????. 1).
?????????? ?????? ? ???????? ? ??????? ??????????? ?? 40 ?? 56 %. ??????? ?????????? ? ????????? ?????????? ? 1-4 %. ????????????????? ???????? ???????????? ?????????, ?????????? ? ???????????. ?????????? ?????? ????????? ?????????? ???????????, ??? ??????
????????????? ???????????? ???? ???????? ??????-????????? ?????? [1].
?????????????? ???????? ??????? ????? ??????? ?????????? ????????. ??????????
?????? ????????? ????? ???????????. ??????????? FeO ? Fe2O3 ? ???????? ????????, ???
?????????? ??? ????????????? ? ???????-??????????? ?????????. ?? ????? ??????,
??? ??????????? ~235 °? ??????? ??????????? ?? ????? ??? ?? 20 %, ? ? ????????? ???????
??????????? ????????? ????????? ? ??????? ????. ??????? ????????, ??? ??? ???????? ?
????? ??????? ??????????? ???????? ?????????? ?????????? ??????? ??? ??????????.
???????? ???????????????? ????????? ? ???????? ???? ???????? ???????. ??????????
?????? ? ??????? ?????????? 4-5 %, ?????? ? ?????????????????? ???????? ?????????
8ч10 %.
??? ??? ?????? ??????? ???? ???????????? ???????? ????????, ????????? ???????
? ??????? ?? ???? ????? 17ч18 % (? ?????????? ??????? ????????? 19ч20 %), ? ? ?????????
??????? ??????????? ?? 23 %. ??????? ???????? ?????? ??????????????? ??????????
??????????? ?????, ?????????? ???????? ??????????? ?? 0,02 ?? 0,061 % [2].
??????????????? ???????? ? ???? ??????????? ??????????
??? ???????? ??????? ???? ? ???????????? ??????????????? ????? ???????????? ???????????? «????» ?????? ??? ??????????????? ???????, ????????????? ??????????????? ???????:
? ??????? ?????????? ????? ? ???????, ???????? ? ?????????? ???????;
# 526 #
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Evgeniy V. Pustynnyh, Aleksey A. Nifontov? Optimization of the Technology of Alumina Refi nery of Branch Ojsc?
? ?????????? ????????????? ? ???????? ???????????? ?????????????;
? ?????????? ?????????? ????? ??? ???????? ?? ??????????? ??????? ? ????????? ??????? ~ 6,5 ??????;
? ??????? ?????????? ?????????? ? ???????????? ????????? ??????????? ???????;
? ?????????? ??? ??????????, ???????????? ? ???????-??????????? ??????? ? ???????? ???????????? ?????????????;
? ?????????? ?????????? ?????? ? ???????? ????????? ?? ???? ???????????????? ? ???????????? ??????;
? ?????????? ?????????? ?????????????, ????? ??? ????, ????, ???????? [2].
?????????? ???????? ???? ??????????? ??????????? ??????????:
? ??????????? ?????? ???????;
? ???????? ???????????? ?????????? ????????, ??????????? ???????? ?????????????;
? ???????? ????????????? ??????;
? ???????? ??????????? ???????????? ????????????? ??????? ???????? ???????????
?? ~228 °?;
? ??????????? ???????? ??????????? ????????? ??? ?????????? ?????? ???????? ?????;
? ?????????? ??????????????? ??????? ???????? ???????.
??????????? ?????? ???????
?? ?????????????, ??????????? ????????????? ??? «????? ????», ??????????????
??????? ???? ? 1,3ч1,5 ???? ????, ??? ??????? ????, ? ??? ??????????? ? ????????? ???????
«????» ?? ??????????? ?????????? (???????????????? ?? ???? ? ???????????? ??????? ????)
???????? ? ????????????? ??????????????? ??????? ????. ??? ???? ?????????? ???????
«?56 ???» ? ?????????? ?????? ????????? 87ч89 %.
??? ??????????? ?????? ??????? ???? ?? ????? ?? ??????????????? ???????? ???????????? ???????????? ????????? ????????? ? ? ????????? ????? ???????????? ????? ? ??????????? ??????????? ???????? ???????: 2ч3 ???????? ???????? (Ш2,7 ? L 3,6 ?) ? ???? ????????
??????? ??????? (Ш2,2 ? L12,0 ?) ? ????????????? ?????????????? ?????????? ??????. ????????????? ???????????? ????? ? ???????????? ????????? ??????? ??????????????? ? ???????? ????????? ?????????? ?????? ?? ?????? «+160 ???» ?? 3,5 %, ??? ???? ?????????????????? ??????? ??????? ???????? ~?? 30 %.
? ?????? ?????? ? ???? ?????????? ????? ???????? ???????????? ????????? ?? ?????????? ????? ????????????? ????????????? ??????. ?? ??????????????? ??????????? ????????????? ?????? ????? ??? ??????????? ?????? ??????? ?????????? ?????????? ? ???????
???????? ?????? ??????????????.
???????? ???????????? ?????????? ????????,
?????????????, ????????? ??????????????? ???????
???????????? ????????? ?? ???????? ???????????? ???????????? ?????? ? ????????? ???????? ???? ????????????? ????????? ??? ??????????? ????? ???????? ???? ? ????
# 527 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Evgeniy V. Pustynnyh, Aleksey A. Nifontov? Optimization of the Technology of Alumina Refi nery of Branch Ojsc?
? ??????????? 1:3 ? 3:2. ???????? ???????????? ? 295ч301 ?? 285ч291 ?/??3 ??????? ? ?????????? ?????????????????? ???????? ??????? ?? ??????? ???????? ?? ~ 6 % ? ??????????
??????????????? ????? ???????? ??????? ?? ~ 20 %. ????? ???????? ??????? 7 ???. ????
???? ?????????? ?? ?????? 0,032ч0,05 ???? ?? 1 ? ?????????. ?????? ?? ???????? ????????????
????????????? ???? ???????? ???????? ??????????? ?????????? Al2O3 ?? ??????? ? ???????
?? ???????????? ?????????? ? ??????? ?? 0,51ч0,71 % ? ?????????? ??????? ????? ?????? ??
~ 3,7 % ? ??????? ?? 1 ? ?????????.
??????????? 100 % ???????? ???? ??????? ? ????????? ?????????? ? ??????????
??????? ??????????? ????????? ? ??????? ?????????? ???? ? ???, ??? ??????? ?????????
????????????? ? ???????? ???????? ?? ????????? ?? ???? ????????? ????. ????? ?? ????????? ????????? ??????? ?????? ???????? ???????? ?????? ??????? ???????? [4]. ??? ????????? ????????????? ? ?????????? ???????? ????????? ??????? ? ???????????? ????????
???? ?????????? ?????????? ????? ????????? ???? ??? ???????? ? ????????????? ????????
??????? ??????? ???????? [3]. ????????? ????????? ? ???? ??????? ?? ?????????? ???????
???? ? ????????? ??????????? ????????: 80 (??? ??????? ????????), 130 (1-? ?????), 145 ?/??3
(2-? ?????) ?? ???????? ?????? ? 21 ??????? ? 11, ??? ???? ??? ??????????? ???? ?????? ????????? ??????? ?????? ?? ?????????????? ?? ???????? ???????. ?? ??????????? ?????????
????????? ???????????, ???????????? ????????? ?? ??????? ????????? ????????? ?????? ?
???????????? Na2O?? (???. 1?4).
??????? ?????????? ?????? ???????? ??????? ??? ?????? ? ??????? ????????? ? ??? ???
???????????? ? ????. 2.
???????? ????????????? ??????
????????? ???????????? ????????? ?? ???????? ????????????? ?????? ???????????? ?????? ? 1,59ч1,67 ?? 1,53ч1,61 ??. ??? ??????????? ??????? ???? ? ?????????? ???????
6,6ч7,3 ??. ??????????? ???????? ??????? ?????????? Al2O3 ?? ??????? ? ??????? ?? ~2,2 %.
???????? ????????????? ?????? ???????????? ?????? ????????? ???????? ?????? ???????????? ????????, ???????????? ? ??????? ????????????, ?? 0,02ч0,04 ??. ?, ??????????????,
????????? ????????? ?????????? ?? ~4,5 %.
1,500
295
????????????????????????,
?/??3
????????????Na2O??,?/??3
290
285
280
275
270
265
260
255
250
1
5
9
13
17
???????????????????????,?
21
???. 1. ????????? ???????????? Na2O?? ?? ???????
(1-? ?????)
1,490
1,480
1,470
1,460
1,450
1,440
1,430
1
5
9
13
17
???????????????????????,?
21
???. 2. ????????? ????????? ????????? ?????? ??
??????? (1-? ?????)
# 528 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Evgeniy V. Pustynnyh, Aleksey A. Nifontov? Optimization of the Technology of Alumina Refi nery of Branch Ojsc?
1,500
????????????????????????
?/??3
295
????????????Na2O??,?/??3
290
285
280
275
270
265
260
255
250
1
5
9
13
17
???????????????????????,?
1,490
1,480
1,470
1,460
1,450
1,440
1,430
21
1
???. 3. ????????? ???????????? Na2O?? ?? ???????
(2-? ?????)
5
9
13
17
???????????????????????,?
21
???. 4. ????????? ????????? ????????? ?????? ??
??????? (2-? ?????)
??????? 2. ??????? ?????????? ?????? ???????? ???????
????????????? ?????
?????????? ??????? ???? ? ????????? ??????, ?/??3
??? ???????
????????
1-? ?????
2-? ?????
80
130
145
?????????????? ??????, ?
17,5
24,3
44,3
??????? ?????? ????????? ????, ??
0,179
0,300
0,398
???????????? Na2O??, ?/??3
285,12
277,15
283,95
????????? ?????????? ????????, ?/??3
1,430
1,448
1,472
???????? ??????????? ????????????
????????????? ??????? ?? 230ч228 °?
??????????? ????????? ??????? ???? ???????-??????????? ????????? ? ???? ?? ???????? ????????, ???????????? ??????? ?????????? Al2O3. ????? ?????????? ????????????
????????? ? ??????-??? 2013 ?. ???????? ??????????? ??????????? ???????? ???????????
????????????? ?? 230ч228 °? ??? ?????????? ?????????????????? ???????? ????????????? ?????? ? ??????????? ?????????? Al2O3 ?? ??????? ? ???????. ????????? ????????, ???
??? ????????????? ??????? ???? ? ?????????? ??????? ~6,35 ??. ??? ??????????? ~228 °?
???????? ??????? ?????????? Al2O3 ?? ??????? ? ??????? ?? ????????, ??? ???? ??????????
????????? ? ??????? ? ??????? ?????????? ????? 97,0 % ?? ???????????? ??????????. ???????????? ???? ????????????? ?????? ???????? ??????????? ?????????? Al2O3 ?? 1,5ч2,0 %, ?????????????, ????????, ???????????????? ????????????????? ??????? ?????????? ??????? ??
?????????? ? ??? ????????.
?????? ????????? ??? ???????????? ??????????
?????? ???????? ?????
?????? ???? ??????????????? ??????????? ????????????????? ? ??????? ????????
???????? ??????????. ??? ???????? ???????? ????????? ????????? ???????? ????? ??? ??# 529 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Evgeniy V. Pustynnyh, Aleksey A. Nifontov? Optimization of the Technology of Alumina Refi nery of Branch Ojsc?
???????? ???????? ??????????????? ?????????? ?????????? ???????????? ????????? ??
??????? ???????? ??????????? ????????? ? ??????????? ?????????? ???????? (??????????
???????? ? ?????? ??????? ???????????, ????????? ? ???? ?????????? ? ????????? ?????, ??
???????? ??? ????????????? ????????).
???????? ??????????
??????????? 100 % ??????? ???? ???????? ? ???????????? ?????????? ????????????????
????????????:
? ??????? ?????????????? ? ?????? ?????? ?? ??????????? ????????;
? ?????????? ???????? ??????? ??????????? ??????? ? ??????? ???????? ????;
? ?????????? ???????? ?????? ??????????? ??????? ????? ???????? ? 5-6 ?? 3-4
???????;
? ?????????? ?????????? ?????? ????????????? ????? ??????.
???????? ?????????? ???????? ??????????? ?????????? ??????, ?? ??? ??????????
???????????? ????????????? ???????????? ??????? ????? ?????? ? ??????? ? 14 ?? 9 ????
?? ???? ??????????? (?????????? ????????? ???????? ???????? «Woma», «Hammelman») ?
??????????? ???????????? ??????. ?????????? ?????? ????????? ??? ?????????? ??????????
??????? ?????????????? ????????????.
?????????? ??????????? ????? ?? ??????????? ??????????
1. ????????? ?????????? ????????? ??????? ??????? ??? ????????????? ??????? ????
????? ???????? ????????? ????????? ????????? ????????????. ?????????? ????????????
?????????? ???????? ??? ?????- ? ???????????????????????? ??????????. ?????????????????????? ?????????? ?????????????? ?? ???????????? 240 ?/? ?? ???????????? ??????. ???
????????? ???? ???????????? ?????????? ???????? ?????????? 300 ?/? ?? ???????????? ??????.
2. ??????? ???? ????????? ??????? ??? ????????? ??????????????????????? ?????????? ???????? ??? ?????????????.
3. ?????????? ??????????? ???????? ??????? ??????? ? 3 ? ???? ?? ??????? ? ????.
4. ?????????? ???????????? ????????? ?? ???????? ?????? ???????????? ??????
??? ????????????? ???????? ??????????? ??????????.
?????????? ??????
? ??????? 3 ???????????? ???????? ????????? ???????????? ?? 1 ? ????????? ???
??????????? ????? ???????? ? ??????????? 50/50 ? ??? 100 % ????.
??????
1. ? ???? 2012 ?. ??? ??????????? ??????? ?? ??????????? 100 % ??????? ???? ?
??????????? ???????????? ??????? ??? «????» «??? ? ????».
2. ?????????? ???????? ????????? ???????? ???? ??????????? ??????????, ??? ????????
????????????? ???????? ??????????? ?????????? Al2O3 ?? 1,5ч2,0 % ?? ???????? ????????????
?????????????.
# 530 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Evgeniy V. Pustynnyh, Aleksey A. Nifontov? Optimization of the Technology of Alumina Refi nery of Branch Ojsc?
??????? 3. ??????? ?????????? ?????? ???????????? ???????????? «????»
????????????
??????? ?????????
50 ???? / 50 ????
5 ??????? 2012 ?.
100 % ????
5 ??????? 2013 ?.
?????? ( ???)
?
2,4460
2,5834
????????????
????
3,5544
3,3148
??????????????
???
422,46
400,84
????
??
108,85
147,15
?????????
??
0,7110
0,9373
???????
?
0,0527
0,1074
3. ?????????? ???????? ??????????????? ???????? ??? ????????? ???????? ???????,
???????? ???? ??????? ??????????????? ???????, ???????? ??? ??????-????????????
?????????, ??????????? ????????????? ??????????????? ??????? ?? ?????????: ??????,
??????????? ?????????????, ???????? ? ???????? ???????? ?????, ?????????????.
4. ?????????? ???????? ??????? ???????????? ?? 6,75 % ? ?????????????? ?? 5,12 %
??? ??????????? 100 % ??????? ???? ???????????? ?????? ???????????? ???????????? ???
??????????? ????? 50 % ??????? ???? ? 50 % ??????? ????.
?????? ??????????
[1] ???????-????????????? ??????????? ?????????? ? ????????????? ??????-??????????
??????????? ??????? ??????????????????? 2 250 ???. ? ? ??? ? ?????????? ???????? ???????:
? 6 ?. / ??? «????». ???., 1999.
[2] ????????? ?.?., ????????????? ?.?., ???????? ?.?. ? ??. // ??. ???????? ?III
????????????? ??????????? «???????? ??????». ??????????, 2007. ?. 221-225.
[3] ????????? ?.?. ?????????????? ?? ????????? ? ?????????? ??????????????. ?.:
?????, 1968. 304 ?.
[4] ????????? ?.?., ?????? ?.?., ???????????? ?.?. ? ??. // ??. ???????? IV ?????????????? ????????? «??????? ???????». ??????????, 2012. ?. 337?344.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Evgeniy V. Pustynnyh, Aleksey A. Nifontov? Optimization of the Technology of Alumina Refi nery of Branch Ojsc?
??????????? ?????????? ???????????? ????????????
? ??????? ??? «????» «??? ? ????»
??? ??????????? ??????? ????
?.?. ??????????, ?.?. ?????????,
?.?. ?????????????, ?.?. ??????
?
?????? ??? «????» «??? ? ????»
??????, 623406, ???????????? ???????,
???????-?????????, ??. ?????????, 4
?
???????????? ?????????????
??? «????? ???» ?. ?????-?????????
??????, 199106, ?????-?????????, ??????? ??., 86
???????????? ?????? ?? ??????????? ??????? ???? ? ??????????? ???????????? ???????
??? «????» «???-????», ???????? ?????????? ??????-???????????? ????????? ??
?????????: ??????, ??????????? ?????????????, ???????? ? ???????? ???????? ????? ???
????????? ???????? ??????? ???????????? ???????????? ? ?????????? ??????????? ?????????????????? ????????? ? ??????????? ????????????.
???????? ?????: ??????????? ????????????, ?????? ????, ?????, ?????????????, ????????
????, ??????????? ?????????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 533-543
~~~
??? 669.213, 66.046.8
Process Development for Refractory
Gold Concentrates Treatment on Pokrovsky POX Hub
Peter V. Zaytsev*, Yakov M. Shneerson,
Alexander Y. Lapin, Lev V. Chugaev,
Mikhail V. Klementiev, Mikhail A. Pleshkov,
Ilia V. Fomenko and Stepan S. Bakhvalov
SRC Hydrometallurgy LLC
Of. 626, 151 Leninskiy, St. Petersburg, 197046, Russia
Received 26.02.2014, received in revised form 14.06.2014, accepted 11.08.2014
The chemical composition and mineralogy of Malomir and Pioneer gold-bearing ores were
discussed. The main gold forms in the ores were indicated: the preferential gold association with
sulfide minerals was noted. The chemical composition of sulfide flotation concentrates was shown.
The laboratory and pilot tests results of concentrates pressure oxidation were introduced. The
influence of organic carbon content in the concentrate and chloride ion content in the liquid phase
of pressure oxidation slurry on the gold extraction from materials were noted and researched.
The effect of preliminary treatment stages on POX indicators was shown. The positive effect of hot
autoclave slurry conditioning on gold recovery was noted. The process flow sheet for treating both
Malomir and Pioneer ores was developed and advised.
Keywords: gold ores, separation of the pressure oxidation, pressure oxidation technology.
Introduction
Malomir and Pioneer mine sites are located in the Russian Far East in Amur region. Petropavlovsk
PLC Group of Companies owns and operates both mines. Petropavlovsk is the second largest gold
producer in Russia producing 710 400 ounces (22,1 tons) of gold in 2012.
Malomir and Pioneer gold ores are refractory due to the gold association with sulfides. Refractory
materials constitute approximately half of the Group?s current gold reserves. That makes processing of
refractory ores a strategic priority for Petropavlovsk.
The prefeasibility study of POX, bio oxidation and roasting of Malomir and Pioneer ores revealed
that POX is the most suitable pre-treatment technology.
Malomir and Pioneer ores will be subjected to flotation and upgraded to high-grade concentrates.
Flotation concentrates will be trucked by existing roads to Pokrovsky mine site for processing in highpressure autoclaves, which are currently being installed as well as oxygen plant and filtration site. POX
hub on Pokrovsky site benefits from existing infrastructure and RIP facilities.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: peterzaytsev@gidrometall.ru
# 533 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Peter V. Zaytsev, Yakov M. Shneerson? Process Development for Refractory Gold Concentrates Treatment?
This article provides the results of Malomir and Pioneer material analysis and POX process
development, batch and pilot tests.
Ore chemical composition and mineralogy
The studied Malomir ore samples mostly consist of lithophile components with predominance of
silica (55?63 %). Sulphur and arsenic are found mostly in the sulphidic form. The share of sulphidic
iron accounts for 36 to 54 %. Malomir ore is also characterised by the presence of organic carbon in
an amount of 0.10 to 0.16 %.
The Pioneer ore had a smaller content of metallic minerals components and insignificant levels of
arsenic. The lithophile component content is slightly higher with predominance of silica (72.4 %).
The main valuable component of the ores is gold. Malomir ore assays at 1.45 to 2.0 g/t with
Pioneer lower at 1.2 g/t.
The bulk of Malomir and Pioneer ore samples are rock-forming minerals with predominance of
quartz (38?44 %). In addition, feldspar, hydromicaceous clay and carbonates are present in significant
amounts. Sulphide minerals are mostly pyrite (2.2?3.8 % in Malomir and 2.0 % in Pioneer) and
arsenopyrite (1.2?1.3 % in Malomir and insignificant amounts in Pioneer). In addition, iron hydroxides
are present. Malomir ore is also characterized by the presence of carbonaceous matter.
Gold association
The following forms of gold occurrence are typical for the studied ore samples: leachable by
direct cyanidation; leachable by cyanidation after treatment with hydrochloric acid (locked in iron
hydroxides, carbonates, etc.), nitric acid (locked in sulphides), roasting (locked in carbonaceous
matter and in sulphides fi nely distributed through rock-forming minerals); locked in rock-forming
minerals.
The Table 1 data shows that Malomir and Pioneer ores are refractory to direct cyanidation. Gold
available for cyanide leaching is 12?17 % in Malomir ore and 30 % in Pioneer ore. The primary reason
for the refractory ore is gold association with sulphides.
Flotation concentrates
Malomir and Pioneer ores require flotation concentration before being fed to the POX stage. The
main flotation product is sulfide concentrate comprising most of the gold from the ore. Moreover the
Table 1. Gold association in Malomir and Pioneer ores
Forms of gold
Malomir
Pioneer
Leachable by direct cyanidation
12-17 %
30 %
Locked in iron hydroxides, carbonates, etc.
12-18 %
20 %
Locked in sulphides
Locked in carbonaceous matter and in sulphides finely distributed
through rock-forming minerals
51-56 %
39 %
Locked in rock-forming minerals
# 534 #
10-13 %
?/?
2-5 %
9%
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Peter V. Zaytsev, Yakov M. Shneerson? Process Development for Refractory Gold Concentrates Treatment?
Table 2. Malomir and Pioneer sulfide concentrates chemical composition
Malomir
Component
26c
Pioneer
24d
21b
26a
24d
21b
24d
?
24.6
?
?
22.5
?
25.7
21b
26d
24d
21b
25.9
?
27.0
19.7
Component content ( %)
Fe tot.
S tot.
?
23.0
20.6
21.0
18.9
21.3
23.5
24.3
23.9
23.0
20.4
S sulfide
?
22.8
20.5
20.9
18.8
21.1
23.3
24.2
23.7
23.0
20.4
As tot.
?
7.81
?
?
?
?
9.19
8.53
?
7.10
0.66
? org.
0.31
0.41
0.55
0.65
1.10
1.14
1.20
1.48
2.04
2.40
?/?
Au (g/t)
21.2
22.0
28.6
24.4
24.3
24.6
24.3
23.8
25.7
23.5
26.5
carbon flotation is introduced to the Malomir flotation flowsheet in order to remove carbonaceous
matter.
Chemical composition of the Malomir and Pioneer pilot flotation concentrates is shown in
Table 2.
The Malomir concentrate samples were produced according to the different flotation flowsheets.
The main difference in chemical composition of these concentrates is organic carbon content as shown
in Table 2. The Pioneer pilot concentrate samples were relatively even in chemical composition. Hence,
chemical composition for only one Pioneer sample is shown in Table 2.
Malomir sulfide concentrate yield, depending on ore sample origin and concentration flowsheet
details, is 4.5?5.6 %. Gold recovery to the concentrate is 86?87 %. Pioneer concentrate yield is 2.9?
3.6 %; gold recovery is 82?85 %.
POX process development
Initially POX technology was extensively tested in SRC Hydrometallurgy laboratory in
St. Petersburg. Every flotation concentrate sample was subjected to batch tests in laboratory autoclaves.
In order to test and confirm the laboratory batch tests results as well as to achieve a better understanding
of the process, a series of continuous pressure oxidation tests on Blagoveshchensk Pilot Plant was also
carried out.
Laboratory tests
Experimental methods. In all the laboratory tests, distilled water was used in order to
eliminate the influence of chloride impurities contained in tap water. A sample of concentrate
was ground and treated with sulfuric acid to remove carbonates. The resulting slurry was fi ltered,
the cake was washed with water on the fi lter to remove chloride ion dissolved from concentrate
during acid treatment. The washed cake was loaded into a titanium autoclave by Bьchi Glas Uster
with the capacity of 1100 cm 3 equipped with a turbine stirrer with adjustable rotational speed.
The temperature of the slurry was kept constant by the automatic control system with an accuracy
of ±0.5 degrees. A Bronkhorst flow and pressure meters was used to control and regulate total
pressure and oxygen flow. Oxidized slurry was cooled and conditioned. The resulting slurry was
then fi ltered. The fi lter cake was then washed and diluted with water, neutralized and treated
# 535 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Peter V. Zaytsev, Yakov M. Shneerson? Process Development for Refractory Gold Concentrates Treatment?
with cyanide using standard RIL methods. After RIL, the solids of the slurry were separated and
subjected to gold assay.
Results. During initial POX testwork the influence of the following primary parameters was
investigated:
? Temperature (190?230 °?),
? Oxygen overpressure (450?730 kPa),
? Regrinding (size of 90 % of particles less than 15, 40 and 70 microns).
The results (as predicted) showed that high POX temperature, high oxygen overpressure and fine
particle size favor a high oxidation rate. As long as there was complete decomposition of sulphides
high gold recovery was achieved. The following basic parameters were fixed for the rest of laboratory
tests: temperature 225°C, oxygen overpressure 730 kPa, and particle size of 90 % of particles less than
40 microns.
Under these specified conditions a number of flotation concentrates samples were tested. As noted
earlier, the main difference between various Malomir concentrates samples is organic carbon content.
Pioneer concentrate tends to be a relatively simple material to treat using POX. Maximum
achievable gold recovery from Pioneer is 98 % (and higher). In order to achieve high gold recovery
from Pioneer it is necessary to oxidize the sulfides (at least 98 % of them).
Gold recovery from Malomir strongly depends on carbonaceous matter content as well as chloride
concentration in the autoclave slurry.
Malomir concentrates pressure oxidation with potassium chloride addition and subsequent
cyanidation results were shown and discussed in the paper [1]. It is seen that with the increasing
levels of organic carbon content in concentrate, gold recovery from the autoclave residues decreases
proportionally. For low-carbonaceous concentrate T-24d gold recovery is 96.6 %, while for the
concentrate T-16 recovery is 84.3 %. The concentration of chloride ion in all the experiments is similar:
the range is 2 to 5 mg/dm3.
For all tested concentrates a significant decrease in gold recovery occurs with increasing of
chloride content in the autoclave slurry. It is clear that the negative effect of chloride ion manifests
itself to varying degrees. High-carbonaceous concentrates are more sensitive to increased amounts
of chloride compared to low-carbonaceous concentrates. When the concentration of chloride in the
autoclave slurry reaches 15 mg/dm3, gold recovery from low-carbonaceous concentrates (0.3-0.6 %)
decreases to 90 %, from high-carbonaceous concentrate T-16 ? to 65 %.
Gold recovery from Pioneer concentrate is 98 % (and higher) even with chloride ion concentration
up to 10 ? 20 mg/dm3. A noticeable decrease of recovery occurs only when chloride ion content reaches
100 mg/dm3 or higher.
Special testwork was carried out to investigate the influence of concentrate pre-treatment on
gold recovery. It was found that water washing of concentrate before feeding to the autoclave allows
washing out a water-soluble part of chlorides and chlorides contained in porous moisture. Furthermore
acid pretreatment of concentrate, along with carbonate decomposition, allows further dissolution
of chloride-containing minerals. The subsequent water wash results in chloride removal from the
concentrates.
Water washing of acid pre-treated concentrate removes chloride, which in turn leads to increased
gold recovery as shown in Fig. 1.
# 536 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Peter V. Zaytsev, Yakov M. Shneerson? Process Development for Refractory Gold Concentrates Treatment?
Fig. 1. Concentrate preliminary treatment effect on gold recovery
Pilot POX testwork
Experimental methods. Continuous pressure oxidation tests were carried out on a Pilot Plant in
Blagoveshchensk Test Facility [2], a schematic of which is shown below in Fig. 2.
Flotation concentrate sample was ground in a ball mill to 90 % of particles passing 40 microns.
The ground sample was then diluted with water to 30 % of solids and treated with concentrated sulfuric
acid or recycled acid solution to remove carbonates.
The resulted slurry was then filtered. The cake was diluted with water to 45 ? 55 % solids content
and loaded into autoclave feed reactors. The slurry was fed to the autoclave by high pressure pump
by Netzsch. The slurry was continuously oxidized in a titanium four-compartment autoclave with a
capacity of 50 dm3. The autoclave is equipped with five agitators with adjustable rotational speed.
Slurry temperature was maintained at 225 °C by feeding cooling water to the autoclave compartments.
An oxygen flow rate was controlled and measured by Bronkhorst flow meters. A working pressure was
maintained at 3 250 kPa by continuous autoclave gas venting. Oxidised slurry was then discharged
from the autoclave last section, cooled to the temperature of 95 °C and conditioned for two (2) hours.
The resulting slurry was filtered. The filter cake was washed and then diluted with water, neutralized
and treated with cyanide using standard RIL method. After RIL cyanidation the solids in the slurry
were separated and subjected to gold assay.
In the process of continuous pressure oxidation each autoclave compartment was also slurry
sampled and the solids were treated in the same way as the autoclave discharge. The retention time was
calculated in each autoclave compartment by dividing the volume of a compartment and a sum of feed
slurry and cooling water fed to the compartment.
Results and discussion. Chemical composition of the concentrates produced on flotation Pilot
Plant and corresponding gold recovery achieved after POX are shown in Table 3.
In total, over 50 pilot autoclave runs lasting 10 to 15 hours each were made to oxidize Malomir
concentrates and 15 more runs for Pioneer concentrates. Various pressure oxidation parameters
# 537 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Peter V. Zaytsev, Yakov M. Shneerson? Process Development for Refractory Gold Concentrates Treatment?
Fig. 2. POX Pilot Plant schematics
Table 3. Concentrates and POX results on Pilot Plant
Chemical composition
Date of flotation
Sample
Au
(g/t)
Deviation from
design ( %)
S (S2-)
( %)
Deviation from
design ( %)
?org
( %)
Gold
recovery ( %)
Malomir
Design
April 2011
?S-1
24.3
0
24.9
0
0.6
23.3
-4 %
19.8
-20 %
1.7
90-93
December 2011
?S-1
27.9
15 %
23.5
-6 %
0.6
89-96
March 2012
?S-2
36.1
49 %
19.8
-20 %
0.6
90-94
September 2012 (1)
?S3-4
24.8
2%
19.8
-20 %
1.7
78-83
September 2012 (2)
?S3-4
26.4
9%
21.4
-14 %
1.0
85-89
September 2012 (3)
?S3-4
29.9
23 %
25.6
3%
0.7
92
December 2012
?S-5
34.0
40 %
24.8
0%
0.3
91-93
Pioneer
Design
2010 ? July 2012
27.9
21.0
27.0-32.0
23.0-28.0
98-99
were tested, such as feed concentrate type, autoclave throughput, oxygen overpressure, concentrate
pretreatment method, etc. In general, the dependencies observed in batch laboratory tests were
confirmed by the results of continuous pilot tests.
Gold recovery from Pioneer concentrate was 98 to 99 % provided there was adequate level of
sulfide oxidation (more than 98.5 %). Autoclave residence time was close to 30 minutes.
# 538 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Peter V. Zaytsev, Yakov M. Shneerson? Process Development for Refractory Gold Concentrates Treatment?
A brief description of the factors affecting the gold recovery after POX of Malomir is shown
below.
Organic carbon and chloride-ion. The combined negative effect of carbonaceous matter and
chloride on gold recovery from Malomir concentrates was observed and confirmed.
With the organic carbon content increase from 0.3 % to 1.7 %, gold recovery decreases by 8?10 %
with the chlorides amount in the autoclave slurry was 2-5 mg/dm3 (Fig. 3). Chloride concentration
increase leads to significant gold losses (Fig. 4). The mentioned negative effect is more pronounced for
higher carbonaceous materials.
Preliminary treatment of flotation concentrates. During the pilot tests, it was confirmed that
preliminary acid treatment and water washing of concentrates to remove dissolved chlorides improves
gold recovery. Graphically this effect is shown in Fig. 5.
Fig. 3. Gold recovery versus organic carbon content in the concentrate
Fig. 4. Gold recovery versus chloride concentration in autoclave slurry for the concentrates with various organic
carbon content
# 539 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Peter V. Zaytsev, Yakov M. Shneerson? Process Development for Refractory Gold Concentrates Treatment?
Fig. 5. Concentrate preliminary treatment effect on gold recovery
Fig. 6. Gold recovery versus retention time of low-carbonaceous Malomir concentrate (Corg = 0.6 %) in the
autoclave
It was observed that as the organic carbon content in Malomir concentrates increases, gold
recovery decreases; but also the positive effect of washing increases.
POX retention time. The very special effect of continuous oxidation in multi-compartment
autoclave was noted. The continuous process revealed the need to limit the retention time. Oxidation
duration should be sufficient to liberate most of the gold from sulfides and concurrently to prevent
?over-oxidation? of the material. Graphically gold recovery versus retention time of low-carbonaceous
Malomir concentrate is presented in Fig. 6.
It is seen that the curves strongly depend on the chloride content in the autoclave slurry. Gold
recovery gradually increases with increasing oxidation duration. Obviously, this is due to the continued
oxidation of sulphides and liberation of gold.
# 540 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Peter V. Zaytsev, Yakov M. Shneerson? Process Development for Refractory Gold Concentrates Treatment?
The maximum gold recovery in the low-chloride test (3?7 ppm of chloride ion) is 90 % when
retention time is 30 to 35 minutes. The further increase in retention time causes a gradual decrease of gold
recovery. With increasing retention time, the proportion of decomposed sulfides as well as the amount
of liberated gold also increases. This leads to subsequent elevated gold extraction to cyanide solution.
Simultaneously oxidizing conditions in the autoclave favor the increasing proportion of ferric iron in
solution also favoring conditions for reaction of gold complexation with chloride [3]. The gold complex is
then adsorbed on the organic carbon and becomes inaccessible to recovery by conventional RIL.
Gold recovery from autoclave residues subjected to oxidation with excessive amount of chloride
in the slurry (15 to 20 ppm of chloride ion) is lower. The maximum of gold recovery is also reached
when retention time is near 30 minutes, but it is not higher than 85 %. Further ?over-oxidation? of
14 concentrate leads to decrease of gold recovery. However, the negative effect of chloride is more
pronounced due to elevated chloride concentration.
Thus, the optimal residence time for continuous process is reached when the most of sulfides are
oxidized but no ?over-oxidation? is allowed.
POX slurry conditioning. At the end of the pressure oxidation process the ferric ion is a subject
to a hydrolysis forming basic ferric sulfate and mixed arsenates and sulfates. The hydrolysis reactions
occur under high temperature and could be reversed: the hydrolysis products are dissolved when slurry
is cooled. The general practice is to condition slurries under 90 to 100 °C [4].
Conditioning allows (a) decreasing solids yield due to basic iron sulfate decomposition and thus
(b) decreasing reactants consumption (mainly lime for neutralization of cake before RIL). Moreover,
as shown in Fig. 7, POX slurry conditioning leads to gold recovery increase.
The hydrolysis products formed lock gold and prevent it from being dissolved by cyanide. The
subsequent conditioning liberates the gold which is then leached by cyanide. The conditioning of POX
slurries consistently leads to gold recovery increase (2.0?4.5 %).
Flowsheet development
The laboratory and pilot tests data evaluation made by SRC Hydrometallurgy resulted in the
following recommendations for the Pokrovsky POX technology design:
Fig. 7. Conditioning effect on gold recovery
# 541 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Peter V. Zaytsev, Yakov M. Shneerson? Process Development for Refractory Gold Concentrates Treatment?
1. Malomir ore flotation flowsheet and reactants addition should be aimed to minimize organic
carbon recovery to sulfide concentrate. As a result of the testwork, organic carbon content was
reduced from 2.4 % to 0.5 %. This allows increasing gold recovery and significantly reducing
recovery sensitivity to the presence of chlorides during POX.
2. Malomir and Pioneer concentrates should be processed separately. This allows organizing a
relatively complex pretreatment stages (acidulation and counter-current decantation washing
to remove dissolved chlorides) necessary to achieve a high gold recovery from carbonaceous
materials to process Malomir only.
3. Only fresh chloride-free water should be fed to Malomir pretreatment and POX stages. The
entire amount of neutralized recycle solution (both from Malomir and Pioneer process lines),
containing significant amount of chloride, should be used to process Pioneer.
4. POX parameters should be the following: temperature 225 °C, oxygen overpressure 700 kPa.
Pilot tests results along with mathematical modeling of the oxidation process allowed calculation
of the effective volume of POX equipment.
5. POX slurry should be conditioned under 95°C for at least 2 hours to decompose hydrolysis
products (basic iron sulfate, mainly) and unlock gold for subsequent cyanidation.
A simplified block flowsheet is shown in Fig. 8.
Fig. 8. Pokrovskiy POX flowsheet
# 542 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Peter V. Zaytsev, Yakov M. Shneerson? Process Development for Refractory Gold Concentrates Treatment?
References
[1] ?????? ?.?., ?????? ?.?., ??????? ?.?. ? ??. // ????????? ????????????? ????????
«??????? ??????? ? 2012». ??????????: ?????, 2012. ?. 561-567.
[2] ??? ?.?., ?????????? ?.?., ???????? ?.?. // ????????? ????????????? ????????
«??????? ??????? ? 2012». ??????????: ?????, 2012. ?. 584-589.
[3] Qing Liu J., Nicol M.J. // Canadian Metallurgical Quarterly. 2002. P. 409-416.
[4] Fleming C.A. // SGS Minerals Services Technical Bulletin. 2009.
?????????? ?????????? ???????????
??????? ???????????????? ????????????
?? ??????????
??????????-????????????????????? ?????????
?.?. ??????, ?.?. ????????,
?.?. ?????, ?.?. ??????, ?.?. ??????????,
?.?. ???????, ?.?. ???????, ?.?. ????????
??? «????????????????»
??????, 197046, ?????-?????????, ????????? ??., 151, ??. 626
?????????? ?????????? ?????? ? ??????????? ??????????? ? ?????????? ????????????
???. ??????? ???????? ????? ?????? ? ?????: ???????? ???????????????? ??????????
?????? ? ??????????? ??????????. ??????? ?????????? ?????? ?????????? ????????????
????????????. ???????????? ?????????? ???????????? ? ???????????????? ?????????
????????? ???????????? ??? ?????????. ???????? ? ??????????? ??????? ??????????
????????????? ???????? ? ???????????? ? ?????????? ????? ??????? ? ?????? ????
????????? ????????? ??? ????????? ?? ?????????? ?????? ?? ??????????. ???????? ???????
??????????????? ?????? ????????? ?? ??????????? ?????????? ???????????? ?????????.
???????? ????????????? ??????? ????????? ??????? ??????????? ?????????? ?? ??????????
??????. ??????????? ? ????????????? ??????????????? ????? ???????? ?????????
??????????? ? ?????????? ???.
???????? ?????: ???????????? ????, ????????? ????????? ??? ?????????, ??????????
???????????? ?????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 544-551
~~~
??? 542.61:546.742
Octyl Amine Influence
on Redox Processes During Cobalt Extraction
with Bis(2,4,4-Trimethylpentyl)Dithiophosphinic Acid
Natalya A. Grigorieva*, Isaak Y. Fleitlikh,
Gennady L. Pashkov and Lidiya K. Nikiforova
Institute of Chemistry and Chemical Technology SB RAS
50/24 Akademgorodok, Krasnoyarsk, 660036, Russia
Received 14.02.2014, received in revised form 20.03.2014, accepted 07.08.2014
The redox processes proceeding in the organic phase at cobalt extraction with mixtures bis(2,4,4trimethylpentyl)dithiophosphinic acid (HR, trade mark CYANEX 301) and octyl amine (??) are studied.
It is shown, that reduction of Co (III) dithiophosphinate to Co (II) dithiophosphinate in the presence of
?? proceeds very quickly: for 10 minutes cobalt reduces on 94 %, whereas in other systems (??R3 and
??R3 + trioctyl amine, ???) for this period cobalt reduction practically was not observed).
Keywords: liquid-liquid extraction, Cobalt, Bis(2,4,4-trimethylpentyl)dithiophosphinic acid, octyl
amine, Redox process.
????????
? ????????? ????? ??????? ??????? ??? ???????????????? ???????? ???????????? ?????????? ??????? 301, ???????? ??????????? ???????? ???????? ???(2,4,4-??????????????)
??????????????? ??????? [1]. ??????? ????????? ? ??????? ?????????? ??????????? ????
???????????? ??? ??????????? ????????? ????????????? ?????????? ????????? ??? [2], ???????? ?????????? ???????? ? ?????? ? ????????? 301, ?????????? ?? ???????????? ?????????
??????? [3]. ?????????? ? ????????? ???????? ?? ????????? [4] ? ??????????? ????????? ?
????????? ??? ?? ???????? [5].
????? ???? ???? ???????? [6], ??? ? ???????? ????????????? ??(II) ?????? (?2 ???)
??????????? ????????? 301 ? ???????????? ???? ? ???????????? ????????? CoR 2 ??????????????? ????????????. ? ???????? ???????? ??????? ???????? ?????????? ?????????? ??????? ?? Co(III) ? ???????????? ????????? CoR 3 ?????????????? ????????????. ???????????? ????????????? Co(III) ? ?????????? ?????????????????? ?? ????????????? Co(II)
? ????????? ??????????????? ???????. ? ??????? ?? ?????????? ?? (II) ????????? ?? (III)
????? ???????, ? ???????????????? ??????? ?? ???????????? ???? ?????????? ???????????
?????? ??? ??????? ?????????? ??????????? ??????????? ??????????. ????? ?? ????????
?????????????? ????????? ???????? ? ???????????? ???? ? ??????????????? ???????? ??*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: natasha@icct.ru
# 544 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Natalya A. Grigorieva, Isaak Y. Fleitlikh? Octyl Amine Influence on Redox Processes During Cobalt Extraction?
??? ???? ???????? ? ???????????? ???? ????????? ??????????-???????? ???????. ????
????????, ??? ???????? ??????????????? ??????????? ??????? ???????? ?????????, ? ? ??????????? ????????????????????? ? ?????????????? ????????? ???????? ????????? ??????????????? [7].
?????????? ???????????? ? ???? ??????????? ???????????? ???????????? ??????? ?
???????????? ???????, ??? ??? ???????? ??????????-???????? ??????? ? ???????????? ????
????? ???????? ? ????????? ????????? ?????????????? ?????????? ???????? ?, ??????????????, ?????????????? ?????????????.
? ????????? ?????? ????????? ?????????? ???????????? ?? ???????? Red-Ox-?????????,
??????????? ??? ?????????? ???????? ?? ??????????? ????????? ???(2,4,4-??????????????)
??????????????? ???????? ? ??????????? ?????????? ????? ? ??????????, ? ????? ????????
?????????? ???????? ? ???? ???????.
????????????????? ?????
? ?????? ???????????? ???(2,4,4-??????????????)??????????????? ???????, ????????? ?? ???????? [8]. ????????? ??????? ???????? 98 % ????????? ????????. ?????????
???(2,4,4-??????????????)??????????????? ???????, R 2P(S)-S-S-(S)PR 2, (R-R) ???????? ??
???????? [9]. ? ???????? ??????????-???????? ??????? (???, L) ????????????: ????????????
(???), ???????????? ??????? ?7-?9 (???) ? ????????? (??).
???????? ?????????? ????????????? ?? ?????????? ???????? ? ?? ???????? Red-Ox????????? ? ???????????? ????????? ????????? ? [10].
??????????? ???????? ????????? ? ?????? ???? (?????????) ??????-????????????? ???????, ????? ?????????? ???????? ? ???????????? ???? ?????????? ?? ???????? ????? ??? ???????? ? ???????? ??????????? ? ?????? ???????? ????? ??????????. ????? ????, ????????????
Co (III) ? ?????????? ????????????? ?????????????????????, ?? ???????? ?????????? ????????? (? =455 ??; l = 1 ??), ? ???? ?????? ???????????? ??(II) ???????? ?? ???????? ????? ?????
????????????? ???????? ? Co (III).
?????????? ? ??????????
????? ?? ????? ????????????????? Red-Ox-????????? ??? ?????????? ???????? ????????
??????? ?????????????? ???????? (III) ?? ???????? (II). ????????? ????????? Red-Ox-???????
???????????? ????????? ????:
2??R3 ? 2??R 2 + R-R.
(1)
? ?????????? ???????? ??? ??????? ??????????????? ?????? ?????? ?????????, ?????? ??? ????????? ??????????? ?? ???????? ??????????? ?????????? ? ?????????? ????????
(III) ? ????????? ??????????? (???. 1, ??. 1). (?? ??? ??????? ???????? ???????? ??????????
????????? ??? ? = 455 ??, ??????? ????? ??????????????? ????????????? ???????????
????????.)
????? ????????????, ??? ?????????????? ???????? ? ?????????????? ??(III) ??????????
?? ???? ??????? ????? ?????? ? ???? ? ?????????, ? ??????????? ???????????? ??????????.
??? ???? ???????????? ??????? ???????? ???????? ?????? ??????.
# 545 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Natalya A. Grigorieva, Isaak Y. Fleitlikh? Octyl Amine Influence on Redox Processes During Cobalt Extraction?
1.0
?
0.8
0.6
1
0.4
2
0.2
3
0.0
0
4
8
12
16
20
24
?????,?
???. 1. ??????? ??????????-???????? ??????? ?? ?????????????? ??R 3 ? ???????. ?????? ??????????:
???????????? ????????-??R 3(???) = 0,0005 ?; ???????????? ??????? ? 0,1 ?; 1.??R 3; 2. ??R 3+ ???; 3.
??R 3 + ?? ?0?: 1-60; 2,3 ? 50
???????? ? ????????, ?????????? ????????????? ??(III), ??? ??????????? ?? ?????? ??
????????? ???????? ??????? ?????????????? (???. 1, ??. 2). ?????? ? ??????? ? ??? ?????????????? ???????? ?? ??????? ???????? ??????? ??????, ??? ? ?????????? ??????? (??. 1 ? 2).
??-????????, ??? ?????????????? ???????? ? ???????? ??R3 ? ???, ??? ? ? ??????????????
??????????????? ??(III), ????????? ??????? ???????? ?????? ????? ????? ????? ???????
? ?????. ? ?????????? ?????????????? ?????????? ?? (II), ????????, ?????? ????????????
?????????????? ??????? (???) ? ???????????? ?????????? ?????????. ????? ???????????
????????-????????? ?????????? ?????????????? ???????? (II) ? ??? ???????? ? [7]. ????????? ????????? ????????? Red-Ox-??????? ? ??????????? ??????? ????? ???????? ? ????????? ????:
2??R3 + nL ? 2 [??R 2? nL] + R-R,
(2)
??? L ? ??? ??? ??; n = 1,2.
? ??????? ?? ?????????? ?????? ???????? ? ??????????? ????????? ?????????? (???. 1,
??. 3) ???????? ? ????? ???????? ?????????????? ????????: ?? 10 ??? ??????? ???????????????? ?? 94 %, ????? ??? ? ?????? ????????? ???????? (??R3 ? ??R3+ ???) ?? ???? ?????? ?????????????? ?? ??????????? ?? ??????????? (< 2 %). ?????? ??????? ?????????? ? ????? ? ??
??????? ?????????? ?? ??????? ? ?? ??????????? (??R3) ?? ???????? (??-????????, ?????????????????? ????????? [??R 2?n??]). ????? ????, ?????????????? ??R3 ? ??????? ? ?? ????????
?????????? ?????????? ? ??????????? ?????????? ??? ??? ?????????? ?????? ????????????,
?= 30 °?, ?.?. ? ????????, ??????? ? ??????????. ????????? ??????? ????????? ?????????????? ??R3 ? ??????????? ??????????-???????? ???????, ? ??? ????? ? ? ??, ???????, ????????,
?????????????? ????????????, ????????? ?? ????? ????????? ??????.
?????????????? ??????????? ????????? ?????????? ??(II) ? ?? ???????? ?????????
??????????? ???????? ?????????? ?????????? ????????? ????????? CoR 2 ? ???????????
?????????? (???. 2).
# 546 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Natalya A. Grigorieva, Isaak Y. Fleitlikh? Octyl Amine Influence on Redox Processes During Cobalt Extraction?
2.0
?
2
3
1.5
4
1.0
1
5
0.5
0.0
500
550
600
650
700
750
800
850
????? ?????, ??
???. 2. ??????????? ??????? ?????????? ??????????? ?????????? ? ???(2,4,4-??????????????)
??????????????? ???????? ? ?????? ? ??????????? ?????????? (??). ?????? ??????????: 1. ??R2 -0,02 ?
(I); 2. (I) + 0,1 ? ??; 3. (I) + 0,3 ? ??; 4. (I) + 0,5 ? ??; 5. (I) + 0,8 ? ??
? ??????????? ???????? ?????????? ?????????? ???????? (II) ? ?????????? ???????
??????? ?????? ? ??????????? ? ??????? 620, 675, 735 ? 790 ??, ??????????? ? ??????????????? ???????????? CoR 2 (???. 2, ??. 1). ???????? ??????? ?? ???? ??????? ???????? ? ????????? ????? ????? ?????????? ? ??????????? ? ??????? 575, 600 ? 650 ??
? ???????? ?????????? ? ?????????? ????????????? ????? ????????? ????????????????
????????? CoR 2 (??. 2-5). ????????? ????????????? ????? ?????????????? ?????????? ?
????????? ? ???????? ?????????? ??????????????? ? ??????? ? ???????? ?????????? ?
??????????????? ?????? (?.?.) 5 ??? 6 [11]. ?? ??????? 2 ?????, ??? ? ??????????? ???????????? ??????? ????????????? ????? ??????????????? ?????????? ??????, ??? ??????????????? ? ??????????? ?????????? ?????????. ??-????????, ? ?????? ?????? ?????
????? ??????? ?? ?????????????-????????????? ??????????? ???? ??R 2?OA ? ??????????
?????????????? ???????????? ??R 2?2OA.
???????????? CoR 2 ??????????? ???????????? ????????? ???????? ???????????
???(2,4,4-??????????????)??????????????? ???????, (R-R), ?????????????? ? ???????????
??????????? ??????? 301. ??????? (2) ??????????? ????????? ??????? ?????? ? ???????????
??. ??? ????? ????? ?? ???. 3. ? ?????????? ?????????? ????????? ????????? ???????? ?? ??????????? (??. 1), ????????? ??????? ???????? ????????? ???????? ??????? (1) (??. 2). ????????? ??????????? ????????? ????????? ???????? (?????? 1 ? 3 ??????????? ???????).
????????????? ?????????? ?? ???????????? ?????????????? ???????? (II) ??????????? ????????? ??????????? ??????????? ????????????? ???? ??????? ??? ???????????, ??????????? ? ????? ??????? ????????? ??????????????? ???????, ?????????, ??? ????????
???? ????? [6, 10], ????? ?? ???????? ???????? ????????, ???????? ?? ???????? ?????????
????????, ???????? ??????????? HR ? ???????????? ????. ?????????? ?????? ????????? ?????
??? ????????????????? (???. 4).
# 547 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Natalya A. Grigorieva, Isaak Y. Fleitlikh? Octyl Amine Influence on Redox Processes During Cobalt Extraction?
1.2
?
2
1.0
0.8
0.6
0.4
3
0.2
1
0.0
0
4
8
12
16
20
24
?????, ?
???. 3. ??????????? ????????? CoR 2 ? ??????? ??????????? ? ?????????? ? ??????????? ?????????? ??
??????? ???????? ??????????. ???????: 1 ? 0,001 ? ??R 2 ; 2 ? 0,0005 ? ??R 2 + 0,02 ? R-R; 3 ? 0,001 ?
??R 2 + 0,02 ? R-R + 0,01 ? ??
2.0
?
2
1.6
1.2
0.8
0.4
3
1
0.0
0
1
2
3
4
5
?????, ?
???. 4. ??????????? ????????? CoR 2 ? ??????????? HR ? ?????????? ?? ??????? ???????? ??????????.
1. 0,001 ? ??R 2 ? ???????. 2. 0,001 ? ??R 2 + 0,2 ? HR+ 0,2 ? ?????????? ? ???????. 3. 0,001 ? ??R 2 + 0,2
? HR+ 0,2 ? ?????????? ? ??????; ?=22 °?
?? ??????? 4 ?????, ??? ??? ? ????????????? ???????????? (???????, ??.2), ??? ? ?
????????????? (??????, ??.3), ??????????? ???????? ????????? ????????. ???? ????????,
??? ? ?????? ????????? ???????? ???? ??????????? ??????, ??? ? ???????. ??? ?????? ?????????? ???????????, ????????? ????? ???? ????????, ??? ? ??????????? ????????????
?????? (???, ???) ????????? ???????? ? ?????????????? ????????? ???????????????
[7]. ????? ????? ???? ????????? ??????????. ????????????? ????????? ????????? ??(II)
? ??????????? ??????? (L) ??????????? ??????????????? L ? ??????????????? ????????
? ???????? ?????????????? ?????????? ??R 2. ?????? ?????????????? ???????? ? ??????? ?????????? ??????????? ?, ??????????????, ???????????? ????????? ????????, ?????? ? ???????????? ??????????? ????????? ??????? (?2) ? ???????? ??R 2 ?? ???? ??????????? ????????-????????? ?????????? ? ??? ????? ????? ???????????????? ?????????
????????.
# 548 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Natalya A. Grigorieva, Isaak Y. Fleitlikh? Octyl Amine Influence on Redox Processes During Cobalt Extraction?
1.5
lg DCo
1.0
0.5
1
2
0.0
-0.5
-1.0
-1.5
3
-2.0
-lg CH+
-2.5
-0.5
0.0
0.5
???.5. ??????????? ?????????? ???????? 0,4 ? ????????? ???(2,4,4-??????????????)- ???????????????
??????? ? ?????? ? ??????????? ??????? ?? ??????????? ?????? ????. 1 ? HR ??? ???????; 2 ? HR+??+15 %
????????; 3 ? HR+???. ?L = 0,4 ?; ?Co ? ???????? ???????? ? 0,05 ?; ?=5 ???
???? ?? ?????????? ??????, ???????????? ??? ?????????? ????????? ????????
? ???????? HR ? ????????????? ??????? ???????? ?????????????? ???? ??????????? ? ???????????? ?-??????????. ? ?? ??? ????? ???????, ??? ? ???, ? ?????????? ???? ??????????
????????? ????????.
??? ???????? ???????????? ?????????? ?? ?????????? ???????? ???(2,4,4??????????????)??????????????? ???????? ? ??????????? ??? ? ?? (???. 5). ?? ???????
????? (??. 2), ??? ? ??????????? ?? ??????????? ????????? ?????????? ???????? (?????????), ????? ??? ? ??? ????? ????? ??????? ????????????????? ?????? (??. 3). ????????, ?
?????? HR ? ??????????? ????????????? ???????? ?????????????? ??????????????? ?????????? (CoR 2) ? ????????, ????? ??? ? ???????? ? ??? ???????????? ??? ?????????? ???????? ?????????? ?????????? ??????????? ??-?? ?????????????? HR ? ??? (???). ?????????
???????? ?????????? ???????? ?? ?????? ????????? ??????? HR ? ??? ?? ???????????, ???
?????????? ????? ??????????? ??? ????????? ??.
? ?????????, ????????????? ?????? ??????? 301 ? ??????????? ?? ?????????????? ????????? ??-?? ??????????? ????????????????????? ???????? ? ??????? ? ???????????? ????
??? ?????????? ???????? ? ????????? ? 0,015 ????/?. ??????? ????????, ??? ????? ??????????
? ???????? ??????? ??????????????? ? ?????? ????????? ?????: ?????????, Primene 81-JMT,
? ????? ?-????????. ??? ??????????? ? ???? ????????? ?????? (????????? ????????, ??????????? ???????, ??????????? ?? ?????? ????????????) ????? ?????????????? ????????? ????????????.
? ????????? ????? ????? ???????, ??? ?? ????????????? ?????????????? ?????? ?????????? ???????????? ??????? ???????????? ????? HR ? ??? ??? ? ????? ?????? ????????# 549 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Natalya A. Grigorieva, Isaak Y. Fleitlikh? Octyl Amine Influence on Redox Processes During Cobalt Extraction?
??? ?????????? ???????? ? ??????, ??? ? (????????) ?? ???????????? [12]. ????????? ??????????? ?? ?????? ???????? ??????? ???????? ???? ???????.
?????? ??????????
[1] CYANEX® 301, Extractant, 2007, Technical Brochure, CYTEC INDUSTRIES INC., West
Paterson, New jersey. 14 p.
[2] Mihaylov I. et al. CIM Bulletin, 2000. V. 93. ? 1041. P. 124-130.
[3] Mihaylov I. et al // Hydrometallurgy of nickel and cobalt 2009. Proceedins of the 39th Annual
Hydrometallurgy Meeting conjuction with the 48th Conference of Metallurgists of CIM (August 23-26,
2009), Sudbury, Ontario, Canada. P. 383-391.
[4] Vorde I.V., Pinoy L., Courtijn E., Verpoort F. // Hydrometallurgy, 2005. V. 78. N. 1-2. P. 92106.
[5] Ocana N., Alguacil F.J. // J. of Chemical Technology and Biotechnology 1999. V. 73. ? 3.
?. 211-216.
[6] ?????????? ?.?., ???????? ?.?., ??????? ?.?., ?????? ?.?. // ??????? ???????? ?????????? ?????????????? ????????? «??????? ???????-2012».; ?????? III; ???????????? ???????, ?????? ? ?????????? ????????. ??????????, ??????; 5-7 ????????, 2012. ?. 143-144.
[7] ???????? ?.?., ?????????? ?.?., ?????? ?.?. // ??. ???????? ???????? ?????????????? ????????? «??????? ???????-2011». ??????????, 2011. ?????? IV. ?. 302-303.
[8] Zhu Y., Chen J., Jiao R. // Solvent Extraction and Ion Exchange. 1996, V.14, Issue 1.
?. 61-68.
[9] ??????? ?.?., ???????? ?.?., ????????? ?.?. // ???. 1998. ?. 43. ? 5. ?. 877?880.
[10] Fleitlikh I.Yu., Grigorieva N.A., Kuz?min V.I., Pashkov G.L. // Hydrometallurgy. 2012. ? 129130. ?. 43-49.
[11] ????????? ?.?., ???????? ?.?. // ???. 1979. ?. 26. ???. 11. ?. 3064-3069.
[12] Fleitlikh I.Yu., Pashkov G.L., Grigorieva N.A et al. // Solvent Extraction and Ion Exchange.
2011. 29 (5-6). P. 782-800.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Natalya A. Grigorieva, Isaak Y. Fleitlikh? Octyl Amine Influence on Redox Processes During Cobalt Extraction?
??????? ??????????
?? ????????????-????????????????? ????????
??? ?????????? ???????? ???(2,4,4-??????????????)
??????????????? ????????
?.?. ??????????, ?.?. ????????,
?.?. ??????, ?.?. ??????????
???????? ????? ? ?????????? ?????????? ?? ???
??????, 660036, ??????????, ?????????????, 50, ???. 24
??????? ????????????-????????????????? ????????, ??????????? ? ???????????? ????
??? ?????????? ???????? ??????? ???(2,4,4-??????????????)??????????????? ???????
(HR) ? ?????????? (??). ????????, ??? ?????????????? ?????????????? ????????
(III) ?? ?????????????? ???????? (II) ? ??????????? ?? ???? ????? ??????: ?? 10 ???
??????? ????????????????? ?? 94 %, ????? ??? ? ?????? ????????? ???????? (??R3 ? ??R3+
????????????) ?? ???? ?????? ?????????????? ?? (III) ??????????? ?? ??????????? (< 2 %).
???????????? CoR2 ??????????? ???????????? ????????? ???????? ??????????? ???(2,4,4??????????????)??????????????? ???????, (R-R), ?????????????? ? ???????????
???????????. ????????, ??? ????????? ??????????????? ??????? ???????????? ?????????
?????????????? ???????? (II) ? ??????????? ??.
? ?????????????? ??????????? ???????? ?????????? ?????????? ???????? ???????????
????????? ?????????? ??(II) ? ??, ???? CoR2·n??, ??? n = 1, 2. ?????????? ?? ? ???????????
?? ???? ??????? ?????????? ? ????: HR+????????? > HR >> HR+ ????????????.
???????? ?????: ?????????? ??????????, ???????, ???(2,4,4-??????????????) ??????????????? ???????, ?????????, ????????????-????????????????? ???????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 552-560
~~~
??? 669.713.7
Electrical Resistance Preheating
of High-Amperage Cells
Ilya I. Puzanov*,
Andrey V. Zavadyak, Yaroslav A. Tretiyakov,
Mikhail M. Morozov, Anatoliy A. Gubin,
Vitaliy V. Platonov and Aleksandr V. Darkin
RUSAL ETC Ltd, RUSAL,
37/1 Pogranichnikov Str., Krasnoyarsk, 660111, Russia
Received 12.03.2014, received in revised form 07.06.2014, accepted 11.08.2014
At present, there is no single opinion on which cell preheating method is best. In most cases, such a
method (that is to be chosen for a smelter) is chosen based on a number of objective and subjective
factors. It is often when a method is chosen that power expenses (either electricity or power generated
from fuel combustion) for such a method are not taken into account. However, it can play a crucial role
for different regions and influence the production cost of Al. This paper discusses the results of testing
the method of electrical preheating in a pilot cell area (RA-400 cells) at OJSC RUSAL Sayanogorsk.
Keywords: RA-400 high-amperage cell, electrical preheating, technology development and technology
management, experiment performance.
????? ??????? ? ???? ???????????? ??? ?????? ????????????? ??????? ?? ?????? ????????, ????? ??? ???????? ???????? ??????, ??? ??????? ?????, ??????????? ???????????
??????? ?? ???????????????? ????????.
??????????????, ????? ?????? ?????? ? ??? ???????????? ?????? ???????? ?? ???????
??????? ??????????? ????????????? ??????? ??? ?????????? ???????? ?? ?????????? ????????????? ? ?????????, ??????? ? ????????????????? ? ??????????? ?????? ?????????? ????????? ?????? ? ?????????? ?????? ????????????? ? ??????????? ??????.
? ????? ?? ??????????? ??????????????? ???????????? ???? ?? ????????-????? ???????? ??????????? ??? ???????, ????? ??????????? ??????? ????????? ????????? ????????
????????? ?? ?????? ??????????????. ?????? ?????????????? ????????? ????????? ?? ????
???????? ???????? ?? ???? ????????? ???????????? ????????. ??? ???? ???????? ????????? ?? ????????? ????????????? ????????.
?? ?????????? ???? ????????? ?????? ??????????????, ???????????? ????? ???? ???????????? ?????????? ????????????? ? ????? ? ???????? ?????? (??? ???????? ????? ??????
?????????????) ? ????? ?? ?????????????? ???????????? (?????????????? ????????? ??? ??????) ??? ???????????? ???????????? ??????? ?????????????? ???? ??? 400.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: IliyaPuzanov@rusal.com
# 552 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Ilya I. Puzanov, Andrey V. Zavadyak? Electrical Resistance Preheating of High-Amperage Cells
???? ????????????? ?????? ?????? ?????????????? ? ??????? ????? ????????? ????????????? ??? ???????????????, ?? ?? ???? ?????? ? ????? ?????????? ????? 25 % ?? ????? ????
??????? ??????? ??????????????, ????????? ?? ???? ?????? ?????????????.
???????? ????? ????????, ??? ?? ???????? ?????????? ?????? ?????????????? ??????????????? ?????? ??????????? ????? ????????????? ???????????, ??? ?????????? ????????????? ??????? ? ?????????? ????? ?????? ??????????????, ???, ? ???? ???????, ?????? ????? ?
???????? ????????????? ??????????? ?????????.
????? ?????? ???? ?????? ???????? ?????????? ????????????? ? ?????????, ??????? ?
?????????????????, ??? ??????????? ??????????, ???????????? ? ?????? ????? ?? ???????????? ???? ? ?????????? ??????? ???????????.
????? ?????????? ? ????????? ????????????? ????? ??????:
? ???????? «??????» ??????? ?? ??????????? ?????? ?????????????, ??????? ? ??????????? ??????? ?????, ? ????????? ??????, ??????? ? ???????????????? ???????????? ?????????????, ? ??????????? ??????????? ??? (???????? ????????? ??????????)
????????????? ??????????;
? ??????????? ??? ????????? «???????????» ?????, ???????????????? ? ??????????
??????? ??????????? ??? ??? ????????? ???????????????? ????????????, ????????
????? ????????? ?? ?????? ????? ??????????? ???????;
? ?? ???? ???????????? ???????? ???? ????? ????????? ? ???????? ???????????? ???????? ???? ??????? ????????? ???????? ??????????? ???????? ??? ???????????? ???????? ?? ?????? ?????? ??? ? ????????????, ??? ? ? ?????????????? ???????????;
? ??????? ? ??????????? ????? ??????? ????? ? ????? ?????????? ???????????? ???????????? ? ???????????? ???????? ????? ?????? ? ??????????? ???????????? ?????????? ? ???????????? ????;
? ???????? ? ???????? ?????????, ???????????? ? ???????? ?????????? ? ?????? ??????? ????????? ? ???????????? ? ????? ???????????? ??????????.
? ??????????? ???????? ?????????? ????????? ???????????? ??????? ? ?????????? ????????????? ??????? ?????? ??????????????, ????????? ?? ????????? ?????????? ????? ?
??????????? ?????? ????????? ??????????.
??? ????????? ?? ???:
1. ????? ?? ???? ????????? ????? ??? ??????????? ?????????????? ???? ????? ???? ?????????? ??? ???????? ??????:
? ? ??????????? ?? ??????????? ????? ???????? ?????? (?????????? ??????? 100 %, ?????????? ??????? ?? ????? 30 %, ???????? ??????? ?????) ?????????? ?????? ?????
????????? ???????????;
? ? ??????????? ? ???????? ?????????, ?????????? ?????, ?????, ??? ?????? ?????? ?
??????????? ???????.
2. ????? ? ??????????? ? ???????? ???????? ????? ????????????? ?????, ????????????
? ?????????? ???????? ??????????????? ??????? (????????? ???, ?????, ??????????).
?????? ?? ????????????????? ???????? ????? ??? ????? ??????????? ? ???????????.
???????? ?? ??? ???? ???????? ?????? ?????????? ????????????? ? ??????????? ??????????? ????????, ??????????? ????????????, ? ????? ?????? ?? ????????? ????????????
# 553 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Ilya I. Puzanov, Andrey V. Zavadyak? Electrical Resistance Preheating of High-Amperage Cells
???????????, ??????? ???????? ????????? ??????? ?? ???????????? ???????????? ???????
?????????????? ????????????? ??????????? ???????????????? ????????.
??? ??????:
? ??????????? ???????????? ??? ??????????????, ???????????? ?? ?????????? ???
???????? ??????, ? 100%-??? ?????????? ??????? ? ??????? ??????? ??????. ?? ????
??????? ????????? ? ?????????? ????????????? ?????????????? ???????????? ??????????? ??????? ? ?????????????? ????? ?????????? ???????? ?????? ? ?????? ?????????? ???????? ?????? ? ???????;
? ???????? ???????? ??????? ??????? ??????, ? ? ????????? ?????????? ? ??? ???????, ????????, ?? 30 %, ??? ?????????? ??? ??????????? ??????? ???????? ??????? ??????
??????????? ?????????? ??? ?????? ?????????????? ????????????? ?????? ? ???? ????? ??????????? ???????? ??????? ??????????? ?????? ? ??????????? ????? ????????? ????????? ??????? ??????? ?????????.
????????????? ???????? ??????, ??????? ? ???????????? ?????? ????? ?????????? ??
??????? ????????????? ???????????? ??????, ??????? ?? 1995 ?. ??????????? ????? ?????????????? ?? ???? ????????? ????????? ? ????????? ????? ????????????. ?? ?????? ??????????? ????????????? ?????? ???? ????????? ????? ?????????????? ? ?-175, ?-190 ? ?-255.
??? ?????????? ????????????? ???? ?-175 ? ?????????, ??????? ? ?????????????????,
???? ?????????? ????????? ????????????? ????????? ??? ??????. ??? ?????? ????? ?????????????? ???? ?-255 ? ?-190 ??? ?????? ?????? ?????? ?? ???????? ??????. ???? ???????
??????? ??????????? ? ???, ??? ?? ?????? ????????????? ??????????? ???? ?? ???????? ??????
??? ???????? ???????????????????? ? ?? ???? ????????? ???????? ????? ????????????? ?????? ???????????. ????????????? ????????? ????? ?????? ? ??????? ???????? ??????????????
?????? ??? ?????? ??????? ???????.
? ????? ??????????? ???????? ? ? ???????? ??????? ????????????, ??????????? ???
?????? ?? ???????? ??????, ??????????????. ???? ????????? ??????????? ?????? ?????? ???
????????? ???? ?????? ? ??????? ????????.
??? ??????? ??????? ?? ??????? ?????????? ??????? ???? ??????????????? ? ????????? ?????-???????? ????????? ????????, ????????? ??????? ? ???? ?????????????? ?? ????
???????????? ?????????? ? ??????????? ???????????.
????????? ?????????? ??? ??????????? ?????? ??? ?????????? ??????? ?????? ?????????? ??????? ???????? ? ?????????????????. ? ????? ? ??????????? ????????? ??????????
? ???????? ?????????? ?? ??????? ???? ??????? ??????????? ???????????? ??????????? ?
?????? ? ?????? ?????.
??? ????????????? ????????, ??? ?????????? ??????? ????????????? ?????? ??????????? ???????? ?????? ????????????, ?????? ??????? ???? ???????? ??????? ????? ??????????????, ???????????????????? ?? ?????? ? ????? ??????????????.
? ???????? ??????? ? ? ????????? ?????????????????? ?????? ?????????????? ??????
?? ???????????? ??????????? ?????? ???????? ???????? ? ?????????? ????? ???????, ???
«Hotwork», ??????????????? ??? ????? ? ???????????? ????????????? ?????????????????
????????????. ?????? ??????? ???????????? ????? ???????? ??????????? ??????? ??????????, ??????? ????????????? ? ??????? ???????? ???????. ??????? ?????? «Hotwork» ????# 554 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Ilya I. Puzanov, Andrey V. Zavadyak? Electrical Resistance Preheating of High-Amperage Cells
???? ?????? ?????? ? ????????????? ? ???????????? ??????? ????? ???????? ?????????????
????????. ?? ?????? ???????????????? ?????? ????????????? ????????? ????????????? ????????? ?? ?????????, ??? ????? ??????????? ??????????? ??????? ????????????? ??????? ??
????????. ???????? ?????? ?????? ???????????? ?????? ????????? ???????? ??????????? ??
?????? ? ????????? ???? ? ?????????????? ?????????? ???? ?? ????? 50 ??.
?????????? ??? ?????????? ???? ?????? ?????? ???????? ??????? ??????????? ?? ?????????? ????? ???????? ??????, ?????????? ??????????? ??????????? ? ?? ???????? ? ???????
?????????? ????? ?? ???? ??????????? ???????????.
?? ?????? ?????????? ????????? ????? ????????? ? ??????????-??????????? ????????,
?????????? ??????????? ????????????? ????? (???).
? ?????? ??????????? ????? ????????? ??????????? ??????????????? ??????????
??????????-????????????? ????????? ??? ?????? ????????? ??????????? ?? ??????????? ?????? ? ??? ??????????? ??????? ?????????? ?????????????? ????? ????????? ?????????????
? ??????? ??????? ???????????.
? ????????? ?????? ??? ????????????? ????????????? ???????????? ?????? ??????????
??? ?????? ????????????? ?????????. ? ??????? ????????? ?????????? ?????????????? ??300 ?? ????????? ??????????? ??????, ?? ??????? ? ?? ??????????? ???? ?????????? ???????
?????? ? ????? ???????? ????????? ???????:
???????? ???????? ??????? ? ?????? ??????? ? ?????????????? ???????????? ? ??????? ?
????? ??? ?????? ????????????? ????????? ? ???????? ????????? ?????? ? ??????? ??????????? ? ????????? ????????????? ? ???? ??? ?????? ???????? ????? ? ?????????? ????????????? ? ??????? ???????????????? ??????????.
?????? ?? ?????, ??????????? ??? ????????????? ?????? ?????????????? ???? ??-400,
????????, ??? ??? ????? ????????? ???????? ????????? ? ?????????? ??????? ???????? ?????????? ????? ?????? ?????????? ??????????? ? 72 ?? 96 ?. ? ????? ?????? ????????? ???
????? ??????????? ??????? ??? ??????? ???????? ?????????, ?? ?????? ??????????????
??????, ? ??????????????, ? ??????? ? ??? ???????????????? ??????? ? ????? ?????? ??????????, ??? ????? ?? ??????????? ? ??? ???????????? ??????????? ? ???????? ? ????????
?????????????.
?? ????? ??????????? ???????????? ???? ??????????? ?????????? ?????? ????? ?? ??????
???? ????, ?? ????? ??????? ?? ???????????? ??? ??????????? ???????????? ??? ??????, ??????? ???????????? ??????? (??????? ?????? ? ????), ??????????? ?????????????? ? ????????
? ????????????? ?????? ?? ???? ????? ??????? ??????? ????????, ??????? ?? ?????????????
????? ?? ???? ?????? ?? ???????? ??????????????? ???????.
?????????? ???? ??? ????? ? ???????????? ?????????????? ???????? ??????? ?????????????? ??-400 ???????, ??? ?????????? ????????????? ????? ? ???????? ?????? ???? ??
????????????? ??????????? ?????????? (??? ?????????? ?????????? ????????? ??????????? ?????? ????????????????? ?????? ??????????? ???????????). ?????? ???? ????????
???????????? ??? ???????? ????? ? ???????????? ??????????? ???????????? ??????, ?.?.
???????? ????????????? ?????????? ????? ?????? (????????? ???????, ??????) ???? ??????? ? ???? ????? ????????????? ?????????????? ??????????? ?????????? ?????. ?????
???????? ???????? ??? ??????????? ?????????????? ?? ?????????? ??????????? ??????
# 555 #
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Ilya I. Puzanov, Andrey V. Zavadyak? Electrical Resistance Preheating of High-Amperage Cells
? ?????? ??? ???????? ??? ?????????? ??????? ???????? ?? ????????????? ?????? ???????? ????????? ????????????? ??-400 ? ???? ??? ?????????? ??????????????? ???????? ??
?????.
???????? ??????????? ????????, ??????????? ????????? ????????????????? ??????????, ?????? ?????? ?????????????? ?????? ?????????????? ?? ????? ????????????? ?????.
?????????? ?????????? ?????????????? ?????? ????????:
? ?????????????? ???????? ???????????? ? ???? ??? ?????????? ??? ???????? ?????????????? ???? ?????;
? ????????? ??????? ?? ????????????? ???????????? ??? ?????? ? ??????? (?????????? ????????????? ??????? ??? ???????? ??????? ?????? ? ????????????? ???????? ??
?????????? ?????);
? ??????? ????? ?????? ??????????????.
??? ????????? ??????????? ??????? ?? ?????????? ?????????????? ?????? ? ??????
??????? ????? «???????? ?????????? ??-400» ? 2012 ?. ????????? ????????? ?? ???? ?????????????? ???????? ??????? ??-400 ??? «????? ??????????».
???????????????? ????????
?? ?????? ??????? ??????????? «??????? ???? ? ??????» (??) ??????? ??????????????
???????, ?????????????? ?? ???. 1. ??????????? ???????????? ???????????? ? ?? ????:
? ??????? ?????????, ??????? ? ?????? ??????? ???????????? ????????? ????: ???
???????-??????? ?? ????? 0,6 ?/??2; ??? ?????? ??????????? ?? ????? 1,2 ?/??2;
? ?????????? ? ????????????????? ??????? ??????? ????????????????? ?????? ? ?????????? ??;
? ??????? ? ??? ?????? ???? ?????????????, ????? ????? ???????????, ???????????
???????????? ???????? ???????? ??? ???????????? ??????? ??????.
??? ?????????? ??????????? ????????? ??????????? ?????? ? 39 ?????? (?????????
????? ?????? ?????? ? ???? ??????) ???????????? ????????????:
? ????????? ????? ???-?-3.1-?-1250/2000/3000;
? ?????? ????? ???????? ?? ???????? ???-???-8;
? ?? «??????? ??????????? ??????????? ??????».
??? ?????????? ???????? ????????????? ????? ? ??????????-???????????????? ????????? ????????? ?????????? ??? ????????????? ?????? ????????????? ??-400 ???????????
??? «??????-??????????? ????? ?????» ??????? ???????????? ?????????????? ????????????? ???????? ? ?????????? ?????? ????????? ??????????????.
?? ????????? ?????????? ??????? ??????????? ????????? ????????? ??????????????
????????????? ???????? ?????? ?????????????. ??? ????????????? ???????????? ????????????? ? ????????????? ????. ????? ?????????????? ??????????? ? ???????? ?????????
??????? ? ??????????? ?????? ANSYS 14.5 ??????? ?????? ј ????? ????????????? ??-400. ??
??????????? ???????? ?? ????????? ?????? ????????? ???????? ? ??????????? ????????? ????????? ??????????? ???? ??????????? ?????????, ????????????? ??????.
?? ????????? ??????????? ????????? ? ???????? ??????????, ??? ??????????? ??????????, ??? ??????? ??????????? ??????? ????????? ?????? ????????????? ??-400 ??? ?????# 556 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Ilya I. Puzanov, Andrey V. Zavadyak? Electrical Resistance Preheating of High-Amperage Cells
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????? ??????-????????? ?? ?????? ???? ????, ???????? ?????????? ???????? ????? ??-99
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????????????? ????? ????????????? ? 018
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? ????????? ?? 395 ?? (????).
?? ???? ?????? ????????? ???? ???? ???????? ?????????? ??????? ?? ?????????????
?? ???????????. ????????? ???????????? ?????????? ????????? 2,626 ? (??????? ?????????
?????????? ??? ??????????). ????? 15 ??? ????? ??????????? ????????????? ?? ????? ????????? ?????????? ???? ?????????? ?? ??????? ???????.
??????? ?????????? ?? ?????? ?????? ? ?????? ????????? ??????????, ?????????? ?
??????????? (?????????? ??????), ????????? 1,9 ?, ?? ???? ??????? ?????? ?????????? ?????????. ?????? ?????????????? ?? ?????? ?????? ????????????? ???????? ~ 44 ???Ч?.
# 557 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Ilya I. Puzanov, Andrey V. Zavadyak? Electrical Resistance Preheating of High-Amperage Cells
?? ???? ?????? ?????? ??? ?????????? ??????????? ???????? ?????? ????????? 12 ?????? (???? ??? ? ??? ????? ????????????) ? ???????????? ? ?????????? ?????????? ??????.
????????? ?????????? ?????????? ?????? ????????:
? ????????? ??????? ???????? ?? ????? (????? 20 ??);
? ??????? ???????? ??????????? ????? ????????? ??????????? ??? ????????? ???????? (??????? ??????????? ????? ????????? ??????????? ????? 100 °?).
?? ??????? 1 ???????????? ????????????? ???? ?????? ????? ?????? ?????????????
? 018, ????? 58 ? ????? ?????? ??????.
?? ??????? 1 ?????, ??? ??????????? ??? ?????? ? ?????????? ??????????? ??????
????? 790 °? (????? 10 ? 11-? ???????, ?????????? ? ?????? 3-?? ??????, ????? 16 ? 17-?
???????), ~ 33 % ??????????? ?????? ??? ??????? ???????? ??????? ?? ??????????? 700 °?
? ?????. ???????????? ??????????? ????????? 912 °? (?????????, ????????????? ????? 10
? 11-? ???????), ??????????? ??????????? ??? ????? ???????? ???????? 506 °? (?????????,
????????????? ????? 14 ? 15-? ???????). ???????? ????? 120 °? ??????????? ????? 15 ???????????.
???? ????????????? ? 018 ??????????? 13.09.2012 (?????? ??????? ??????? ????? ??????????? ????????? ??????? ?????). ???? ???????????? ?????????????????? ?????????? ??????????????? ???????? ??? ?????:
? ???????? ??????? ??????, ?????????? ?????? ?????????;
? ??????? ???????????, ?????? ???????? ???????;
? ?????????? ????????????? ? ??????????? ???????????????? ????.
????? ??????? ???????? ??????? ?????? ??? ??????????? ???????? ???????? ???? ?
?????? ?????????? ?????????? 1,63 ?, ????? ? 1,72 ?. ???????????? ??????? ?????? ?????
??????? ??????????? ????? ~ 26 ?.
????? ??????? ??????????? ? ????????????? ????????? ????? ? ????????????? ?????
??? ????? ???????? ???? (? ?????? ?????????? ??????? ? «???????» ?????? ???? ?? ?????
20 ??.). ? ??????? ??????????? ????? ?? ????????????? ????????? ?????????? ??????????????? ??????? ?? ???? ??????. ??????? ??????? ?????????? ????????? ??-?? ?????????
?????????? ? ?????? ?????????? ??????????? ????????? (?????????? ?????????? ???????? ?????????? ????? ??????????????? ??????? ????? ? ???????? ??? ? ??????????? ????? ?
?????? ????????).
????????????? ????? ????????????? ? 021
???????? ????????????? ???????????? ??????? ???????????? ??????? ????????????
? 021 ????????? ?? ????????????? ????? 02.10.2012, ????? ????? ????????????????? ?????????????? ?????? ????????? 72 ? 50 ???.
?????? ???????????????? ????????????, ??????? ???????? ??????? ????????????
??? ??, ??? ? ?? ????????????? ? 018. ?? ????????? ??????????? ????? ?????? ????????????? ? 018 ????????????? ???????????? ?????????????? ?????? ????????????? ? 021
???????:
? ?????????? ????????? ?????????? «???????». ?????????? ???????? ??????????? ??
?????? ? ??????? ?????????? ?????;
# 558 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Ilya I. Puzanov, Andrey V. Zavadyak? Electrical Resistance Preheating of High-Amperage Cells
? ??????????? ????????????? ?? ????? ?? ???? ???? 200 ?? ? ??????????? ???????????????? ??????? ???????????? (???????????? ? ??????? ?????????-???????? ? ???????? ???????);
? ?????????? ????? ?????????? ?????? ?? 72 ?.
???? ????????????? ? 021 ??????????? 05.10.2012. ????? ??????? ???????? ???????
?????? ??? ??????????? ???????? ???????? ???? ? ?????? ?????????? ?????????? 1,6 ?, ????? ? 1,72 ?. ???????????? ??????? ?????? ????? ??????? ??????????? ~ 18 ?.
?? ????? ??????? ??????????? ? ??????? ???????? ??????? ????????? ?????????? ?????? ? 7, 8, 9, 10 (??????? ????? ??????????? ?? ??????? ?????). ???????? ?????????? ??????
???????? ?? ????????????? ????????, ? ??? ??????????????? ???????? ?????? ? ?????? ????????? ??????. ? ??????? ????????? ????? ????? ????? ?????????? ?????????? ????????????????? ?? ??????, ?????? ?????? ??? ???????????? ???????? ? ???????? ???????? ??????????? ????????? ? ??????? ????? ? ?????? ????????? ???????? ???????, ????????? ? ????
?? ?????? ?? ????????????? ? 018. ?????? ????? ??????? ??????? ?? ????????????? ????????
???-??????????????. ???????? ???????? ???-?????????????? ??????? ????????????? ????????????? ???? ?? ?????? ??-?? ?????????? ????? ? ??????? ???????? ? ?????? ?????? (?????? ? ?????????? ??????? ?? ?????, ??????? ??????? ?????????? ????? ?????? ????? ??????,
???????? ?? ????????? ?? ?????? ??????? ?????? ?? ???????? ??????). ????? ?????????
???? ?????? ? ???????? ? ??????? ?????? ???-?????????????? ????????????.
??????
?????????? ????????????? ????? ?????????????? ??-400 ?? ?????????? ????????? ???
?????????? ?????? ????????? ?? ???? ???? 395 ?? ????????. ??????? ???????? ???????????
?????????? ?????? ? ???????? ??????-????? ?? 2013 ?. ????????, ??? ?????????? ?????????????? ?????? ?? ~ 5 % ???????, ??? ?????????? ?????????????? ??????.
??? ????????? ????????????? ????????????? ???? ?? ?????? ? ???????? ??????? ????????????? ??????????? ??????????? ?????? ?????????? ?????????? ?????????? ??????????
«??????? ???? ? ??????», ??????? ???????????? ?? ????????? ??????????? ??????? ??????
????? ?????????? ? ?????????? ???? ?????????????. ? ?????? ?????? ???? «?????????????»
??? ????????? ???????????? ???? ????? ?????????? ???????????? ???????? ???????? ?? ?????????? ??????, ??? ???????? ????????? ?????????? ????????? ???? ?? ???????? ?????? ?
??????????? ??????, ? ??????, ? ??????????? ????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Ilya I. Puzanov, Andrey V. Zavadyak? Electrical Resistance Preheating of High-Amperage Cells
????? ?????????????? ??????????????
??? ?????? ????????????????????
?.?. ???????, ?.?. ???????,
?.?. ?????????, ?.?. ???????,
?.?. ?????, ?.?. ????????, ?.? ??????
??? «????? ???»
??????, 660111, ??????????, ??. ?????????????, 37, ???. 1
?? ??????? ?????? ??? ??????? ?????? ? ???, ????? ?????? ?????? ?????. ? ???????????
??????? ????? ???? ??? ????? ??????? ?? ?????? ??????????? ?????? ????????????
????? ??????????? ? ???????????? ????????. ???????? ??? ?????? ??????? ?????? ??
??????????? ??????? ?? ????????????? ??????? ?? ???? ??????? (????????????? ???
?? ???????? ?????????????? ?????????? ????????? ????? ???????), ??? ????? ?????
???????????? ???????? ??? ????????? ???????? ? ?????? ?? ????????????? ????????????
????????. ? ?????? ?????? ???????????? ?????????? ????????? ?????????????? ??????
?????????????? ???????? ??????? ??-400 ??? «????? ??????????».
???????? ?????: ?????????????? ???????????? ??-400, ????????????? ?????, ?????????? ?
?????????? ??????????, ?????????? ????????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 561-569
~~~
??? 532:537.311.32; 532:541.135.1
Electrolytes Based on the Potassium Kriolit
for Low-Temperature Obtaining of Aluminium
Olga Yu. Tkacheva*, Alexander A. Red`kin,
Alexander. A. Dedyukhin, Alexey P. Apisarov,
Pavel E. Tin`gaev and Yurii P. Zaykov
Institute of High Temperature Electrochemistry, UB RAS
20 Akademicheskaya Str., Yekaterinburg, 620990, Russia
Received 21.02.2014, received in revised form 14.03.2014, accepted 08.08.2014
The general regression equations basic physical and chemical properties (liquidus temperature,
conductivity, solubility of alumina) mixed potassium-sodium cryolite melts with cryolite ratio 1,31,5 with additives LiF and CaF2 are investigated and described. Based on the identified patterns the
electrolyte composition, promising for low-temperature aluminum electrowinning are defined: KFAlF3 and KF-NaF-AlF3, containing 12-15 wt.% NaF, with cryolite ratio of 1,3-1,5 and the liquidus
temperature below 800 C. The solubility of alumina in electrolytes such is not less than 4.5 wt.% in
the temperature range of 700-800 C. In order to increase the electrical conductivity supplements
LiF in an amount of not more than 3 wt.% are recommended. CaF2 in the presence of the electrolyte
is not desirable.
Keywords: potassium cryolite, potassium-sodium cryolite, the electrical conductivity, liquidus
temperature, solubility of aluminum oxide, calcium fluoride, low-temperature electrolysis.
? ????????? ????? ??????????? ???? ????????? ???????? ???????? ??????? ????????, ??????? ????? ??? ?? 100 ??? ?? ????????? ?????????????? ?????????. ?????
??????????? ? ????????????????? ?????????? ?????????, ????????????? ? ?????????
??????????? ???????? (Na 3AlF6 ? ????????? AlF3, CaF 2 ? ??.), ??? ??????????? ?????
950 °?. ??????? ?????????????? ???????? ???????? ?????? ? ???????? ? ?????????
????????????? ?????????? ??????? ????? (??, ??2 ? ???????), ????????? ??????????
??????. ???????????? ??????????? ???????? ???-????? ???????? ??? ?????? ??????????? ???????? ?????? ?? ????????????? ???????? ?????, ??????? ?? ???????????????
? ???????????? ? ???????????? ?? ??? ??????????. ????????????? ????? ?????? (?????????????, ????????????, ?????????) ? ????????? ?? ???????????? ????????? ???????? (????????, ?? ?????? ???????? ??????) ???? ??????????? ??????????? ?????????
??????????? ?????????? ? ??????????? ?????????????? ? ??????? ?????? ??????????????. ?????????? ????????????? ? ?????? ?????? ?????? ? ????????????? ???????????? ?????????? ???????? ?????????????? ????????????? ? ??????????? ??????????????
????????????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: elena@lmltd.ru
# 561 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olga Yu. Tkacheva, Alexander A. Red`kin? Electrolytes Based on the Potassium Kriolit for Low-Temperature Obtaining?
?????? ?? ??????? ?????? ??? ?????????? ?? ???????? ?????????? ???????? ?????? ? ???????? ???????????? ??????????. ???????? ???????? ????? ???????? ?????????????
???????-???????????? ???????? ??? ??????? ???????????? ???????????. ??? ?????????????? ???????? ????????????? ?????????? ??????????????? ?????????? ????????? ?????????
??????? ??????????? ????????. ? ???? ????? ????????? ????????????? ???????? ? ????????
????? ?????????? ? ?????????? ??????????????????? ???????????. ???????? ?? ??????????? ?
????????????????, ???????????? ???????? ???????? ?????????? ????? ? ?????????? ?????
?????? ?????????????.
??????? ??????????? ?????????????????? ??????? ????????? ???????? ???? ???????????????? ?? ??????????? ????????????? ??????????? ?? ?????? ?????????? ????????: ????????? ??????????? ?????????? ??????? ??????? ?? ???? ?????????? ?????????? ???????
????????. ?????? ??-?? ?????? ????????????? ????????? ? ????? ????????? ??? ?? ?????
?????????? ? ??????????????.
?????? ????? ??????? ??????? ????????? ????? ????? ???????????? ?? ?????? ?????????
????????. ????? KF-AlF3 ? ??????? (???????????) ?????????? NKF/NAlF3 ?? 1,3 ?? 1,5 ????????
??? ??????????? ???? 800 ??, ? ????????????? ????????? ? ??? ????, ??? ? ????????? ???????
[1]. ?????? ? ????????????? ????? ????? ????????????? ???????? ?????? ? ?????????? ??????? ?????? ? ???????, ??? ??????????? ?????? ?? ???????? ???????????. ?? ????????? ???????
??????-?????????? ???????? ????????? ??????????? ????????? ? ?????? ??????????? ?????????? (??) ??????????? ?? ?????????. ???, ??-????????, ? ????????? ???????? ??????
??????????? ??????? ???????? ?????????? ????????? ????????? ? ???????????? ?? ?????? ????????? ????????, ? ???????????? ??????? ? ????????? ??????? ??? ??????????? 700 °? [2-4].
???????? ????????? ???? ??????? ? ??????? ? ???????????? ??????????? ?? ??????????,
???????????? ???????????? ??????? ????? ?? ???????, ??????????? ??????, ???????????? ???????????? ???????? ?????????? ?? ????????.
? ????????? ?????? ?????????? ?????????? ???????????? ??????? ??????-??????????
??????? (??????????? ?????????, ??????????????????, ????????????? ?????? ????????) ????????????? ?????? KF-NaF-AlF3 (??=1,3-1,5) ? ????????? CaF2 ? LiF, ??????? ????? ???? ???????????? ? ???????? ???????????? ????????????-????????????? Al2O3 ??? ??????????????????? ????????? ????????. ??????? ????????, ??? ??????????? ????????? ? ??? ?????????
??????? ???????????? ??????? ????????? ??????? (NMF) ? ??????? ???????? (NAlF3): ?? =
NMF/NAlF3. ??? ????????? ??????????? ????????? ??????????? ????????? ???????????? ???
????????? ????? ??????? ???????????? ???????? ???????? ???????? ? ??????? ???????????? AlF3. ????????, ??? ????? KF-NaF-AlF3 ?? = (NKF + N NaF)/NAlF3, ? ??? ????? KF-NaF-LiFAlF3 ?? = (NKF + N NaF + NLiF)/NAlF3. ??????? CaF2 ?? ???????? ??????????? ????????? ???????
?? ??????? ?????? (KF-NaF-AlF3)-CaF2. ??? ??????? ?? ???? ?????? ??????? ????????????
CaF2 ?? ?????????.
??????????? ?????????
??? ??????????? ??????????????? ?????????? ???????? ?????? ????????? ???????????
???????? ??????????? ?????????, ?? ???????? ??????? ??????? ??????? ??????????? ?????????????????? ????????.
# 562 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olga Yu. Tkacheva, Alexander A. Red`kin? Electrolytes Based on the Potassium Kriolit for Low-Temperature Obtaining?
???. 1. ??????????? ????????? ????????? KF-NaF-AlF3 ? ????????? ??
??????????? ????????? ???????? ??????? ????????????, ? ????? ?????????? ?? ????????? ????????????? ??????????? ??? ??? ?????????? [5]. ??????? ???????? ??????????, ?????????? ????? ????????, ?? ????????? 5 ????????.
????????? ??????????? ????????? ????????? ??????????? ????????? KF-NaF-AlF3 ? ??????????? ?? ??????????? ???????????? KF ? NaF ? ????????? ?? 1,3-1,7 ???????? ?? ???. 1,
??? ???????? ????? ??????????, ?????????? ? ??????? [6, 7] ??? ?????? ? ??=3 ? 1,8.
??????? NaF ?? 15 ???. % (??????? ???????????? NKF/(NKF+N NaF)=0,67-1,0) ? ???????? KFAlF3 ? ??<1,7 ??????????? ???????? ??????????? ?????????, ????? ??? ????? ?? ???????
NaF ? ????????? ???????? ? ????? ??????? ?? (1,8-3,0) ?? ????????. ??????? KF ? ????????
NaF-AlF3 ? ??????? ???????????? NKF/(NKF+N NaF)=0,0-0,3 ???????? ??????????? ?????????
????????????? ?????? ??? ????? ??.
??? ?????????? ??????????????????? ??????????? ???????-??????????? ????????????
????????? ??????? ????????? KF-NaF-AlF3 ? ??????? ????????????? KF ? ?????? ??????????? ??????????. ??? ??????? ??????????? ????????? ????????? ??????????? ?????????
KF-NaF-AlF3 ? ????????? ?? 1,3-1,7 ? ??????????? ???????????? ???????? ???????? ???????? NKF/(NKF+N NaF)=0,3-1, ? ??????? ???????????? ????????? Origin ???????? ????? ????????????? ?????????:
T??? = 2582.85?2488.7???+211?N ? 655.9? N2 +
+868.9???2 +420.97????N ± 12,
(1)
??? T??? ? ??????????? ?????????, ?; N=NKF/(NKF+N NaF); ??=(NKF+N NaF)/NAlF3. ?????????????
?????? ????????? ??? ?????? ?????????? 0,05. ??????????? ???????????? R 2 = 0,95. ???????????? ?????? ????????? ??? ????????? ?? ? ?????????????????? ??????? (???. 2).
????????????? ?????? ????????
???????? ???????????, ??????????, ???????? ? ????????? ????????????? ?????? ????????. ?????????? ???? ????? ????? ??????? ????????????, ? ??????? ????????????? ??????
# 563 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olga Yu. Tkacheva, Alexander A. Red`kin? Electrolytes Based on the Potassium Kriolit for Low-Temperature Obtaining?
???. 2. ????????????????? ? ???????????? ?? ????????? (1) ???????? ??????????? ????????? ?????????
KF-NaF-AlF3. ????? ? ???????????, ????? ? ??????
???????? ?????????? ?? ????? 4 ???. %; ?????????? ??? ?????? ?????? ??????? ????????
??????? ???????????? ????????? (2-4 ???. %) ? ???????????? ???????????? ?????.
????????????? ?????? ???????? ? ??????????? ????????? ?????????? ??????? ??????????????? ????????? ? ??????????????????? ????????? ????? ????????? [8]. ???????????? ????????????? ??????????? ????? ?????? ?????????? 7,8 %.
????????????????? ???????? ????????????? Al2O3 ? ????????? KF-AlF3 ? KF-NaF-AlF3
(??=1,3-1,5) ? ????? ???????????? KF ? NaF ? ????????????? ????????? ?? 800 °? ?? ?????
????????? ???????? ???????????????? ??????? ???? ???????? ????????????? ??????????
S = ?19.367 + 3.385 ? ?? + 0.015 ? T + 3.494 ? N ± 0.22,
(2)
??? S ? ????????????? ?????????, ???. %; T ? ???????????, ?; N=NKF/(NKF+N NaF); ??=(NKF+N NaF)/
NAlF3. ????????? ???????????????? ???????????? ? ???????????? ?? ????????? (2) ????????????? ?????? ???????? ? ????????????? ?????? KF-NaF-AlF3 ??? 800 °? ???????????? ??
???. 3. ??? ?? ????????? ?????? ?? ????????????? ????????? ? ?????? KF-NaF-AlF3 ? ??=1,3
??? ??????????? 750 °?, ?????????? H. Yan [8]. ??? ?????????? ?????? ??????????? ? ???????????? ? ??????? ????????????? KF.
??????? LiF ? ???????? ??????? ? ??=1,3 ? 1,5 ??????? ????????????? Al2O3 ???????
?? ????????? ? ????????? NaF ????? ?? ???????????? (???. 4). ??? ??????????? ?????????
?????? ??????????? ???????? ????????. ??????? ?????, ???? ??????????? ??????? ?????? ????????? (?(Li+)=1,7), ??? ??????? ?????? (?(Na+)=1,01), ??????? ??????? ? ????? ????? ? ????????-????????? ??????????, ??? ???????? ? ?????????? ???????? ????????????
????????-???????-????????? ?????????? ??? ??????????? Al2O3. ??????? ??????? ????????????? ????????? ? ????????? LiF ?? ???????????, ???? ??? (? ?????????? ?? ????? 3 ???. %)
????????? ? ????????? ???????? KF-NaF-AlF3.
??? ????????, CaF2 ??????????? ? ???????????? ?????????? ??????? ??????? ??? ????????? ??????????? ???????????. ?????? ??????? CaF2 ???????? ????????????? Al 2O3 ?
# 564 #
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Olga Yu. Tkacheva, Alexander A. Red`kin? Electrolytes Based on the Potassium Kriolit for Low-Temperature Obtaining?
???. 3. ????????????????? ? ???????????? ?? ????????? (2) ???????? ????????????? Al2O3 ? ?????????
KF-NaF-AlF3 ??? 800 °?. ????? ? ???????????, ????? ? ??????. ??: 1 ? 1,6; 2 ? 1,5; 3 ? 1,3; 4 ? 1,3 [8]
(750 °?)
???. 4. ????????????? Al2O3 ??? 800 °? ? ???????????? (??=1,3): 1 ? (KF-AlF3)-NaF; 2 ? (KF-AlF3)-LiF;
3 ? KF-NaF-LiF(3 ???. %)-AlF3 (??=1,3)
?????????, ??? ?? ???????? ????????? ? ???????? ????????????? ???????????, ?????????
??????? ???????????? Al 2O3 ??????? ???? ??? ?????????????. ?? ??????? CaF2 ?? ????????????? Al 2O3 ?????????? ????? ???????? ??? ?????????? ??????????????????? ???????????,
??? ???????????? Al 2O3 ?????? ? ?????????. ???? ????????????? Al 2O3 ? ????????? KF-NaFAlF3 ?????????? ? ??????????? ?????????? KF, ?? ???????? ????????? ???????????, ????
? ????????????? ????? ????????? CaF2 (???. 5). ??? ???? ???????????? CaF2 ? KF ? ???????? (KF-NaF-AlF3)-CaF2, ??? ?????? ????????????? ? ??? Al 2O3. ?? ???? ? ????????????,
???????? ??????????? ??????? ?????? ???????? ??????? ? ?????? ??, ??????????? CaF2
????????????.
# 565 #
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Olga Yu. Tkacheva, Alexander A. Red`kin? Electrolytes Based on the Potassium Kriolit for Low-Temperature Obtaining?
???. 5. ????????????? Al2O3 ? ????????????????? ???????????? (??=1,3) ??? 850 °?: 1 ? NaF-AlF3; 2 ?
NaF-KF-AlF3 c N KF/(N NaF+N KF)=0,21; 3 ? NaF-KF-AlF3 c N KF/(N NaF+N KF)=0,46
??????????????????
? ?????????? ??????????? ?????? ?? ?????? ????????????? ?????? ????????, ?? ? ??????????????????, ??????? ?????? ?? ??????????????? ??????? ????????????, ????????? ???????? ?????? ????? ? ????? ????????????? ????????????????? ?????????.
????? ????????? ?????????????????? ????????? ? ????????-???????? ????????? ?????????? ? ??????????????? ????????????? ????? ? ?????????? (BN) ? ? ?????????????
????????????? ??????????? [9]. ???? ?????? ????????????? ??????????? ????????? ?????,
??? ?????????? ???????? ????????? ?????????????????? ??????????? ????????? ? ???????
????????????? ?????????.
?????????????????? ????????? KF-NaF-AlF3 ?????? ? ??????????? ???????????? NaF ?
??. ??? ??????????? ? ????????? ?? 800 °? ?? ??????????? ????????? ???????? ???????????????? ??????? ????? ??????? ??????????
ln? = 3.44?2445.41/T? 2.219?NAlF3 + 0.501?N NaF ?0.6956?(N NaF)2 ± 0.011,
(3)
??? ? ? ???????? ??????????????????, ??-1.??-1; ? ? ???????????, ?; N NaF ? NAlF3 ? ????????????
NaF ? AlF3, ???. %.
?????????????????? ????????? KF-NaF-AlF3 ???????????? ? ?? 1,2-1,5 ??? ???????????? 750-820 °? ?????????? J. Yang ? ?????????? [10]. ????????? ????????? ??????? «????????? ?????????? ????????? ??????». ??????????? ???????? ?????????????????? ?????
???????? ???? ?????????? ????. ???????????? ?????????? ???????? ?????????? ????? 10 %.
????? ??????????? ????? ????????? ???????????? ????????? ???????????? ???????, ? ????? ????????? ?????????????? ?????.
??????? LiF ? ??????? ??????? ??????????? ?????????????????? KF-AlF3 ?? ?????????
? ????????? NaF ????? ?? ???????????? (???. 6). ???? ?????????????????? ???????? KF-NaFAlF3 ?? ???????????? NaF ???????????? ????? ???????? ???????????, ?? ??????????????????
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Olga Yu. Tkacheva, Alexander A. Red`kin? Electrolytes Based on the Potassium Kriolit for Low-Temperature Obtaining?
???. 6. ?????????????????? ????????? ??? 800 °?: 1 ? KF-NaF-AlF3 (??=1,3); 2 ? KF-NaF-AlF3 (??=1,5);
3 ? KF-LiF-AlF3 (??=1,3)
KF-LiF-AlF3 ??????????? ??? ????????? ?????? ???????. ??? ??????? ? ???, ??? ??????? Li+,
???????? ??????????? ?????? ? ???? ????????????, ??????? ??????? ?????? ???????????,
???????? ??????? ?????????????????? ????? ? ???????????? ???????? ????????, ??? ?????
????? ???? ???????????, ??? ??????????? ?? ???????? ??????????????????.
???????????? ???????????? ??????? Al2O3 ?? ???????? ?????????????????? ????????, ????????? ??????????? ????????? ? ?? ?????? ? ?????? ?? ? ????????? ?????????? 700-800 °?
????????, ??? ??????? Al2O3 ? ???????? ? ?????? ?? ???????? ? ????????? ?????????????????? ? ??????? ???????, ??? ??? ?????????? ? ???????????? ? ??????? ??.
?????????? ?????? ??? ????????? ?????-????????? ?????????????????? ????????? ?
??????????? ?? ??????? ? ??????????? ???????? ??????????
ln? = 2.24 ? 0,029·NAl2O3 + 0.00296·N NaF + 0.319·?? ? 2624.4/T ± 0.012,
(4)
??? ? ? ???????? ??????????????????, ??-1.??-1; NAl2O3, N NaF ? ???????????? Al2O3 ? NaF, ???. %;
??=(NKF+N NaF)/NAlF3; T ? ???????????, K. ????????? (4) ??????????? ? ??????? ????????????? Al2O3 ??? ???????????? ?? 800 °? ?? ??????????? ????????? ???????????????? ???????
???????????.
????? ??????????? ??? ??????????????????? ???????????
??????????? ?? ??????-?????????? ??????????????? ?????? ????????? ? ??????????
?????????, ????? ??????? ?????? ????????????? ??????????? ? ???????????? ??????????
??? ?????????? ??????????????????? ??????????? ?????????. ??????? ??????????? ???????? ??????????? ????????????? ????????? ? ????????? ??????????? ??? ??????? ??????????? ???????????. ?????????? ?????????, ??? ??? ????????????? ??????? ? ??????? NaF-AlF3
????????? ??????????? ????????? ?????????????? ????????????? ?????, ?????? ??? ???????
? ???????? ?F-AlF3 ? ?? < 1,7, ???????? AlF3, ???????? ??????????? ?????????. ????????
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Olga Yu. Tkacheva, Alexander A. Red`kin? Electrolytes Based on the Potassium Kriolit for Low-Temperature Obtaining?
??? ????????? ?? ????????, ??? ???????????? ??????????? ????????, ??????????? ? ????????? ??? ??????????????????? ????????? ????????, ????? ????????? ?? ??? ??????:
1. ???????????, ?????????? ?? ????????? ???????? NaF-AlF3 ? 1,7>??>2,0 ? ????????
??????? ?????????? 800-900 °?;
2. ???????????, ?????????? ?? ???????? ???????? ?F-AlF3 ? 1,3>??>1,7 ? ???????? ??????? ?????????? 700-800 °?.
??????????? ???????????, ???????????? ????????? ??? ??????????? ????????? ? ??????????? ?????????, 700 °?, ??????? ????? ?????????? ?????????? ??????? ?F-AlF3 ? ??=1,3.
?????? ??????, ???????? ?????? ? ?????????? ? ?????????? ??????????????? ? ????????????? ?????, ??????????? ???????? ??????????? ????????? ????????? ????????. ??? ???? ????? ???????? ???? ????????, ????????????? ??????? ???????????? KF-NaF-AlF3 ? ??=1,3-1,5,
?????????? 12-15 ???. % NaF, ????????? ????????? ??????????? ???????????? NaF ????????
???? ? ???????? ??????????? ?????????. ??????????? ?????? ??????? ????? ?????????????
????????? ?? ????? 4,5 ???. % ? ????????? ?????????? 700-800 °?. ??? ?????????? 1 ???. %
Al2O3 ??????????? ????????? ????????? ?F-AlF3 ? KF-NaF-AlF3 ? ??=1,3 ? 1,5 ??????????, ?
???????, ?? 3-4 ???????.
?????????????????? ???? ????????????? ????????? ??????????? ???? ?????????????????? ???????????? ????????????, ???????, ??? ???????, ?????????? ?? ????? 2,1 ??-1???-1.
??????? 12 ???. % NaF ??????????? ?????????????????? ???????? KF-AlF3 (??=1,3) ?? 6 %, ?
??????? LiF 3 ???. % (????? ?????????? LiF ??????? ???????? ?????????????? ??? ????????) ?
???????? KF-AlF3 ??????????? ?????????????????? ?? 8 %. ??? ??????? ????? ??????????????
???????? ??????????????????, ????????? ???????????? ????????? (4 ???. % Al2O3 ???????
?????????????????? ????????? KF-NaF-AlF3 ? ??=1,3 ?? 7 %).
??????????? CaF2 ? ???????????? ???????????? ?? ?????? ????????? ???????? ????????????, ??? ??? ?? ????????? ?????? ?? ??????????? ?????????, ?????????????????? ? ????????????? ????????? ? ??????????????? ?????????.
??? ????? ??????? ??????????? ????????? ??? ?????????????????? ????????, ??? ? ????????????? ? ??? Al2O3 ??????????, ?? ??? ???? ??????????? ????????????? ??????????? ????????? ? ???????? ??????? ???????????? ???????????? ???????? ???????????? ? ???????????
????????? ?????????? ? ??????? ? ????????? ??????? ??? ??????????? ???? 800 °?.
?????? ????????? ?? ??????????????? ??????? ??? ??? 12-?-3-2056.
?????? ??????????
[1] Robert E., Olsen J. E., Danek V., Tixhon E., Ostvold T., Gilbert B. // J. Phys. Chem. B. 1997.
Vol. 101. ?. 9447.
[2] Yang J., Hryn J., Krumdick G. // Light metals. 2008. P. 421.
[3] Wang J., Lai Y., Tian Z., Liu Y. // J. Cent. South Univ. Technol. 2007. P. 768.
[4] Zaikov Yu., Khramov A., Kovrov V., Kryukovsky V., Apisarov A., Chemesov O., Shurov N.,
Tkacheva O. // Light metals. 2008. P.505.
[5] Kryukovsky V., Frolov A., Tkacheva O., Redkin A., Zaikov Yu., Khokhlov V., Apisarov A. //
Proceedings of 12 International Conference «Aluminum of Siberia 2006», Krasnoyarsk. 2006. P. 46.
# 568 #
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Olga Yu. Tkacheva, Alexander A. Red`kin? Electrolytes Based on the Potassium Kriolit for Low-Temperature Obtaining?
[6] Danielik V., Gabcova J. // J. Thermal Analysis and ?alorimetry. 2004. Vol. 76. P. 763.
[7] Grjotheim K., Mikhaiel S.A., Hytta R., van der Hoeven M. G.,. Swahn C.-G // Acta Chemica
Scandinavica. 1973. Vol. 27. N 4. P. 1299.
[8] ???????? ?.?., ????? ?.?., ?????? ?.?. // ??????????? ??????? ? ?????? ????????:
????????? 2-? ????????????? ???????????. ??????????: ???? ?? ???, 2003. ?. 2. ?. 48.
[9] Kryukovsky V., Frolov A., Tkacheva O., Redkin A., Zaikov Yu., Khokhlov V., Apisarov A. //
Light metals. 2006. V. 2. P. 409.
[10] Yang J., Li W., Yan H., Liu D. // Light metals. 2013. P. 689.
??????????? ?? ?????? ????????? ????????
??? ??????????????????? ????????? ????????
?.?. ???????, ?.?. ???????, ?.?. ???????,
?.?. ????????, ?.?. ????????, ?.?. ??????
???????? ??????????????????? ???????????? ??? ???
??????, 620990, ????????????, ??. ?????????????, 20
??????????? ? ??????? ?????? ?????????????? ??????????? ???????? ??????-??????????
???????? (??????????? ?????????, ??????????????????, ????????????? ?????? ????????)
????????? ?????-????????? ??????????? ????????? ? ??????????? ?????????? 1,3-1,5
? ????????? LiF ? CaF2. ?? ????????? ?????????? ??????????????? ?????????? ???????
????????????, ????????????? ??? ??????????????????? ?????????????????? ?????????
????????: KF-AlF3 ? KF-NaF-AlF3, ?????????? 12-15 ???. % NaF, ? ??????????? ??????????
1,3-1,5 ? ???????????? ????????? ???? 800 °?. ????????????? ????????? ? ?????
???????????? ?????????? ?? ????? 4,5 ???. % ? ????????? ?????????? 700-800 °?. ???
????????? ?????????????????? ????????????? ??????? LiF ? ?????????? ?? ????? 3 ???. %.
??????????? CaF2 ? ??????????? ????????????.
???????? ?????: ???????? ???????, ?????-????????? ???????, ??????????????????,
??????????? ?????????, ????????????? ?????? ????????, ?????? ???????,
?????????????????? ??????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 570-578
~~~
??? 621.777
Main Characteristics and Future Development
of Aluminum Alloys with High Dispersion Ability
of Phase of Alloying Elements
Juri A. Gorbunov*
Engineering and Technology Center «SIAL» Ltd
103 Pogranichnikov, Krasnoyarsk, 660111, Russia
Received 09.03.2014, received in revised form 11.05.2014, accepted 11.08.2014
This article present main characteristics of aluminum alloys with high dispersion ability of phase
of alloying elements. Examined future development in the field of obtaining heat-resistant and highstrength aluminium alloys, as well as alloys for special purposes.
Keywords: aluminium, microalloying, continious casting, high-temperature strength, mechanical
properties.
For semi-finished aluminum alloys produced by traditional methods of semi-continuous casting
billets and pressure treatment, potential for significant improvement of physical and mechanical
properties to date largely been exhausted. Therefore, special importance attaches new ways to improve
the performance characteristics of structural alloys, in particular, through a combination of alloying using
not traditional components and increasing the degree of dispersion of all elements of their structure.
The combination of these two exposure approaches on metals properties can be implemented in
various ways, including, for example, increasing the doping level by group of transition metals with
simultaneous application of high velocity cooling melts (more than 103 K/s) during the crystallization. In
this case, along with fundamental morphological changes in the metal structure can observe anomalous
supersaturated solid solution of transition metals. This factor provides additional opportunities to
obtain materials with unique characteristics
The most significant part of research and pilot works of the last decade to achieve high cooling
rates during crystallization of aluminum alloys, based on the dispersion melt in various ways, with
the subsequent crystallization of received particles in a gaseous medium, an aqueous medium or on
a metal base. Hereafter, these particles were heated in an inert atmosphere or in vacuum then were
compacted and processed into various kinds of semi-finished products by traditional methods of metal
treatment under pressure. In studies of these semi-finished products was established that high cooling
rates during the crystallization of molten aluminum, besides the increasing of many mechanical
properties semi-finished products, allowed discovering unique opportunities to obtain materials with
exclusive physical properties.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: gja@sial-group.ru
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Juri A. Gorbunov. Main Characteristics and Future Development of Aluminum Alloys with High Dispersion Ability?
On the basis of a great number of researches in this way performed domestic and foreign scientists,
were created a number of new, so-called rapidly solidified alloys (including granular alloys) aluminumbased alloys. Some of these alloys have been widely used in the pilot production number of plants.
Analysis of published research data of different organizations linked with the data obtained by the
author and his colleagues during the work in ?All-Russian Research Institute of Aviation Materials?
(?VIAM?) and in Research and Development Center of Krasnoyarsk Metallurgical Plant (?KraMZ?),
allows to identify the following main features of these alloys.
High-temperature alloy. At the first stage the efforts of Russian scientists were aimed at the
creation of alloys characterized by abnormal supersaturation of solid solution by transition metals. In
this direction most actively worked domestic scientific schools in the ?VIAM headed by Fridlyander
I.N. and in the ?All-Russian Institute of Light Alloys? (?VILS?) under the guidance of Dobatkin V.I.
and Yelagin V.I. They proceed from the fact that the segregation of anomalously supersaturated solid
solutions recorded during casting, in the processing of particles rapidly crystallized alloys in the semifinished products leads to formation of dispersed intermetallic phases which resistant to coagulation
to a defined temperature level. It was found that the higher melting temperature of hard-melting
components included into the alloy, the higher the heat resistance of the alloy. Based on this principle
have been developed weldable alloys 01419 (Al-Mn-Cr-Zr-Ti-V), 01435 (Al-Cr-Zr) and others. Longterm strength for the alloy 01419, for example, is 65-70 MPa, and for alloy 01435 is 60-65 MPa.
Abroad first generation of heat-resistant alloys were created by heterogenization of cast structure
used as insoluble additives iron, nickel, cerium, cobalt and other elements (companies ?Alcoa?,
?Lockheed?, ?Pratt and Whitney?, ?Allied Signal Inc?. etc.).
At the next stage, both domestic and foreign metallurgists turned to complex alloying heat-resistant
alloys. As a result, metallurgists from ?VILS? were created 01489 alloy of system Al-Fe-Cr-Zr-Mo,
having short-term strength with of 210-240 MPa and foreign metallurgists were created FVS0812 alloy
of system Al-Fe-V-Si and a series of alloys of system Al-Fe-Mo.
Comparative analysis of the characteristics of the developed heat-resistant alloys showed that
heterogeneous alloys have an advantage under short term operation, under elevated temperatures; and
for prolonged operation, under elevated temperatures (up to 250 °C) are more suitable alloys which
form the homogeneous structure during casting.
In domestic practice, heat-resistant alloys - the first of rapidly solidified materials, have found
practical applications in engineering (including aeronautical engineering). First pilot production of
semi-finished products from these alloys were organized in Moscow in the ?Plant of Light Alloys?. Semifinished productsofalloy01419usedin products continuously operating under elevated temperatures (up
to 350-400 o?), for example, in heat exchangers, pipe connections, manholes, plugs; 01435 and 01489
alloys used as body parts, launching racks, compressor blades etc.
Practical applications of these materials has shown that the alloy 01419 possesses complete
insensitivity to solidification cracks during welding. The strength of weld joint is close to the strength
of the base material, which is a consequence of the high stability of the heterogeneous structure of
the material. It should be pointed that the depth of corrosion damage of semi-finished products from
alloy 01419 during use in aggressive coastal environments in several times lower than any series of
aluminum alloy. According to the developers of the material it is associated with higher than billets
alloys; passivation properties caused by the formation of solid solutions of transition metal in the
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Juri A. Gorbunov. Main Characteristics and Future Development of Aluminum Alloys with High Dispersion Ability?
aluminum, as well as partly also due to entering of transition metals into the protective oxide film. Th
ealloy01435hassimilarcorrosionproperties.
High-strength alloy. During creation of alloys of this group, as well as the development of hightemperature alloys, in the 70-80s, Russian scientists were originally used principles of anomalous
supersaturating by transition metals of solid solution based on aluminum. Dobatkin V.I., Yelagin
V.I. and Fedorov V.M. was shown that increased strength rapidly solidified alloys of this group in
comparison with traditional alloys, obtained by standard technology, is determined by a combination
of the two hardening mechanisms:
? Precipitation hardening connected with the release of solid particle reinforcing phases formed
by copper, magnesium, zinc and silicon, as the result of quenching and aging deformed semifinished;
? Precipitation hardening connected with the formation of anomalously supersaturated solid
solutions of transition metals in aluminum at high cooling speed and release of aluminides of
transition metals during subsequent thermal and deformation treatments.
Additionally, elevated concentration of the transition metals leads to significant increase the
temperature of alloy recrystallization and, accordingly, leads to enhance the effect of structural
strengthening.
For the first stage of work based on the research results and based on Al-Zn-Mg and Al-Zn-MgCu systems, specialists from ?VILS? and ?Russian State Technological University? (?RSTU?) were
created 01949, 01995, 01996 alloys and others. For the next stage - production development stage of semifinished products specialists of ?VILS?, basic scientific research laboratory of ?VIAM? and ?KraMZ?
were evaluated behavior of these alloys under thermal desorption of grains and under deformation and
heat treatments of semi-finished products. For the first time, during compaction of experienced alloys
into semi-finished products relative small size and their following deformation, allowed to obtain and
to analyze semi-finished products having inconsistent, until that time, the complex of characteristics.
Alloys 01949 and 01995 are the only high-strength alloy that can be welded by argon arc
welding. From these alloys by experimental-industrial method were obtained extruded, stamped
and rolled semi-finished products for using in a wide range products of responsible engineering.
According to their mechanical properties, these alloys are close to well-known ?95 and 7075 alloys,
but 01949 and 01995 alloys completely have not a tendency to hot cracking during the welding. Alloys
have high corrosion resistance, tensile strength of welded joints from these alloys is superior to all
the best weldable alloys (tensile strength is 480-550 MPa). The presence of foreign analogues of these
alloys is still not known.
Extruded and forged semi-finished products from alloy 01996?1 possess sufficient tensile strength
(700-730 MPa) at the level of the other characteristics that are close to ?96??1, but at the same time
the corrosion resistance of the alloy 01996?1much higher than for the ?96??1. Verification nature
tests of stamped products from 01996T1 alloy in a range of constructions showed their high functional
reliability and wide opportunities of applications.
For the organization of industrial production of semi-finished products made from listed granular
alloys, ?KraMZ? has been developed and started the technology of degasification and compaction
large-sized capsules by vertical hydraulic presses. This is the first time in the practice allowed to
produce briquettes with diameter of 470Ч1100 mm for the followed by extrusion into rods with diameter
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Juri A. Gorbunov. Main Characteristics and Future Development of Aluminum Alloys with High Dispersion Ability?
from 10 to 280 mm and forging these rods into plates with size of 80Ч1100Ч3500 mm by vertical
presses for the followed by hot rolling into sheets. However, during practical applications of industrial
technology of treatment large-sized semi-finished product from alloy 01996 was found insufficient
stability of structure during prolonged heating over a range of deformation temperatures and high
extension appropriate of production of thin-walled semi-finished products.
At this time, foreign specialist more preferred to use alloying aluminum by hard soluble elements
such as cobalt and nickel. Entering of cobalt was the result of the formation of dispersed particles during
crystallization. These particles allow to connect together detrimental impurities into complex phase
(??, Fe)2Al9 and increase the fatigue strength and corrosion resistance of semi-finished products. Using
this method Laboratory of company «Alcoa» created 7090 and 7091 alloys, and the Production Base
(California) started industrial production of workpieces with the weight of 50-160 kg for the followed
by production of semi-products from it. Indicators of fracture toughness, fatigue crack propagation
velocity, corrosion resistance and other performance characteristics of these alloys were close to the
domestic high-strength alloys, but much inferior to them on the strength characteristics.
Combining alloying methods of aluminum alloys using transition metals, which formed
anomalously supersaturated solid solutions, and with difficult soluble elements, domestic specialists
with participation of the author of this article was developed a group of alloys of aluminum-zincmagnesium-copper system. The alloys of this system contain the most positive effects of the alloys of
the previous generation. The best combination of strength and corrosion resistance in these alloys was
achieved by additional alloying using manganese, chromium, zirconium, titanium, cobalt, and nickel.
Alloying by transition metals has the most effective impact on hardening semi-finished products
with minimum content or full absence of phase T. This leads to a slight fall in strength properties, but
at the same time significantly increasing the characteristics of structural strength. Considering this
phenomenon was developed alloy 01959. Considering this phenomenon was developed alloy 01959,
semi-finished products made from this alloy are recommended for products with increased resource of
critical applications, see Table 1.
As seen from the data presented in the table, the ratio of strength, fatigue and corrosion
characteristics of extruded semi-finished products of alloy 01959 T2 significantly surpass all alloys
produced by traditional methods of casting ingots and their deformation. Similarly describe largesized sheets produced by rolling forged plates.
Extruded and rolled semi-finished products from alloy 01969 have almost the same strength
characteristics as of alloy 01996, but it has a higher elongation and, most importantly, it has higher
structural strength characteristics.
Level of strength properties of hardness and corrosion resistance of semi-finished products of
alloy 01969 have an advantage compared with the analogous semi-finished products from ingots.
During hot stamping of rods be absent softening alloy unlike rods of alloy ?96?1 that allows using this
alloy to produce details, which during of operation take up critical static and dynamic force with a high
level of operational reliability. Therefore, semi-finished products from this alloy are recommended for
a number of aerospace products.
Concentration of the main alloying elements in the alloy 01979 was increased. This alloy is
recommended for engineering and instrumentation products of general purpose, as well as for a
single-purpose. For characteristics of the structural strength of this alloy are not applied such highest
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Juri A. Gorbunov. Main Characteristics and Future Development of Aluminum Alloys with High Dispersion Ability?
Table 1. Averaged data of physical and mechanical properties of semi-fi nished products produced by extruding
high rapidly solidified alloys
Properties
of extruded semi-finished products
Alloy identifier, thermal treatment identifier
01959?2
01969?1
01979?1
Ш80mm
01979 ?1
Ш30mm
Tensile strength, MPa
680
720
780
840
Yield strength, MPa
640
670
760
820
10
6
9,5
10
200
70
Elongation, ?10, %
Impact strength, kJ/m
2
Endurance strength based on 2?106 cycles, MPa
- for smooth specimen
- for notched specimen
Low-cyclefatiguebasedon2Ч106 cycles
at ?t =2,6 ? max =157 MPa
195
117
478600
Depth of grain-boundary corrosion, mm
0,21
Tendency to layer corrosion, score
3-4
4-6
4,5-5
requirements, as for semi-finished products for critical application. In relation to the conservation
in the alloy structure 01979, up to the latest technological operations, partially supersaturated solid
solution of transition metals, semi-finished products have very high strength characteristics. In pilot
production this alloy used in the production of bands with cross-section up to 20x300mm, rods with
diameter of 10-80mm and profiles. All of these products can be used at defense industry, during of
production elements for ring spinning machines and friction units, in electronic devices for various
applications, for single-use products, etc.
Highly-modularized alloys with low density. In the 70-es of the last century by the initiative
of Fridlyander I.N. aluminum alloys with lithium have been actively used in domestic technology,
providing it with a competitive advantage in terms of weight and a number of other characteristics.
Therefore 1420 alloy - one of the first domestic materials of this group, had a density of 2.47 g/cm3. The
use of this alloy in a number of aircraft designs allowed reducing their weight by 12-15 %. In further
research work of ?VIAM? and ?KraMZ? Basic Scientific Research Laboratory was found that rapidly
solidified aluminum alloys containing lithium have the best combination of strength and stiffness than
their analogues produced by traditional technological schemes. Used methods of rapid solidification
alloys allowed entering more alloying elements than used conventional casting processes and as a
result to obtain the proportional distribution of particulate phase components.
The fi rst domestic rapidly solidified alloy with lithium obtained used protective alloying by
beryllium is 01429 of Al-Mg-Li system. The fatigue strength and the fracture characteristics of the
extruded semi-products from this alloy is for 10-15 % higher than from alloy 1420 which produced
by traditional technology. The following modification of this alloy with cipher of 01429? has a higher
concentration of anti-crystallizers elements and increased values of strength, hardness and wear
resistance. This alloy has found application in domestic technology, at the production of strips, rods
and forgings from them. Pilot production of products from this alloy was organized by ?KraMZ?
with the guaranteed level of tensile strength is more than 520 MPa, yield strength is more than 380
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Juri A. Gorbunov. Main Characteristics and Future Development of Aluminum Alloys with High Dispersion Ability?
MPa, hardness is more than 140 HB with the elongation is more than 7 % and density is less than
2.47 g/cm3.
Foreign companies such as ?Alcan?, ?Lockheed? and others have focused on the development and
research of alloys containing lithium up to 4 %.The task of these companies was to increase strength,
toughness, corrosion resistance and specific rigidity by 30 %.
Alloys with low linear expansion coefficient. The basis of aluminum alloys with low thermal
expansion is the Al-Si system. At high cooling rates in this system alloys are solidified in accordance
with the metastable phase diagram, even when content of silicon is up to 35 % it produces eutectic
structure and good deformability of the material. Taking this factor, domestic specialists developed
a large enough group of aluminum-silicon alloys with the following coefficient of linear expansion
?0-100°?Ч 10 -6 = 13,5-15,5 1/°?.
Under the guidance of Frindlyander I.N. (?VIAM?) were created several ternary alloys of type
Sintered Aluminum Alloys (SAA), containing as an additional alloying elements Ni, Fe or Cr. Take
into account the characteristics of these alloys it should be noted that the best alloy is SAA-1 having the
lowest coefficient of linear expansion (close to steel), and higher ductility. This can be explained more
preferred form of Ni-intermetallic in comparison with form of Fe- and Cr- intermetallic. However,
elongation of alloys type SAA obtained by powder metallurgy methods, does not exceed 0.6-1.5 % that
limit their use in all other areas except tool engineering.
Shmakov Y.V., Litvintsev A.I. and others (?VILS?) developed 01379 alloy containing 17-19 % of
silicon, copper, magnesium, and transition metals. This alloy has average strength at room temperature
and high strength, hardness and wear resistance, sufficiently low coefficient of linear expansion at
temperatures up to 300 °C. The task of further reducing the coefficient of linear expansion was solved
by entering in alloy 35-40 % of silicon, during solidary alloying by increased amount of transition
elements. The specialists of Dnepropetrovsk Metallurgical Institute offered the most doped alloy with
Al-35 % Si-2 % Fe for manufacturing of pistons engines internal combustion with maximum wear
resistance and dimensional stability. The specialists of ?VIAM? and ?KraMZ? Basic Laboratory were
developed production technology of rods from this alloy with diameter up to 120mm and forgings
from rods for the following application in pistons engines internal combustion. This technology is
characterized by high wearing resistance and functional reliability.
Research showed that the operational properties complex of rapidly solidified 01379 and Al35 % Si-2 % Fe alloys surpass all known piston materials, including Al-12 % Si. Indicators of longterm strength, fatigue strength and wear resistance of alloys 01379 and Al-35 % Si-2 % Fe exceed the
corresponding indicators of Al-12 % Si alloy, and also have low values of linear expansion coefficient,
providing dimensional stability during operation.
Work on creation of rapidly crystallized alloys and products made therefrom are geared not only
to manufacture mechanically assembled structures. Within the development of production technology
brazed constructions also was developed method of producing an effective filler material made from
hypereutectic silumin (Al - 18-35 % Si) using modifier Al ? 1 % Sc or Al ? 5 % Ti ? 1 % B.
The material is melted and sprayed onto the baffling element in the form of a cylinder with a
diameter of 150-160 mm. Then material is pressed at 450 °C into rod with diameter of 8.6 mm and
drawn into wire with diameter of 1.2 mm for use as the filler material during laser welding; or roll
into band with thickness of 1.2 mm. Such operations are possible with the use of high silicon material
# 575 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Juri A. Gorbunov. Main Characteristics and Future Development of Aluminum Alloys with High Dispersion Ability?
(usually fragile) due to the very fine-grained structure obtained during spraying. Compared with
eutectic additional elements (Al ? 12 % Si) the new filler materials much reduce weld cracking during
laser welding of aluminum alloys, such as AA6082 alloy.
Conducting alloys with extra high temperature strength. In the works of specialists from ?VILS?
and ?KraMZ? shown that the most promising alloys for creation of current electricity conductor for
flying machine on-board systems are aluminum alloys of rare-earth metals. Dispersed additives of rareearth metals practically insoluble in aluminum, also at a concentration of 2-3 % it provides a significant
increase in strength and heat resistance of semi-finished products without significant influence on the
electrical conductivity of materials.
Technological works have shown that the most functional alloy is the 01417 containing about 7 %
of rare-earth metals. It has high electrical conductivity (? = 0,029-0,031 mc Om m) and can be used in
products operating at temperature up to 250 °C. The alloy has high corrosion resistance, good welded
and soldered. Alloy properties are almost not change after heat treatment within the temperature range
from -60 °C to +250 °C for curing period up to 500 hours.
Specialists of ?VIAM? and ?KraMZ? Basic Laboratory were developed pilot production of
wires from alloy01417 for use in on-board systems of supersonic aircraft. Such application allowed
to provide a significant weight advantage as compared with the use of electric conductors based on
copper. However, the drawing technology of small diameter wire, which is necessary for production
cables, was not stable enough due to frequent breakages (due to the presence of internal defects) and
due to not high enough yield ratio. In addition, there were problems with repair wiring from aluminum
alloys during maintenance of products. Therefore, at this stage wire of 01417 alloy have not received
wide application.
X-ray contrast materials. One of the methods of nondestructive testing of welded joints from
aluminum alloys is X-raying cast zone. On the border of this zone is artificially created chemical
heterogeneity by using foil material with high X-ray absorption coefficient between the welded
parts
As a result of prospecting work performed by ?VILS?, Research and Manufacturing Association
?Composit?, ?Siberian Federal University Institute of Nonferrous Metals and Material Science? and
?KraMZ?, as the foil material has been chosen alloy containing 01415 misch metal from aluminum
and cerium.
Production of aluminum foil was realized by two- technological schemes. On the first stage (in
Laboratory of ?Siberian Federal University Institute of Nonferrous Metals and Material Science?) was
implemented scheme continuous rolling of heated granules from alloy 01415 into bands sized 2?120mm
with followed by rolling it into foil. The next stage was development stage of industrial technology
containing volume reduction of granules, extrusion of billets into bands sized 5Ч130mm and followed
by cold rolling to final dimension. Using foil from alloy 01415 instead of band from aluminum alloy
with silver during nondestructive inspection of flying machines welded joints provided to realization
the clear radiopaque picture and excluded using of silver.
The review shows the uniqueness and variety of physical, mechanical and operational factors
of alloys with highly reduced structure, as well as the prospects of applying the developments
of topics under consideration of various fields of modern industry. However, the technology
chosen for the research and development of alloys above groups, namely melt dispersion, thermal
# 576 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Juri A. Gorbunov. Main Characteristics and Future Development of Aluminum Alloys with High Dispersion Ability?
desorption, rapidly solidified granules, it volume reduction and followed by treatment into semifi nished products by methods of metal forming, characterized by a number of drawbacks, the main
of which are:
? greater labour intensity of processing, low yield ratio of the product and as a result the high cost
of produced semi-products.
? difficultly controlled thermal desorption of particle surface of rapidly solidified alloys in
different areas of large-sized capsules and granulation surface oxides during volume reduction
and deformation of alloys
? insufficiently stability of technology parameters of equipment used at the stage of research
and development; and at the stage of experimental-industrial production engineering of semifinished products.
The consequence of listed disadvantages is not always stable behavior of semi-finished products,
as well as it high cost. Based on these reasons, can conclude that in recent years in Russia the activity
of works on rapidly solidified alloys has decreased significantly. At the same time, as the search for
compromise solutions to resolve some of the above problems have been proposed and explored other
approaches.
Micro Alloying melt by transition metals with ultrasonically-actuated during solidification.
Specialists of ?VILS? under the guidance of Eskin G.I. and Pimenov Y.P. were proposed cost reduction
of deformed semi-finished products from aluminum alloy by using as a basis of charging material with
silicon the ligature Al-Si, obtained by ecologically clean methods. Scientists have proven that the use
of this charge from cheap raw materials during preparation of aluminum alloys containing silicon
up to 17-19 % can enhance the effect of the modification, due to the presence of microquantity of
macroquantity of active metals in the ligature. The result of using charge with phosphorus-containing
ligature and complex treatment with ultrasonic vibrations of melt on the way into casting mold allowed
to obtain a homogeneous structure of ingot with primary crystals of silicon sized 20-30 micron. Alloys
with such a structure, as well as rapidly solidified alloys are well deforms and provides high-quality of
semi-finished products.
As a result of research conducted by the authors with colleagues were developed a series of
aluminum-silicon alloys with the following ciphers 01390, 01391 and 01392, and were proposed the
piped semi-finished products with diameter up to 200mm for use in oil and gas fields, as well as in
other industries.
Continuous casting of billets small diameter in to electromagnetic casting mold and their aftertreatment in the wire of different diameters. Author proposed the use of continuous casting billets
with sections into electromagnetic mold to obtain aluminum alloys of systems Al-Si and rare-earth
metals for semi-finished products with finely divided structure that would not contain deficiencies
materials produced by powder diffraction and granular technologies. The proposal was implemented
by a group of specialists under the guidance of Professor Timofeev V.N. and Docent Pervukhin M.V.
used developed by them the pilot unit.
Effective cooling of the melt Al-12 % Si during crystallization provided production using of
equipment for continuously casting of billets with diameter of 12-15 mm and unique combination of
mechanical properties. Tensile strength of castings produced by methods of electromagnetic casting
is 280-300 MPa and elongation is 18-20 %. For comparison it can be noted that the tensile strength of
# 577 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Juri A. Gorbunov. Main Characteristics and Future Development of Aluminum Alloys with High Dispersion Ability?
well modified castings from this alloy, obtained by low-pressure molding does not exceed 170-180 MPa
and elongation is up to 10.7 %.
Author in collaboration with professor Sidelnikov S.B. and Kravtsov D.V. using methods of
continuously casting billets has been developed an effective technology for producing wire with
diameter of 1 ,2-2mm for solder, including extrolling by section mill and cold drawing to finished
size. Tests of produced wire during production and maintenance of structural elements for spacecraft
showed that technological characteristics and properties of welded joints exceeds domestic analogue,
previously produced at ?KraMZ?, this wire is quite competitive with wire from alloy 4047 European
production. Another example of implementation of the proposed process was to obtain by specialists
of Metal Treatment under Pressure academic department of ?Siberian Federal University Institute of
Nonferrous Metals and Material Science? wire from alloy 01417? which free from defects granulated
predecessor.
Therefore, extensive materials obtained during development and research of various groups of
rapidly crystallized alloys show the production possibility of semi-finished products with a unique
correlation of physical and mechanical characteristics. Semi-finished products of all groups of these
alloys can and should find wide application in various industries. However, this requires the development
of new, more fuel-efficient than the methods of powder and granular metallurgy. However, this requires
the development of new, more fuel-efficient than the methods of powder and granular metallurgy,
methods for producing compact billets from these alloys milled with disintegrated structure and
conservation of congenital effect of structure during processing from incoming workpieces to semifinished products.
???????? ??????????????
? ??????????? ???????? ??????? ????????
? ??????? ????????????? ???
?????????? ?????????
?.?. ????????
?????????-??????????????? ????? «????»
??????, 660111, ??????????, ??. ?????????????, 103
? ?????? ???????????? ???????? ? ???? ???????? ?????????????? ??????????? ??????? ?
??????? ???????????? ??? ?????????? ?????????. ??????????? ??????????? ???????? ?
??????? ????????????? ??????????? ? ????????????? ??????????? ???????, ? ????? ???????
???????????? ??????????.
???????? ?????: ????????, ????????????????, ??????????? ?????, ?????????????,
???????????? ????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 579-586
~~~
??? 546.78; 54.057;669
Investigation of SHS Process in W-TI-C System
for Production of Tungsten Carbides WC and W2C.
Application of Carbides Mixture
for Cast Iron Modification
Vladimir A. Poluboyarov*, Aleksandr A. Zhdanok,
Zoya A. Korotaeva and Victor A. Kuznetzov
Novosibirsk State Technical University
20 K. Marksa, Novosibirsk, 630073, Russia
Received 06.06.2014, received in revised form 11.08.2014, accepted 16.08.2014
Powders of tungsten and titanium carbides have been produced from the mixture of tungsten,
titanium and soot by the method of self-propagating high-temperature synthesis (SHS) with the use
of mechanochemical treatment (MT). To synthesize tungsten carbides, there has been used SHS of
titanium carbide in the mixture ?tungsten-titanium-soot?, which has further initiated the synthesis
of tungsten carbide (carbides). Optimal conditions for the production of composition with maximum
tungsten content have been found. Powders (mixture of tungsten and titanium carbides) with minimum
particle size of about 30 nm have been produced. It has been revealed that the output tungsten
carbides WC and W2C considerably depends on the composition of mixture ?tungsten-titanium-soot?
and time of its MT. Modifiers, which have been investigated for the processes of intra-mold cast iron
modification, were produced with the use of MT based on SHS products and powders of metals. The
usage of modifiers of the composition 35-40 % WC ч 10-15 % TiC ч 50 % Zr has allowed to increase
Brunell hardness by 13,1 %, tensile strength ? by 19,8 %, relative wear resistance ? by 69 %, corrosion
resistance in hydrochloric acid ? by 28 % of cast iron samples at the content of modifier active particles
being 0,038 %.
Keywords: modification, wear resistance, tungsten and titanium carbides, corrosion resistance, metalprotector, mechanochemical treatment, tensile strength, SHS, cast iron, hardness.
? ????????? ????? ?????? ??????????????? ???????? ? ??????? ???????????????
????????? ??????????? ?????????? ??????????????? ?????????? ??????????. ??? ????
????? ????? ?????????? ? ??????? ???????? ????????? ? ???????????????? ?????????.
?????? ???????? ????????? ??????? ??? ??????? ??????, ??, ? ?????????, ??-?? ????????????????? ??????????? ??? ?? ???????? ?????? ????????? ??????????. ?????????
??????? ????????? (WC) ??????????????? ????????? ? ????????? ? ????? ????????, ????????? ?????????, ???????????? ??????? ??? ????-??????????? ??????? ? ????????? ? ???????, ??????????? ????????? ????????? W(CO)2 ??? ???????????? 900-1630 °? ???????????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: elena@lmltd.ru
# 579 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Poluboyarov, Aleksandr A. Zhdanok? Investigation of SHS Process IN W-TI-C System for Production?
? ??????? [1-3]. ??? ????????? ??????? ????????? W2C ????????? ????? ??????? ???????:
?????????????? ????????? ? ????????? ? ????? ???????? ????????? ??? ???????????? 30003200 °? [2].
???????? ??????? ????????? ?????? W2C ??? WC ??? ?? ?????? ? ?????????????? ???????????????? ??????? [4, 5].
??? ??????? ???????? ????????? ???? ??? ????????? ????? ??? ??????? ?????? ?
????? «????????-?????-????». ??? ??????? ?????? ??????????? ????? ? ?????????? ??????
???????? ?????????. ??? ?????????? ???????? ???? ?????????? ?????? ????????? ??????: ???????? ???????, ??? ??????? ???? ?????? ???????? ????????? WC ? W2C ? ???????
W-Ti-C; ?????????? ??????? ???????????????? ????????? ?? ???????? ???????; ?????????? ???????????????? ?????????? ????? ???????? ? ?????????-???????????? ????????
????????????, ??????? ????? ??????????? ??? ????????? ???????????????? ??????????????? ??????.
????????? ? ?????? ????????????. ??? ?????????? ??????? ???????????? ??????? ?????? ????-2, ????????? ??? ? ???? ??-15. ????? ???????? ?????????? ????????????????
?????????? ? ??????????? ???????????? ?????????? ???-2 ??? 60 g. ???????????? ????????? ????????? ? ??????? 1-5 ???. ????? ??????? ? ???? ???????. ???????? ????????? ???????????? ????????? ??????. ??????? ?????? ????????? ??????? ??????????? ??????? ???. ??
????????? ??? ????????? ??????? ?????? ???????????? (???).
??????? ????????? ????????????????? ?????????? ????????, ??????????? ??? ??????????? WC ? TiC, ? ?????????? ? ? 2 ? 2,5 ????. ? ????????? ?? ??????? WC ? TiC ??????? ?????????? ???? ?????????:
1) 20 % WC ч 80 % TiC (?? 1 ???, ????????????????? ?????????? ????);
2) 40 % WC ч 60 % TiC (?? 1 ???, ????????????????? ?????????? ????);
3) 60 % WC ч 40 % TiC (?? 1, 2, 3 ???, ????????????????? ?????????? ????);
4) 70 % WC ч 30 % TiC (?? 1 ???, ?????????? ???? ? ??????? ? 2 ? 2,5 ????);
5) 75 % WC ч 25 % TiC (?? 1 ???, ?????????? ???? ? ??????? ? 2 ????);
6) 80 % WC ч 20 % TiC (?? 5 ?????, ?????????? ???? ? ??????? ? 2 ????);
7) 50 % WC ч 50 % TiC (??? ??, ????????????????? ?????????? ????).
???????? ?????????????? ?????? ?????? ????? ??20 ? ??25 ????????? ? ???????????? ???? ???-281 ?? ?????????? ????????????????: ??????? ????? 750 ??, ????????? ?????? (????? ? 3%-??? ?????? ???????). ??????? ? ???????? ????? ????????? ??? ???????????
1350-1380 °?. ? ???? ????????????? ???????? ????? ???? ???????????????. ? ??? ????????????? ??? ???????????? ???????, ????? ???????? ???????? ???????????. ????? ??????? ?????????????? ?????????? ????????????. ? ???????? ????????? ??? ????????????
???????? ???? ???????????? ????? ???????-????????? ????? (???). ? ???? ????????????
????????????? ??????? ?? ?????? ????? ???????????? ?????? ???????? (?????? ???????? ? ?
?????????? ??????????????, ??????????? ? ??????????? ??????, ???? ? ??? ????????????, ?? ?????? ?????? ???????? ?????? ??????????? ??????), ??? ?????? ??????? ??????
???????? 20 ??.
?????????????? ???? ????????, ??? ??????????? ?? ????????????? ????? ????????? ?
?????????? ?????????????? ?? ????? ?????? ???????? ?????.
# 580 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Poluboyarov, Aleksandr A. Zhdanok? Investigation of SHS Process IN W-TI-C System for Production?
????????? ??? ?????????? ???????????? ?????????? ???? ???????? ?? ???????? ??????
?? ???? 1497-84. ??????? ???????? ??????? ????????? ?? ?????????? ???????? ?? ????? ??????????, ??? ???????????? ???????????? ?????????? ??????.
????????? ????????? ?? ???????? ????????? ?? ??????? ???? ??-2. ?? ?????? ????????????? ??????? ?????? ?? ????? ???? ??????????. ?????????? ?????? ?????????? ?? ??????????, ???????????????? ?? ??????????? ???????.
????????????? ??????????????? ?????????? ?? ???? 17367-71 ? ???????? ????????? ??
?????????? ??????????? ??? ?????? ? ???????????? ?????????? ???????.
???????????? ????????? ??????????? ?? ???? 9.908-85. ????????? ????????? ?
25%-??? ??????? ??????? ? ? 25%-??? ?????? ???????.. ?????????? ?????? ???? ???????????
??? ?????????????? ???????? (?????????? ?? ??????? ? ????? ? ???????? ????? 10 %). ??????? ???????? ? ???????? ?????? ??? ????????? ??????????? (20 °?). ????? 24 ? ???????
???????? ?? ?????????, ????????? ????? ? ???????? ?????? ????? ????????????????? ?
???????????? ????????.
?????????? ???????????? ???????? ???. ??? ???? ?? ???? ????????. ????????? ????????, ??? ??? ???????? ?????????? ?????? ? ????? ??????? ???? ? ??????? ?????????.
? ????? ??????? «1» (20 % WC ч 80 % TiC, ?? 1 ???) ?????? ????????? WC ?? ??????????.
?????????? ?????? W2C ? ???????? ??????? ?????????. ????????? ?????, ??????????? ? ?????
???? ????? 3200 °?, ??? ??? ???????? ???????? ? ????????????? ?????????.
? ?????? ??????? «2» (40 % WC ч 60 % TiC) ? «3» (60 % WC ч 40 % TiC) ? ??????? ??
1 ??? ????? ??????????? W2C ? ????????, ?? ? ????????? ??????????? ??????????? WC.
??? ??????? «3» (60 % WC ч 40 % TiC) ???? ????????? ????? ?? ?? 2 ? 3 ???. ??????????, ??? ?????????? ??????? ??????????????? ?? ????? ???????? ? ?????????? ??????????
???? WC ? ????????? ???, ?? ????? ???????????? ???? W2C ? ????????? (???. 1).
????? ???? ??????????? ??????????? ??????????? ??? ? ???????? ? ???????????
??????????? ??????. ????? ??????? «6» (80 % WC ч 20 % TiC), ???????????? ? ??????-
???. 1. ?????????????? ????????? ??? ????? ??????? «3» (60 % WC ч 40 % TiC), ??????????????? ??
3 ???
# 581 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Poluboyarov, Aleksandr A. Zhdanok? Investigation of SHS Process IN W-TI-C System for Production?
???. 2. ?????????????? ????????? ??? ????? ??????? «5» (75 % WC ч 25 % TiC), ?????????? ???? ? 2
???? ?????? ??????????????????, ??????????????? ?? 1 ???
?????????? ?????????? ?? 1 ?? 3 ???, ?????? ?? ???????. ??? ?????????? ??????? ????????? ????? ?? 5 ??? ? ?????????? ???? ? 2 ???? ?????? ?????????????????? ??????????
? ????????? ??????? ????????? WC, ? W2C ???????????. ? ????? ??????? «5» (75 % WC ч
25 % TiC) ??????? ???????? ??? ????? ??????????????? ?? ? ??????? 1 ???. ????? ???
? ????????? ??????? ?????????? ????????? ?????????? ???? W2C ?????? ???????? ???
WC ? TiC (???. 2).
??????? ??????? «4» (70 % WC ч 30 % TiC) ? ??????????? ???? ? 2 ? 2,5 ???? ?????? ?????????????????? ?????????? ???? ?????????? ? ???-2 ? ??????? 1 ???. ?? ???????????????
????????? ??? ???????????? ???? WC, W2C ? W. ??????????, ??? ?????????? ??????????
???? ????? ??? ? ??? ???? ?? ?????????, ??? ??? ??? ?? ???????? ? ???????? ?????? ???? ??????? ????????? WC.
??? ???????????? ????????? ????? W-Ti-C ?????????? ?????? ??? ??????????? 1ч1, ??????????????? ??????? «7» (50 % WC ч 50 % TiC). ????? ??? ? ????? ???????? ????? ?????????
? ??????? ?????????? ???? W2C (???. 3).
? ??????? 1 ????????? ?????? ?? ???????? ??????????? ? ???????? ????????????,
???????????? ?? ??????????????? ??? ????????? ???: WC, W2C ? TiC. ????????? ?????,
?? ????????? ??????? ???????????? ???, 2?, ????????: 41,85 ??? TiC, 39 ??? W2C, 35 ? 48
??? WC.
????????? ?????????????. ??? ??????????????? ??????? ? ???????? ???????????? ??????? ? ??????????? ????????? 70-80 % ? ????????? ?? WC.
?????? ?????? ????? ???????? ?????? ? ?????????, ?????????? ??????? ???, ?? ????????? ?????? ??????????? ??????????? ??????????? ?????????? ????? 100 ?? (???. 4).
??? ????????? ????????????? ????? ?????????? ???????? ??? ????? ?????????? ????????? ? ??????????? ??????????? ????????? ? ?????????? ????????? (?r, Ni, Fe, Zr). ??????,
??????? ?? ???? ? ????. 2. ??????? ?????? ?????? ????????????? (????????? ? ????. 2), ???????????? ?? ?????? ???????? ???????????, ?????????? 44-139 ??. ??? ?????????????? ????# 582 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???. 3. ?????????????? ????????? ??? ????? ??????? «7» (50 % WC ч 50 % TiC), ?????????? ???? ? 2
???? ?????? ??????????????????, ??? ??
?
??????
?????????? ????
????? ??
??
???, ???
??? ??
W2C, ??
??? ??
TiC, ??
??? ??
WC, ??
S??, ?2/?,
?? ?????
???
1 ???
??????? 1. ?????? ???????????? ????????? ???
1
20 % WC/80 % TiC
????????????
1
30,16
32,72
-
-
2
40 % WC/60 % TiC
????????????
1
36,69
38,65
-
-
3
60 % WC/40 % TiC
????????????
1
31,24
32,68
-
-
4
60 % WC/40 % TiC
????????????
2
26,39
29,34
29,05
-
5
60 % WC/40 % TiC
????????????
3
26,39
25,02
25,62
-
6
70 % WC/30 % TiC
??????? ? 2 ????
1
28,16
28,37
33,52
6,12
7
75 % WC/25 % TiC
??????? ? 2 ????
1
-
34,03
34,85
-
8
80 % WC/20 % TiC
??????? ? 2 ????
5
-
28,35
33,50
18,45
9
100 % TiC
????????????
1
-
35,42
-
9,59
???. 4. SEM-??????????? ???????, ??????????? ??????? ??? (????? ??????? 30 % TiC ч 70 % WC)
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Poluboyarov, Aleksandr A. Zhdanok? Investigation of SHS Process IN W-TI-C System for Production?
??????? 2. ??????, ??????? ?? ? ???????? ?????????????
????????
?
1
2
3
4
5
6
7
???????? (?)
?????? (??)
?????? ??????
(???)
?r
?r
Ni
Fe
Zr
????? ????????
????????? ?
?????? (???)
?????????
? ч ??
1ч1
1ч1
1ч1
1ч1
1ч1
??, ???
S??., ?2/?
1
2
1
1
1
1
1
9,59
7,11
10,10
11,71
8,99
10,08
5,48
???????? ???????? ????????? ?????????????? ??????, ????? ????? ?????????? ???????????
(7), ?????????? ?????? ??????????.
?????????? ???????????? ????????? ???????????????? ??????????????? ??????
????????????? ??????? (WC-TiC) ? ????????-??????????? ????????? ???????????? ? ????.
3. ?????????? ?????????? ????????? (13,1 %) ? ??????? ????????? ?? ?????????? (19,8 %) ??????????? ? ?????? ??? ???????????? ???????? ?????? ???????????? 0,038 % (??????? 1). ???
???????? ???????????? ???????? ?????? ? ??? ???? (??????? 2, ???????????? 0,013 %) ?????????? ????????? ????????? 4,9 %, ? ??????? ????????? ?? ?????????? ? 8,5 % ????????????
???????????? ??????? (3).
????????????? ??????????????? ??????, ????????????? ????????????? ??? ???????????? ???????? ?????? ???????????? 0,038 %, ??????????? ?? 69 %, ???????????? ????????? ?
??????? ??????? ? ?? 28 % ?? ????????? ? ??????????? (??????????????????) ???????? (3).
???????????? ????????? ? ?????? ??????? ?? ??????????.
??? ?????????? ???????????? ???????? ?????? ???????????? ?? 0,1 % ?????? ?????????
???????? ?? 5,2 % (??????? 4), ? ???????????? ????????? ? ?? 18 % ???????????? ????????????
??????? (5). ??? ??????? ? ???, ??? ??????????? ???????????? ??????? ???????????? (???????? ??????) ????????? ? ??????? ???? 0,1 %.
??????? ????????, ??? ????????? ?? ???????? ?? ??????????, ?? ? ?????????????????
??????? (4) ??????????? ?????????? ???????????? ?? ??????? ??????? ? 197 ?????? ?? ????
?????????? ??????, ? ??????? ?? ???????????? ??????? (5), ??? ??????????? ??????? ????????
? ???????? 197-201 ??.
??????
1. ??????? ??????? ????????? ??? ???????? ????????? WC ? W2C. ? ???????? «1» (20 %
WC ч 80 % TiC), «2» (40 % WC ч 60 % TiC), «3» (60 % WC ч 40 % TiC), ??????????????
???????????? ? ??????? 1 ??? ? ?????????? ????????????????? ?????????? ????, ?????????? ???? W2C, ? ? ????????, ???????????? 2, 3 ???, ?????????? ???? WC. ? ????????
(70 % WC ч 30 % TiC), ?????????? ?????????? ???? ?????? ?????????????????? ? 2 ? 2,5
????, ??????????? ??? ???????. ? ??????? (80 % WC ч 20 % TiC), ???????????? 5 ???, ?
?????????? ???? ? 2 ???? ???????, ??? ?????????????????, ?????????? ?????? WC.
# 584 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Poluboyarov, Aleksandr A. Zhdanok? Investigation of SHS Process IN W-TI-C System for Production?
??????? 3. ???????? ???????? ??????
????????? ??
????????, HRB
???????
?????????, %
??????
????????? ??
??????????, ???
??????? ???????
????????? ??
??????????, %
??????????
???????????????,
%
???????????
????. ?????????
? ??l, %
1
2
3
4
5
??????????
???????? ????,
%
1
???????? ???????? ??????
??????
????????????
?
???????????
????? ??????
??????? ??????
2
3
4
5
6
7
8
9
10
(WC-TiC) + Zr
(WC-TiC) + Zr
???????????
(WC-TiC) + Zr
???????????
0,038
0,013
0
0,1
207,0
192
183
197
198,3
13,1
4,9
0
280,5
254,0
234,2
264,7
279,2
19,8
8,5
69
28
??-20
??-25
-5,2
-18
2. ????????? ????????????????? ??????? ????????? ??????? ??? ????? ? ???????????? ??????????? ??????? ????????? WC ? ??????? W-Ti-C, ??????????????? ???????:
«6» 80 % WC ч 20 % TiC (5 ??? ??), ???? ????? ??????????????? ?? ?????????? 1 ???,
?? ???????????? ?????????? ??????? ????????? ??? ??????????? ??? ????????? ??
75 % (?????? «5», 75 % WC ч 25 % TiC).
3. ??????? ??????? ????????? ????? ???????? ????????? ? ?????? ? ??????????? ???????? ?????? ??????? 30 ??.
4. ??????????, ??? ????? ???????? ????????? ??????? ?? ??????? ????? «????????-?????????» ? ??????? ?? ???????????????? ?????????.
5. ?????????? ????? ????????? ??? ? ???????? ???????? ? ?????????? ??????? ??????????? ??? ??????????????? ????????? ??????, ??????? ????????? ????????? ?????????
?? ???????? ?? 13,1 %, ?????? ????????? ?? ?????????? ? ?? 19,8 %, ?????????????
??????????????? ? ?? 69 %, ???????????? ????????? ? ??????? ??????? ? ?? 28 % ???
???????????? ???????? ?????? ???????????? 0,038 %.
?????? ??????????
[1] ???. ?? ? 2414992 ?????? ????????? ??????????? ??????? ????????? / ??????? ?.?.,
???????? ?.?., ???????? ?.? ? ??. // ?????. 27.03.2011.
[2] ?????????? ?.?. ???????. ?., 1968. 300 ?.
[3] ???. ?? ? 2418742 C????? ????????? ??????-??????????????? ??????? ??????? /
??????? ?.?., ?????????? ?.?. // ?????. 20.05.2011.
[4] ???. ?? ? 2388689 ?????? ????????? ??????? ????????? W2C / ???????? ?.?., ?????? ?.?. // ?????. 10.05.2010.
[5] ???. ?? ? 2394761 ?????? ????????? ??????? ????????? WC / ???????? ?.?., ?????? ?.?. // ?????. 20.07.2010.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Poluboyarov, Aleksandr A. Zhdanok? Investigation of SHS Process IN W-TI-C System for Production?
???????????? ???????? ??? ? ??????? W-TI-C
??? ????????? ???????? ????????? WC ? W2C.
?????????? ????? ????????
??? ??????????????? ??????
?.?. ??????????, ?.?. ??????,
?.?. ?????????, ?.?. ????????
????????????? ??????????????? ??????????? ???????????
??????, 630073, ???????????, ??. ?. ??????, 20
??????? ??????????????????????? ???????????????????? ??????? (???) ?? ?????
?????????, ?????? ? ???? ? ?????????????? ???????????????? ????????? (??) ????
???????? ??????? ???????? ????????? ? ??????. ??? ??????? ???????? ????????? ???
??????????? ??? ??????? ?????? ? ????? «????????-?????-????», ??????? ?????
??????????? ?????? ???????(??) ?????????. ??????? ??????????? ??????? ??? ?????????
??????? ? ???????????? ??????????? ?????????. ???????? ??????? (????? ????????
????????? ? ??????) ? ??????????? ???????? ?????? ??????? 30 ??. ??????????, ???
????? ???????? ????????? WC ? W2C ??????????? ??????? ?? ??????? ????? «?????????????-????» ? ??????? ?? ??. ?? ?????? ????????? ??? ? ???????? ???????? ?
?????????????? ?? ???????? ????????????, ??????? ???? ??????????? ??? ?????????
???????????????? ??????????????? ??????. ?????????? ????????????? ??????? 3540 % WC ч 10-15 % TiC ч 50 % Zr ????????? ????????? ????????? ?? ???????? ?? 13,1 %,
?????? ????????? ?? ?????????? ? ?? 19,8 %, ????????????? ??????????????? ? ?? 69 %,
???????????? ????????? ? ??????? ??????? ? ?? 28 % ???????? ?????? ??? ????????????
???????? ?????? ???????????? 0,038 %.
???????? ?????: ???????????????, ???????????????, ??????? ????????? ? ??????,
???????????? ?????????, ??????-?????????, ???????????????? ?????????, ?????? ?????????
?? ??????????, ???, ?????, ?????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 587-595
~~~
??? 669.71
Development of Annealing Conditions
wire Rod Alloy of Al-Zr System
to Reach Required Properties
Viktor A. Berngardt*a, Tatiana N. Drozdovaa,
Tamara A. Orelkin?a, Sergey B. Sidelnikova,
Olga V. Fedorovaa, Leonid P. Trifonenkovb,
Viktor F. Frolovb and Aleksandr V. Salnikovb
a
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
b
RUSAL ETC
37/1, Pogranichnikov Str., Krasnoyarsk, 660111, Russia
Received 07.03.2014, received in revised form 15.07.2014, accepted 11.08.2014
In this article was considered the influence of continuous and stepped annealing on resistivity and
mechanical properties of dilute alloy wire rod of a Al-Zr system for reaching of required properties.
There was determined the connection between concentrations of alloying elements, structure and
properties of investigated alloys wire rod. The stepped heat treatment conditions was developed and
recommended for application at the factories of aluminum industry, that allows producing wire rod
with properties of international standards.
Keywords: alloy of a Al-Zr system, wire rod, annealing, resistivity, microstructure, mechanical
properties.
????????
???????? ?????????????????? ?????????????? ? ??????????? ???????? ?????????????
?? ????????????? ???????????????? ??????????, ??????? ????????? ??????? ????????? ???
???????????????? ????????. ?????????????? ?????????? ??????????? ??????????? ? ??????? ??????????????????? ? ?????????? ?? ??????????? 250 °? ???????? ????????????????
????????? ??????????? ??????. ????????????? ????????? ?????????????????? ? ???????????? ??????? ????? ??????? ??????????? ???????????? ? ?????????????-??????????? ?????????? [1-6]. ?????????????? ??????????? ???????????? ?????????????? ?? Al-Zr ???????, ????????????? ?? ??????????? ?????????? ????? ? ????????? ?????????, ???????? ????????????
??????? ??????????????? ?????????? ?? ????????? ? ???????? ????????????? ?????????????
????????? [1, 2]. ???????? ?????????????? ?? ???????????????? ????????? ??????? ???????????? ? ???????????? ??????? ????????, ???????? ???????????? ? ??????????? ???????????
?????????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: Berngardt19@mail.ru
# 587 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktor A. Berngardt, Tatiana N. Drozdova? Development of Annealing Conditions wire Rod Alloy of Al-Zr System...
???????? ????? ?????? ???? ???????? ??????? ?????? ?? ???????? ????????????? ????????????? ? ???????????? ???????? ??????? ?? ???????????????? ??????? ??????? Al-Zr ?
?????? ????????????? ???????? ??? ?????????? ????????? ?????? ???????.
?? ?????????????? ????????? ASTM B941-05 ???????? ????????????? ?????????????
(???) ??????? ?? ?????? ????????? 0,0285 ??·??2/?, ????????? ????????????? ??????? ?????????? ?? ????? 120 ???, ????????????? ????????? ? ?? ????? 8 %.
???????? ????????????
????????? ???????????? ???? ??????? ??????? ?? ????????????????? ???????
Al-0,2 %Zr; Al-0,24 %Zr; Al-0,27 %Zr. ????????? ?????? ???????? ???????? ?????????? ?????????? ??????, ??????? ??????? ??? ??????????????? ?????????? ??????????????.
??????? ????????? 9,5 ?? ?? ??????? ??????? Al-Zr ????????????? ??????????? ??????
????????? ?? ?????? ???????-?????????? ???????? (???) ? ??????????? ???????? ?????????
?? ?????????????? ????????? ?????.
???????? ????????????? ????????????? ??????? ???????? ? ??????? ??????? «?????»
?? ????????? ????? 1 ? ? ???????????? ? ???? 7229-76. ????????? ?? ?????????? ???????? ??
??????? ????????? ?? ?????? Walter+Bai ?G LFM 400 kN.
???????????? ?????????????? ??????? ???????????? ?? ?????????? Carl Zeiss Axio
Observer ?1m. ???????? ????????? ???????? ??????? ????? ???????? ????????????? ? ???????????, ????????? ?? ??????? ???????? ?????????? ? ?????? ??????. ??????? ?????? ??
???????? ???????? ? ??????? ?????????????? ????????????? ?????? ? ?????????? ????????? ATM Kristall 620. ??????? ????? ????????????? ????????? ? ?????????????? ?????.
???????????? ?????? ??????????? ???????????? ???????? ?? ??????? ?????????? ???????
?????????????????????????? ??????? ?? ????????? ??????????? ?????????? Carl Zeiss EVO
50 ? ?????????????? ???????????????????? ???????????? INCA Energy.
???????????? ????????? ? ??????? ??????? ???????
??????? Al-Zr ? ??????????????? ?????????
?? ????????? ????? ?????? ????????? ???????????? ??????? ? ????????? ??????? ?? ???????????????? ??????? ??????? Al-Zr ? ??????????????? ?????????. ?????????? ??????????? ???????????? ??????? ? ????????? ?????????????? ????????????? ????????? ???????
????????? ? ????. 1.
????????, ??? ????????? ?????????? ???????? ? ??????????? ????????? ????????????
?? ?????? ?? ????????? ???????. ???????????? ??????? ?, ??????????????, ??????????? ? ????????????? ?????????????? ??????????? ??????????? ? ??????????? ???????????? ???????? ? ??????.
???????????? ????????? ????????? ?????????????? ????????????? ? ?????? ???????????? ???????? ????????????, ??? ?? ???????????? ? ????????. ???????? ??? ??????? ? ??????????????? ????????? ????????? ??????? ??????????? ????????? ?????????? ?????????
ASTM B941-05.
???????????? ????????? ??????? ??????? Al-Zr ? ??????????????? ????????? ?? ??????? ????????? ?????????? ???? Al3Zr, ??? ??????????????? ? ?????? ??????????? ???????? ?
# 588 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktor A. Berngardt, Tatiana N. Drozdova? Development of Annealing Conditions wire Rod Alloy of Al-Zr System...
??????? 1. ???????? ??????? ??????? ??????? Al-Zr ? ??????????????? ?????????
????????????
Zr, %
?20, ??·??2/?
??,???
?, %
0,20
0,03178
141
12
0,24
0,03272
142
9
0,27
0,03297
142
7
?
?
???. 1. ?????????????? ???????? ??????? ?????? Al-0,27 %Zr ? ??????????????? ?????????:
? ? ? ??????? ????, Ч500; ? ? ? ?????????????? ?????, Ч50
??????????? ??????? ???????? ??? ????????????? ??????. ?????????????? ???????? ??????? ?? ??????????????? ? ??????????? ???????? ????? ????????????? ????????? ?-????????
???????? ?? ?????? ???????? ? ????????????? ?? ???????? ?????????? ????? ?????????
?????????? ???, ??????? ???????? ???????????? (???. 1).
????????????????????????? ?????? ???????? ??????? ? ??????????????? ????????? ??????? ??????????? ? ????????? ??????????? ??????? ?????????? ???, ?????????? (Al, Fe, Si).
???????????? ????????? ? ??????? ??????? ???????
??????? Al-Zr ? ?????????? ?????????
?????????? ?????????? ASTM B941-05 ?? ??? ? ???????????? ????????? ? ??????? ???????????????? ????????? ??????????? ??????? ???????? ????? ??????????? ???????????
?????????.
???????????? ??????? ?? ???????? ?????????? ??? ??????????? ????????? ???????????
???????, ? ??? ????? ? ??? ??????, ????????? ????????. ????????, ??? ??? ?????? ???????????????? ????????? ??????? ??? ???????????? 300-600 °? ???? ???????? ??? ??????????, ??? ?
?????????????. ????????????? ????????? ??? ?????? Al-Zr ??????? ??????????? ???????? ????????????? ???????? ???????? ? ???????????? ?????? ??????????? ?????????????? ???? Al3Zr
(L12). ???????? ??? ?????????? ?????? ? ??????? ???????????? ????????? ??????????? ?????????? ???????? ????????????????, ?.?. ???????????? ???????????? ?????????? ??? ??????
???????. ???????? ???????? ? ????????????????, ??????????? ??? ?????? ???????????????
??????????????, ????? ??????????? ?????? ?? ???????? ? ???????? ? ????????????? ???????.
# 589 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktor A. Berngardt, Tatiana N. Drozdova? Development of Annealing Conditions wire Rod Alloy of Al-Zr System...
?????????????????? ????? ??????? ????????? ???????????? ?????????? ?????????
? ??????? ???????? ?, ??????????????, ??????? ???????? ????????????? ?????????????. ???????? ????????????? ??????? ?? ????????? ????????? ?????????????? ????????????? Al-Zr
??????? ??????, ???????? ????????? ???????? ???????? ?????? ????????????? ?????????
???????? ???????? ? ?????????? ????????????? ?????? ???? Al3Zr [4-6].
???????????? ????????? Al-Zr ??????? ??? ??????????? ???????????, ?.?. ??????????????, ????????????, ? ?????????, ????? ????????????? ???????? ???????? ? ???????? ?
????????????? ?????????? ?????? ???????????????.
? ?????? ??? ???????? ??? ??????? ?? ??????????? ??????? ????????? ???????????
? ??????????? ?????????????????? ????? ??? ???????????? ?? 300 ?? 500 °? ? ?????????
3-48 ?. ??????????? ? ???????????? ?????? ?????????? ?????? ??????? ????????????? ???????? ????????, ????????????? ? ???????????? ????????? ???? Al3Zr, ????????????????????
????????, ? ? ?????????? ???????? ???????????????????? ? ????????? ???????.
? ??????? 2 ???????????? ???????? ??????????? ??????? ??????? Al-Zr ? ?????????? ????????? ????? ?????????? ???????? ??? ???????????? 300?450 °?. ?? ??????????? ?????????
???? ????????? ??????????? ??? ??????? ?? ???????????????? ????????? ???????????
??????? ?? ???????, ??????????? ? ???????????? ???????????? ?????? (???. 2).
?????? ???????? ??? ??????? ?? ??????????? ??????? ???????, ??? ??? ????????? ?????????? ???????????? ?????? ?????????? ???????? ??? ?? ???? ??????????. ???????? ?????,
??? ????????????????? ?????? ??? ???????????? 350 ? 400 °? ??????????? ?????? ?? ???????? ??? ? ??????? ? ?????? ????????????? ???????? ??? ?????????? ????????? ?????? ????????? (????. 2). ??????????? ???????? ??? ??????? ???????? ????? ?????? ??? ?????????
36 ? ????? ?????.
??????? 2. ???????? ??????? ??????? ??????? Al-Zr ? ?????????? ?????????
?????
Al-0,2 % Zr
Al-0,24 % Zr
Al-0,27 % Zr
????? ??????
?, ??·??2/?
??, ???
?, %
300 °?, 36 ?
0,02958
127
20
350 °?, 24 ?
0,03186
121
25
350 °?, 48 ?
0,03073
118
25
400 °?, 48 ?
0,03019
117
29
450 °?, 48 ?
0,03059
86
32
300 °?, 36 ?
0,03110
131
18
350 °?, 24 ?
0,03168
134
22
350 °?, 48 ?
0,03194
131
23
400 °?, 48 ?
0,03100
123
24
450 °?, 48 ?
0,03037
112
27
300 °?, 36 ?
0,03034
134
18
350 °?, 24 ?
0,03275
136
22
350 °?, 48 ?
0,03024
135
19
400 °?, 48 ?
0,03066
131
24
450 °?, 48 ?
0,03016
115
26
# 590 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktor A. Berngardt, Tatiana N. Drozdova? Development of Annealing Conditions wire Rod Alloy of Al-Zr System...
?
?
?
???. 2. ??????????? ????????? ?????????????? ????????????? ?? ??????????? ? ???????????? ??????
???????: ? ? Al-0,27 %Zr; ? ? Al-0,24 %Zr; ? ? Al-0,2 %Zr
???????? ?????? ??????? ???????????? ?????? ?? ???????????? ???????? ??????? ?? ??????????? ???????. ????? ?? ????????? ??????? ??????? ????????? ? ???????? ???????????? ???????, ??? ??????? ? ?????????? ???????? ? ????????????????. ???????????? ??????
??? ???????????? 300?450 °? ????????????? ?????? ?? ????????? ????????????? ??????? ?
????????????? ????????? ??????????????.
? ?????????? ??? ???????????? ???? 400 °? ??????? ?? ?????????????????? ?????? Al0,2 %Zr ??????????? ???????? ?? ????????????? ???????? ?????????. ????? ??? ???????????? 350 ? 400 °? ??????? ????????? ????????????? ??????? ??????? ?? ??????? Al-0,27 %Zr ?
Al-0,24 %Zr, ?????? ???????? ????????? ????????? ????????? ???? ??????? ? ???????????
????????????????? ??????, ??? ????? ???? ??????? ? ?????????? ?????? ??????????? ?????????????? ???? Al3Zr ??? ??????? ????????????? ????????? ?-???????? ????????.
????????? ????????????? ??????? ??????? ?? ?????? Al-0,24 %Zr ????? ?????? ??? ???????????? 430 ? 450 °? ?????????? ????? 120 ???, ??? ???? ??????????? ?????? ?????????.
???????????? ????????????? ? ?????? Al-0,27 %Zr ???????? ??? ?????? ??? ???????????
500 °?, ??????? ?????? ??????????? ? ?????????? ???????????? ?? ?????????????.
????????? ????????? ??? ?????? ??????????????? ?????????????? ??????? ??? ?? ????????? ??????? ???????? ????????, ??? ? ?? ????????? ???????? ??????????. ??? ????????? ????????? ???????????????? ? ??????????? ????? ????? ? ?????????? ????????? ???? ???????
?????????????? ???????? ????????? ??????? ? ?????????????? ????? ????? ????????? ???????? ?????? (???. 3).
# 591 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktor A. Berngardt, Tatiana N. Drozdova? Development of Annealing Conditions wire Rod Alloy of Al-Zr System...
?
?
?
???. 3. ?????????????? ??????? ? ?????????? ????????? ?50: ? ? Al-0,2 %Zr; ?, ? ? Al-0,27 %Zr;
?, ? ? 450 °?, 48 ?; ? ? 500 °?, 24 ?
????????, ??? ???????? ??????????? ???????? ????????????? ????? ????????????????
??? ?????? ??????????? ???????. ??????? ????? ??????????? ??????? ?? ??????? 350 °?,
24 ? ? 400 °?, 48 ? ?? ???????? ? ????????? ???????? ?????????, ? ? ??????? ???????????
?????????????, ??????????? ??? ???????????????? ?????????. ?????? ??? ?????? ???? ??????????? 400 °? ? ????????? ????????? ??????? ???????? ?????? ?????????? ????? ? ????????? ???????? ??????????????? ????????? (???. 3?). ?????????????, ? ??????? ?? ???????????????? ????????? ???????, ?????????? ? ?????????????? ???, ??? ??????? ???? 400 °?
???????? ????? ????????????????.
????????? ???????????? ???????? ? ??????? ???????? ???????? ? ?????????? ??? ?????? ????????? ?????????? ????????? ???? Al3Zr, ??????? ?????????? ??????????? ???????? ????????????????, ??????? ? ?????? Al-0,27 %Zr ?????????????????? ????????? ??????????? ?????? ??? ?????? 500 °?, 24 ? (???. 3?). ???????????????? ???????? ????????? ?
?????? Al-0,2 %Zr ??? ?????? ?? ?????? 450 °?, 48 ? (???. 3?) ? ???????? ? ??????? Al-0,24 %Zr;
Al-0,27 %Zr. ????????????? ????????? ? ???????? ????????? ??????? ?????? ?? ??????? ????????? ??????? ????? ???????????????? ??????.
????? ???????, ??????????? ????? ??????????? ??????? ?? ????????? ??????? ????????? ??????? ????????? ????? 120 ???, ?????? ?? ????????? ??????????? ??????? ???. ????
????????, ??? ??? ???????? ??? ??????? ??? ??????????? ?????? ?????????? ????????????
?????????? ????????.
??? ???????? ????????? ???????????????????? ????????? ?? ???????????????? ???????
??????? Al-Zr ?????????? ???????? ????????????? ???????????? ??????????? ????? [1-3]. ?
# 592 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktor A. Berngardt, Tatiana N. Drozdova? Development of Annealing Conditions wire Rod Alloy of Al-Zr System...
?????? ?????? ??????????? ? ?????????? ????? ?????? ???????????? ?????? ??? ??????? ?
???????? ??????? ???????????? ??????? ? ???.
????????? ?????????? ???????? ? ?????? ?????? ?????????? ??? ?????????????????? ?????? ?????????? ?????????? ????????? ?????????????? ??????????? ???? Al3Zr.
??????? ????????? ???????????? ???? ????????? ?? ??????? ?????? ? ???????????? ????????????? ???????? (Al-0,27 %Zr), ??????? ? ?????????? ????????? ????? ??????? ??????? ????????? ? ?????????? ????????????????????? ?????????, ????????????? ?? ??????????? 450 °?.
?????? ??????????? ?? ??????? ?????????? ???????????? ?????? ?? ????????? ? ????????
??????? ?? ?????? Al-0,27 %Zr ???????? ??????? ????????? ??????? ?????? ??????? ??????,
???????????? ??????????? ????????? ????????? ? ???. ??????????? ?????? ??????? ?????? ?????? ?????????? ????? ?????? ?????? ????????????? ???????? ???????? ? ??????????
?????????? ?????????? ??????????? ?????? ???? Al3Zr ?? ??????? ???????, ????????????
?? ?????? ??????? ??????. ?????????? ?????????????? ???????? ???????? ??? ???????????
?????? ??????? ?????? ?????????????? ???????? ???. ??????????? ?????? ????????????
??????, ? ????? ???????? ?????????? ????????????? ??????? ? ??? ??????? ?? ?????? Al0,27 %Zr ????????? ? ????. 3.
???????????? ?????????????? ????????, ??? ? ?????? Al-0,27 %Zr ????? ????????? ??????? ???????????????? ?????? ???????? ???????? ??????????????????? ?????????, ?????????????? ?????????? ??????????? ??????? ??????? (???. 4).
??????? 3. ???????? ??????? ?????? Al-0,27 %Zr ? ?????????? ?????????
?????
?????????
?????????
????? 300 °?, 36 ?
?20, ??·??2/?
??, ???
?, %
0,03034
134
18
???????????
????? 300 °?, 36 ?. + ?????? ???????
0,02779
127
25
?????????
????? 350 °?, 48 ?
0,03024
135
19
???????????
????? 350 °?, 48 ?. + ?????? ???????
0,02803
134
23
?
?
???. 4. ?????????????? ??????? ?????? Al-0,27 %Zr ????? ???????????????? ??????,Ч100: ? ? 350 °?,
48 ? + ?????? ???????; ? ? 400 °?, 12 ? + ?????? ???????
# 593 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktor A. Berngardt, Tatiana N. Drozdova? Development of Annealing Conditions wire Rod Alloy of Al-Zr System...
?????????? ???????? ?????????? ????????????? ??????? ? ????????? ???????????????????? ???????, ?????????? ?? ??????????? ??????? ???????????? ??????, ?????????????
??????????? ?????????????? ????????? ASTM B941-05.
? ?????????? ??????????? ???????????? ??? ????????????? ????????? ? ????? ??????????? ????????? ???????? ??????? ?? ????????? ? ??? ???????, ????????????? ?? ?????? Al0,27 %Zr, ???????????? ??????????? ????? ? ???????????? ?????? ??????? 300 °?, ?????????
36-48 ?. ????????????? ????? ?????? ??? ????????? ?? ???????? ??????????? ??????. ?????????? ??????? ?? ?????? Al-0,27 %Zr ??????????????? ??????????? ?????????????? ????????? ASTM B941-05.
??????
1. ????? ??????? ?? ???????????????? ??????? ??????? Al-Zr ??? ????????????
300-500 °? ? ????????? 3-72 ? ?? ???????????? ?????????? ???????? ??? ??
0,0285 ??·??2/?.
2. ??????????? ? ???????????? ???????? ?????? ???????????? ?????? ??????? ?? ??????? Al?0,24 %Zr?0,28 %Fe ? Al?0,27 %Zr?0,27 %Fe ????????? ???????? ????????? ???????
??? ? ???????????? ???????.
3. ??? ??????????? ????????? ???????? ??????? ?? ????????? ? ??? ??????? ??????
Al-0,27 %Zr ??? ????????????? ????????? ???????????? ??????????? ????? ? ????????????
?????? ??????? 300 °?, ????????? 36-48 ?. ???????, ?????????? ?? ???????? ???????????
?????? ?? ???????????????? ??????, ????????????? ???????? ??????????? ??????????????
????????? ASTM B941-05.
?????? ??????????
[1]. ??????? ?.?., ???????? ?.?., ??????????? ?.?., ?????? ?.?. // ???????? ??????. 2011.
???. 5. ?. 33.
[2]. ??????????? ?.?., ???????? ?.?., ??????????? ?.?. ? ??. // ??????? ???????????????
???. ????. ??-?? ??. ?.?. ??????. 2012. ???. 1. ?. 51.
[3]. ????? ?.?., ????????????? ?.?. // ???. ???. ?????? (?????? ???. ???. ??-?? ??. ?.?.
??????????). 2001. ?. XLV. ???. 5-6. ?. 15.
[4]. ????? ?. ?., ?????? ?. ?., ???????? ?.?. // ??????? ???????. 2009. ???. 10. ?.65.
[5]. ????? ?. ?., ?????? ?. ?., ???????? ?.?. // ???????? ?????. ??????? ???????????.
2009. ???. 4. ?. 42.
[6]. ????? ?. ?., ?????? ?. ?., ???????? ?.?., ???????? ?.?. // ?????????????? ? ??????????? ????????? ????????. 2012. ??? 4. ?. 14.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktor A. Berngardt, Tatiana N. Drozdova? Development of Annealing Conditions wire Rod Alloy of Al-Zr System...
?????????? ??????? ?????? ???????
?? ??????? ??????? Al-Zr
??? ?????????? ????????? ????????? ???????
?.?. ??????????*, ?.?. ?????????,
?.?. ???????? , ?.?. ????????????, ?.?. ?????????,
?.?. ????????????, ?.?. ???????, ?.?. ??????????,
?
????????? ??????????? ???????????
??????, 660041, ??????????, ??.?????????, 79
?
??? «????? ???»
??????, 660111, ??????????, ??. ?????????????, 37 , ???. 1
?
? ?????? ??????????? ??????? ???????????? ? ???????????? ?????? ?? ????????
????????????? ????????????? ? ???????????? ???????? ??????? ?? ????????????????
??????? ??????? Al-Zr ??? ?????????? ????????? ?????? ???????. ??????????? ????? ?????
????????????? ?????????? ?????????, ?????????? ? ?????????? ??????? ?? ???????????
???????. ?????????? ? ???????????? ??? ????????? ?? ???????????? ???????????
?????????????? ??????????? ????? ??????????? ?????????, ??????????? ????????
??????? ? ??????????????? ??????? ??????? ?????????????? ?????????.
???????? ?????: ?????? ??????? Al-Zr, ???????, ?????, ???????? ?????????????
?????????????, ??????????????, ???????????? ????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 596-604
~~~
??? 621.128
Decrease of Nitrogen Oxides
in the Combustion Process Kansk-Achinsk Coal
Andrey V. Zhuikov* and Anatoliy I. Matyushenko
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041, Russia
Received 02.03.2014, received in revised form 19.06.2014, accepted 29.07.2014
The possibility of using exergy concepts to address environmental issues related to improving the
process of vortex combustion Kansk-Achinsk coal in terms of reduction of nitrogen oxides. Exergy is
the only concept in physics, the definition of which includes environmental and technical features of the
system. Set out measures to reduce emissions using the method and apparatus of exergy nonequilibrium
thermodynamics to assess their effectiveness.
Keywords: nitrogen oxides, boiler units, emissions, exergy method of analysis, methods of burning
coal.
????????
???????????? ? ???????????? ????????? ? ???????? ????????????? ??????? ????????
??????????? ?????????????? ?????????? ?????. ???????? ???????? ??????, ????????? ??
???? ????????????, ???????? ??????? ???????????? ????????, ?????????? ????????? ????????????. ?? ???? ???????? ? ????????? ??????????????? ????????????? ???????? ???????? ?????? ????, ????? ? ????????????? ????????. ? ????? ? ?????????? ? ????????? ????
???????????? ? ?????? ?????????? ????? ?????? ? ?????????? ????????? ? ????????? ????????? ?????? ????????????.
????????? ???????????? ?? ???????? ??????????? ??????? ??????? ?????? ?????????????????? ?????????? ???????? ???????, ??????????? ???????? ??????? ??????? ?????????? ??????? ??????? ?? 10?40 %. ?????? ????? ???????????? ??? ?????????????? ????,
????????? ? ???? ????????????? ???????? ?????. ????????? ??????????? ?????????? ? ????????? ? ???????? ?????.
???????? ?????? ???????? ???????
???????????? ???????? ? ?????????
???????? ?????? ? ?????? ????????? ??????? ? ???? ?? ????? ????????????????
???????? ???????? ???????? ??????? ?????. ?????????? ????????????? ??????????? ??? ???????? ? ????????? ??????? ????? = 1,03ч1,05. ??????????? ???????????? NOx ?? ????????????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: a.v.zhuikov@mail.ru
# 596 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Andrey V. Zhuikov and Anatoliy I. Matyushenko? Decrease of Nitrogen Oxides in the Combustion Process Kansk-Achinsk...
??????? ??????? ????? ??? ????????????? ?????? ? ?????????? ? ????????? ????? = 1,1ч1,3.
?????? ???????? NOx ?????????????, ??? ???????, ?????? ???????? ???????????? ???????
???????, ??? ??????? ? ?????? ???????? ??????????? ???????? ?????? ???????? ???????. ?
????????? ????? = 1,1ч1,3 ?????????????? ??????????? ?????????? ?????????? ????????? ? ?????????? ??????? ????????????? ???????. ???????? ? ?????????????? ? ?????? ??????????
???????????? NOx ???????????? ?????????? ? ???????????? ?????????? ?????????, ????????
????? ? ??.
?????? ?????? ?????? ??????? ??????? ???????? ? ?????????? ???????? ?????????????
???????, ??????? ?????? ? ????? ???????? (???. 1), ??? ???????????? ??????????? ??????
?????????? ?????, ? ????? ? ???? ??????? ????? ????????????????? ???????????????????
?????????? ???????? ??????? ? ???????? ??????. ????? ?????????????????? ??????????
?????????, ?????????????? ???????? ????????????? ???????? ??????? ? ??????? ?? ????????
? ??????? ???????? ???????????????? ?????, ????? ????????????????? ??????? ???????
??????? ? ???????? ????????????? ?????????? ??: ??? ???? ???????????? ???????? ???????????? NOx ???????? ??? ?????????, ?? ??? ?????? ??????????? NOx (?????) ?????????? ? ???????
??????? ???????? ??????? (???. 1).
????? ???????, ???????? ?????? ? ?????? ????????? ??????? ??? ???????????? ???????? ????????? ????????? ???????? ???????? ?????? ??? ?????????????????? ??????????
?????????, ??????????? ????????????????? ??????? ???????. ????? ????, ??????? ????????
??? ???? ????? ?????????? ???????????????? ???????? ? ?????, ??? ??? ??????????? ??????
????????? ? ????????? ?????? ? ???????????? ??????????????? ?????????? NOx.
???????????? ????????? ???????? ???????? ? ???? ?????? ???????? ????? ? ???? ??????? ? ???????? ??????????? ????????? ???????? ??????? NOx. ?????????? ????????????
NOx ??????????? ?? ??????? ?????? ???????????? ??????????????? ?????, ??????? ????????? ??????????? ??????? ??-?? ?????????? ????????? ?????? ??????? ??-?? ???????????
???????? ????? ? ???????? ???????????? ??????????? ???????. ??????? ?????????? ?????-
???. 1. ??????????? ???????????? NOx ? ?? ?? ??????? ???????: 1 ? ??????? ???????;
2 ? ?????????????????? ???????
# 597 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Andrey V. Zhuikov and Anatoliy I. Matyushenko? Decrease of Nitrogen Oxides in the Combustion Process Kansk-Achinsk...
?????? ?????? ??????????? ?????????? ??????? ???????????? ????????? ???????? ? ????
???????. ???????????? ???? ???? ? ??????? ?????? ??????? ????? ?? ???????????? ? ????????? ?? 150 ?? 600 °? ? ???? ?? ? ????????? ???? ????????, ??? ?????????? ?????? ????????
??????????? ??????? ????? ??????????? ??? ????????? ????? ?????????? ???????????????
????? ? ???? ????????? ??????? ? ?????? ??????? ?? ???????????????? ????????????? ? ???????? ???????? (???. 2). ? ???? ?????? ?????????? ?????????????? ???????? ???? ?????????
???????? ? ?????????????? ????? ????????? ??? ?????? ?? ? ????? ????? ????????? ??????
??????? (?????? 1, ???. 2). ???? ??????????????? ????? ????? ?????, ????????????? ??? ????????? (?????? 2, ???. 2), ????? ??????????, ? ??? ????? ??????? ????? ????? ????? ? ????
????? (?????? 3, ???. 2) ???????????? NOx ??????????? ?? ????????. ? ???? ??????? ????????
???????? ??????? ?????????? ??????, ??? ??????????????? ???? ??????????? ? ???????????????? ??????.
??????????? ???????????? ????????? ???????? ? ???? ??????? ???????? ?????????????
???????????, ????????? ??????? ?????????????? ??????????? ?????? ?? ????????? ?????????
???????????? ? ??????????? ????????????. ???? ?? ????????? ?????? ?? ???????????? ??????? ?????, ?? ?? ??? ????? ???? ????? ??????????? ?? ????????? ???????.
??? ??????????????? ??? ????????????? ????????? ??????????????? ????? ??????????? ???????? ???????, ????? ????? ??????? ? ???????? ???????? ?????? ? ??????????, ??????? ?????????????????? (?????? ? = 0,8ч0,95), ? ????????? ??????????? ?? ??????? ?????????? ??????? ???????? ? ???????? ?????? ????? ?? ????? ??????. ????? ???????, ?? ??????
????? ??????? ?????????????? ???????? ??????? ??? ?????????? ??????????, ? ?? ?????? ? ????????? ????????? ??????????? ??? ?????????? ???????????? (???. 3). ????????? ????? ? ?????? ?????? ??-?? ?????????? ???????????? ????????? ??????????? ??????????? ?????????
??????? ?????, ? ???????? ?????????????? ?????? ?? ?????? ?????? ????????? ???????????
??????????? NOx.
???????? ????????? ?????????? ???????????????? ???????? ??????? ? ?????????? ??????????? ????? ??????? ??????? ?????? ??????? ? ??? ??????????, ??????? ??? ?????? ???-
???. 2. ???????? ??????????? NOx ? ??????????? ?? ???????????? ???????? ?????
# 598 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Andrey V. Zhuikov and Anatoliy I. Matyushenko? Decrease of Nitrogen Oxides in the Combustion Process Kansk-Achinsk...
???. 3. ??????????? ???????????????? ????????: 1 ? ??????????????? ????????; 2 ? ???????????????
????????
???????? ????????? ????????? ?? ???????? ??????????????. ?????? ?????? ???? ??????
????? ???????, ????? ?????????? ?????? ???????? ? ?????????? ??????? ?????? ???????
??? ?????????? ?????????. ? ?? ?? ????? ??? ???? ?????? ???? ?????????? ??????? ?? ?????
??????? ? ???, ????? ????????? ????????? ? ?????? ??????? ???????? ??????????? ???????.
???????????? ??????????? ???????? ?? ?????? ??????? ????? ???????? ? ????????????? ?????????? ???????? ????????? ????????? ????????.
??? ?????????? ??????????? ??????????????? ???????? ????????? ?? 40-50 % ??????? ??????? NO x ? ?? 10-15 % ????????? ??????????? ??. ?????????? ?????????????
??????? ??????? ?????????? ??????????? ??????? ????? ??????????? ??? ?????????? ????????????? ?????? ? ?????? ????????? ??????? ??? ?????? ? ????????????? ????????
????? (???. 4) [1].
? ????? ?????? ?????? ????????????, ???????????? ????? ? ????? ???? ?????????? ??
??????????? ???????????? ?????? ??? ?? ???? ?????????? ??????????? ????????-??????? ??
?????? ???????, ??? ? ?? ???? ?????? ???????????? ??????? ????? ????? ??? ??????????
??????? ? ??????? ????? ?????. ???????? ????? ??????????? ?????????? ????? ??????????
??????? [1].
?????????????? ???????? ???? ? ??????? (??? ???????????????) ???? ???????? ????????????? ????????? ????? ???????????? ??? ????????? ? ????? ? ?????????? ? ?????????
???????? ???? ? ??????? ???????. ???? ????? ?????????? ???? ????????????? ??????? ?????
???????? ??????, ?? ???????? ????? ???? ????? ??????????? ? ???????????? ???????? ???????.
??????? ????? ???????????? ?? ??? ???, ???? ??? ???????????? ???????? ???????? ???????
????????? ??????? ??????? ?? ?????????? ????????? ??????? ? ???????? ??? ?? ??????????? ? ???. ???????, ??? ?????????? ?????????? ???????? ?????? ???? ?????????? ?????????????????? ? ???????? «??????», ??? ???????????? ???????? ????????????? ??????.
# 599 #
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Andrey V. Zhuikov and Anatoliy I. Matyushenko? Decrease of Nitrogen Oxides in the Combustion Process Kansk-Achinsk...
???. 4. ??????? ??????? ??????? ? ???????????? ?? ??????????? NOx: 1 ? ??????????????? ????????;
2 ? ??????????????? ????????
??????????, ????????????? ? ???????? ??????? ??? ???????? ? ??????? ????, ????????.
??? ???? ?????????? ????? ???????????? ????? ????? ? ????? ????, ? ??? ????? ?????????????????: ???????? ????, ????? ????, ???????? ?????, ??????, ? ????? ??????? ? ?????? ???????? ????????. ??????? ?? ?????? ???? ??????? ? ??????? ?? ??????? ????????????? ?????????
?????????? [2].
???? ????????. ??????? ??????????? ??? ???????? ??????? ???????? ????????? ????????? ????????, ??????? ????? ???? ?????? ? ????? ?????? ? ???????? ??? ????????? ? ????? ?? ??? ?????. ????? ??? ????????? ???????, ??? ??????????????? ??????? ???????.
?????????? ????????????, ??? ???????? ????????????, ??????????? ????????, ?????????? ??????????????????? ??????????. ???? ? ???? ? ??????? ???????????? ???????? ? ????
????? ? ?????? ?????????? ? ????????? ??????? ???????? ?? ???? ????????????? ?????????
?????????? ????????? ??????? ???????? ?????????? ????? ?????????????? ??????? ?????.
???????? ??????? ???? ???????? ?????????????? ?????????????? ? ?????????? NOx. ?? ?????????? ????????? ??????? ?????????? ??????? ????? ?? 15ч30 % ? ???? ?? 40ч60 %.
??? ??????? ?????? ???????? NOx ??????????? ??? ????? ? ????? ??????? ????????
MgCl2. ???? ?????? ???????? ?? ????? ??-41 ? ?????????? 0,05 % ?? ??????? ??????? ????????
????????? ?????? NOx ?? ??????????? ???????? ? ??? ????? =1,08 ? 300 ?? 150 ??/?3. ??????
???????? ??????? ????? ? ?????? ?????? ??????????? ????????? ??????????? ??????? Mg,
????? ? ????.
??????????? ????????? ???????? ??????? ??????????????? ???????? «????????-I».
??????? ??? ? ????????????? ????????? ???????????????? ??????????????? ???????? ? ??????.
????????? ?????? ?????? ? ???? ?????? ?????????????? ????????????? ??? ?????????
?????????? ?????? ?????? ????, ??????????? ???????? ????????. ???????? ???????????
# 600 #
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Andrey V. Zhuikov and Anatoliy I. Matyushenko? Decrease of Nitrogen Oxides in the Combustion Process Kansk-Achinsk...
??????????????? ??????? ???????. ??????? ???????? ??? ???? ????????? ? ????????????
???????????? ??? ? ??????, ??? ? ?? ??? ?????????. ???????? «????????-I» ???????????? ???????? ???????????? NOx, ???????? ?????? ? ????(?)?????? ? ??????? ?????.
?????????? ??????? ?????? ??????? ? ???, ??? ???? ???? ??? ???? ???????? ?????????????? ?????? ????? ? ????????? ??????, ??????? ?????????? ????? ??????????????? ????????
???????. ? ?????????? ????????? ????????? ??? ?????.
?????????????????? ?????????? ????????? ? ???? ?? ???????? ??????????? ????????
?????????????? ???????? ??????? ?????, ???? ? ????????????? ??????? [1]. ?? ???????? ??????????? NOx ?????????? ???????????? ??????? ???????, ???????????? ????????? ???????????????, ??????? ???????, ??????????? ???? ??????????. ??????? ?????????? ?????????? ?
?????????? ???????? ????????? ????????? ???????? ????? ????????? ?? ????????? ????:
??????????? ????????, ? ????????????? ????????? ????????, ?? ??????????? ????????? ???????, ??????????????? ????.
??? ????????????? ?????????? ????????? ? ??????????????????? ????????? ?????
?????????? ???????? ?, ??????????????, ??????????? ????? ?????????? ??????? ? ??????????????????? ???? ???????. ? ?????????? ??????????? ?????? ?????????? NOx ? ?????????
????????. ??? ???? ?????????????? ??????? ???????? ??????? ??? ????? ???????? ??????? ?
??????????? ?????????? ????, ?? ? ????(?)?????? ? ??????? ?????. ??????? ? ????? ??????
??????? ?? ??????????? ??????????? ?????????? ? ???? ??????? ?? ???????????? ??????? ??????? ? ????????.
???????? ??????????? ??????? ????? ??? ?????????? ?????????????? ??????????
????????? ?????????? ?? ???? ???????? ???????? ??????? ? ?????????? ????????? ??????????
?????? ?????. ???????????? ? ?????????? ?????????? ??? ???????? ?????? ??????????? ???????. ????? ?????????? ?????????? ???????????? ????? ?????? ??????????????? ? ???????
??????????? ??.
?????????? ?????? ????? ?????????? ????????? ?????????? ??????????? ?????????
??????? ?????????? NOx ?? 30-50 %, ? ?????? ? ?????, ? ????? ????????? ??????????????? ?
??????? ?????? ??????? ????????? ????????. ??? ???????, ? ?? ??????? ??????? ????????
???????? ????????? ???????, ????????? ??? ? ???????? ?????????? ?????? ?????? [3].
?????????? ??????????? ????????????
? ???????? ?????????? ???????? ? ???????? ??????? ?????????? ??????????? ??????? ????? ??? ???????? ????-??????????? ????? ?? ????? ???-75-39?? ????????? ??????? ???????????? ???????? ???????, ???????????? ?? ????????????? ???????? ????? ?????????????? ?
??????????????? ???????????? (???. 5). ??????????? ???????????? ???????? ???????? ??????? ? ??????? ????? ??????? ???? ???????? ??????? (???????????? ???????) ????????? ???????
?????????? ??????? ????? ?? 40?50 %, ?? ??? ???? ?????????? ????????????? ???? ??????????? ????? ?? ?????? ?? ?????. ??? ??????????? ??? ??????, ????????? ??????-????????
???? (???), ??? ??? ???? ??????????? ?? ?????? ?? ????? ???????? ? ??????? ?????????
????????????? ??????????? ???????????? ???????. ????? ??? ???????? ??????? ???????????
????????? ????????, ? ?????? ???????? ???????? ????????????? ??? ?????????????? ???, ??? ?
??? ??????? ?????? ??????? ??? ?????????? ?? ? ?????????????? ???????? ? ???????? ????# 601 #
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Andrey V. Zhuikov and Anatoliy I. Matyushenko? Decrease of Nitrogen Oxides in the Combustion Process Kansk-Achinsk...
???. 5. ??????????? ??????????????????? ???????????? ????????? ???????? ? ????? ???-75-39??
?? ? ??????? ??????? ?????????? ?? ????? ??????. ??????? ???????? ????? ? ????? ??????????
? ?????????? ????????????????? ?????????????? ?????????? ??????? ? ???????? ?????? ??????? ?????, ????????????? ??????????? ?????????? ????? «???????? ???????». ???????????
?????????? ??????? ??????? ????????????? ??????? ??? ????????? ???????? ??????? ??????
?? ???? ????????????? ?????????? ??????? ?? ?????????? ? ???????? ???????? ??? ????????????? ???????? ? ????? ?????? ??????? ??????????. ????? ???????, ?????? ????? ????? (???????? ???????) ???????? ?????????? ??????????? ? ????????????? ?????????, ??? ?????????
??????? ??????????? ??????? ????? ?? ?????? ?? ?????, ??? ????? ???????????? ??????????? ???????????? ???????????? ??????? ?? ???? ?????????? ???????????? ???????? ???????
?? ????? ?????? ???????? ?????? ? ??????? ??????? ?????????? ?? ????? ??????. ??????????
???????????? ????????????? ????????????? ????????? ???????, ???????????? ??????????
?????? ? ???????? ?????? ? ???? ?????? ???????? ? ???????? ??????????? ?????? ???? ?????????? ???????????? ????????? ? ???????? ??????? ???????, ?????????????? ??????????
??????????? ??????? ?????.
???????????? ?????? ???????????? ???????? ?? ?????? ????? ??????????? ???????????? ?????. ???????? ??????? ????????????? ??????? ?? ???????????? ????? ???????????
# 602 #
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Andrey V. Zhuikov and Anatoliy I. Matyushenko? Decrease of Nitrogen Oxides in the Combustion Process Kansk-Achinsk...
? ???, ??? ?????? ???????? ??????????? ???????? ????? ??????? ?? ???? ??????????? ????
????????. ??-??????, ????????? ? ???????? ?????? ???????????? ????????? ? ??????? ???????? ???? ????????????? ?? ???? ?????????????? ????? ????????-????????? ????? ? ??????? ?????? ?????????? ????????? ???????, ????????????? ??? ????? ? ?????????? ??? ??????.
????? ?????????????? ??????? ? ?????????? ?????? ?? ?????? ????? ? ???????? ?????????????? ???????, ?????????? ? ?????? ????? ???????? ??????? ???????? ??????. ? ????????
????????????????? ?????? ??????????? ??? ???? ???????????, ??? ???????? ?? ????? ??????
?????. ?????? ?????? ?????? ? ??????? ????? ?????? ??????? ???? ?? ???????? ???????, ?????
??? ?? ???????? ??????? ????????? ????????? ??????? ??????. ????? ?????????????? ?????
????????????????? ?????????????? ???????? ? ??????????????, ????????????? ????????
????????????, ???????????????? ?????????????? ???????????? ?????? ??????????? ??????? ????????, ??????????? ?????????????? ?????? ? ?????? ?????. ????????, ??? ????? ?????? ???????? ??????? ????????????? ? ??????? ??????? ????? ??????????? ?????????????
? ?????? ???????? ??????. ?????? ?????????? ? ????? ????????? ??????? ??????? ? ??????
?????? ????? ??????????, ??? ? ???????????? ?????, ??????? ??? ????????????? ????????????? ??????? ????????? ??????? ???????? ?? ??????????? [4-5].
??? ??????????? ?????? ?? ????????????? ????? ?????????? ???????? ???????????
??????????? ????????, ?????????? ? ???? ??????????? ???????? ?? ??????????? ???????
?????, ? ????? ??????? ?????????. ?? ??????????? ????????? ????? ??????????? 100 ???. ???.
??????? ????????? ?????????? 188, 564 ???. ???. ??? ??????? ?? ??????? ????????? ???????????? ?????, ??????? ????????? ???????????? ? ????????? ?????. ??????????? ???????? (???
???), ??????????? ??? ??? ????????????? ?????? ?????, ??????????:
? = ??? + ??? = 100000+159800 = 259,8 ???. ???.
?????: ??????? ?? ????????????? (? ???) ? 306,6 ???. ???.
? ?????????? ??????????????? ??????? ???????? ????????? ??????:
??????? ???? ??????????? (??): ?? = 2,23 ????.
???????????????? ???? ???????????: DPP = 2.35 ????.
?????? ???????????????? ????? ? ??????????? ?????? (??????):
NPV = 1462,44 ???. ???.
?????? ??????????: DPI = 5,8 %.
? ?????????? ??????????????? ??????? ??? ?????????? 82 %.
?????? ? ????????????
?????????? ?????? ??????????????????? ????? ???-75-?9?? ? ?????? ???????????????? ???????, ??????? ????????, ??? ??????????? ??????????????????? ???????????? ???????? ? ????? ??????? ?????????? ??????? ????? ?? 25-49 %. ??????????? ?????? ??????????? ???????????? ? ???????? ?????? ????? ??? ???????, ???????????? ???????? ???????
? ??????? ??????????. ?? ???? ????? ???????? ???? ??????? ? ????? ?????????? ????????????????? ? ????????????? ????. ? ?????? ???? ????????? ???????? ????? ??????? (???????? 65-75 %) ??? ????????? ??????? ???????, ?? ?????? ???? (???? ???????? ???????)
??? ????????????? ??????? ??????? ????? ? ????????? ???????, ? ? ?????? ???? ????????
?????????? ??????, ??????????? ??? ??????? ???????? ??????? ??? ????????????? ?????,
# 603 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Andrey V. Zhuikov and Anatoliy I. Matyushenko? Decrease of Nitrogen Oxides in the Combustion Process Kansk-Achinsk...
????????????? ?? ?????? ?????? ???????? ?????? ?? ?????? ???????? ???????. ??????? ????????, ??? ?????? ?? ????????? ???????? ? ????????? ??????? ????? ? ????? ???????????
????????????? ???????????? ?????????? ?? ???????????? ??????. ??????????? ???????????
??????????? ???????, ????????? ??????????? ???????? ?????, ?????? ? ???????????? ????????? (q4) ???????? ? ???????? ????? ??? ?????? ?????? ????. ? ??????? [5-7] ?????????
???????????, ??????????? ??????????? ??????????? ???????? ??????-???????? ????? ?
?????? ?????????? ???????? ??????? ?????.
?????? ??????????
[1] ??????????? ?. ?., ?????? ?. ?., ??????? ?. ? . ?????? ?????????? ???????? ? ????
?????????? ??????????? ???????? ???????????? ??????. ? .: ???????????, 1975. 51 ?.
[2] ??????? ?.?. ?????????????? ???????????? ???????? ??????????. ?.: ???????????????, 1986.
[3] ?????? ????????? ?? ???????????? ???????????: ?????. ???.: ? 2-? ?. ???. ? ????./
??? ???. ?. ????????, ?.?. ???????. ?.: ???????????, 1988. 760 ?.
[4] ?????? ?.?., ??????? ?.?., ?????? ?.?. // ???????????? ??????????, 2011, ?8. ?. 911.
[5] ?????? ?? ???????? ?????? ? 109527 ??, ???7 F23C 5/00 ???????????????? ????????
????? / ?. ?. ??????, ?. ?. ???????, ?. ?. ????????, ?. ?. ????????; 2011124187/28; ?????. 15.06.11;
?????. 20.10.2011, ???. ? 29.
[6] ?????? ?? ???????? ?????? ? 104670 ??, ???7 F23C 5/00 ???????????????? ???????? ????? / ?. ?. ??????, ?. ?. ???????, ?. ?. ????????, ?. ?. ??????????; 2010154596/28; ?????.
30.12.10; ?????. 20.05.2011, ???. ? 4.
[7] ?????? ?? ???????? ?????? ? 116203 ??, ???7 F23C 5/00 ???????????????? ????????
????? / ?. ?. ??????; 2011149438/06; ?????. 05.12.11; ?????. 20.05.2012, ???. ? 14.
C??????? ??????? ?????
? ???????? ????????
??????-???????? ?????
?.?. ??????, ?.?. ?????????
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
??????? ??????????? ????????????? ??????? ???????? ??? ??????? ????????????? ???????,
????????? ? ?????????????????? ???????? ????????? ???????? ??????-???????? ????? ?
?????? ???????? ??????? ?????. ???????? ???????? ???????????? ???????? ? ??????,
??????????? ???????? ???????? ? ???? ?????????? ????? ? ??????????? ???????????
???????. ???????? ??????????? ?? ???????? ??????? ???????? ? ??????????? ??????
???????? ? ???????? ????????????? ????????????? ??? ?????? ?? ?????????????.
???????? ?????: ?????? ?????, ????????? ????????,
???????????????? ???????, ??????? ???????? ?????.
# 604 #
???????
???????,
?????
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 605-614
~~~
??? 532.528
Features of Influence of Cavitation Effects
on the Physicochemical Properties
of Water and Wastewater
Vladimir A. Kulagin*a, Ekaterina S. Sapoghnikovaa,
Olesya P. Stebelevaa, Ludmila V. Kashkinaa,
Zhi-Ying Zhengb, Qian Lib and Feng-Chen Lib
a
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
b
School of Energy Science and Engineering
Harbin Institute of Technology
92 West Dachi, Nangang District, Harbin, 150001, China
Received 10.04.2014, received in revised form 21.05.2014, accepted 03.08.2014
The results of studies of distilled and tap water after exposure to hydrodynamic cavitation at
different time regimes. The changes of the temperature, conductivity, pH value, redox potential,
oxygen content depending on the exposure time of cavitation. Rational set duration cavitation
treatment for activated water. The experimental results showed the possibility of using technology
to treat wastewater.
Keywords: cavitation technology, activated water, sewage, supercavitation, physico-chemical
characteristics of water.
????????
???? ?????? ?????????? ???? ? ????????????? ????? ?????? ?? ?????. ??????? ? 1991 ?.
???????? ?? ?????????? ?????????????? ?????????????? ????????? ???? (??????) ?????????? ????????? ?????? ????. ? ????????? ????? ???????????, ???????????? ? ??????? 2011 ?.,
?????????? ???????? ?????? ???????? ?? ????? ??????????????????? ??????? ???????????
? ?????????????? ??? ?????????? ????????? ?????????? ???????? ????, ????????? ????????
??????????? ????????? ?????? ??????? ????? ?????????? ??? ????? ??????????.
? ????????? ????? ?????????? ??????? ??????????????? ???????? ?????????? ??? ?????????????????????? ??????? ???? ?? ????? ????? ??????????? ?? ???? ?????????????????
???????????. ????????????? ????????????? ??????????? ??? ??????????? ??????? ???? ? ???
????? ?????????????, ????????????? ?????????????, ??????????? ????????????? ??????????
[1]. ?? ?????? ????????????? ????????? ??? ???????? ?? ????????????? [2, 3]. ?? ?????? ?????
????????? ???????? ??????, ?????????????? ????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: v.a.kulagin@mail.ru
# 605 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
? ???????? ?????? ????????????????? ??????????? ? ???? ????????? ???????????????????? ??????? (???????? ??????? ??? ?????????), ??????? ?? ?????? ???????????? ???????????
??????? ????, ?? ???????? ? ????????? ?? ?????????, ???????? ??????-?????????? ? ????????????? ??????????. ? ???? ????? ?????????? ???????????? ??????? ?????????? «??????????????» ????, ??????????, ??????????, ????????? ???? ???????? ???????, ?? ?? ?????? ?????????? ????????????? ?????????. ???????????? ?????????????? ???????????? ???????????
??????? ?????? ?????????????????? ?????????? ??? ????????? ?????????????? ????.
?????? ? ?????? ????????????
??? ????? ????????? ?? ?????????? ?????????? ????????????????? ????????? ? ???????? ??????????????? ?????????????? ?????? ??????? ????????? ??????. ?????????? ?????????????????? ?????????? ?? ?????? ?????????????, ?? ? ??????????? ?????? ??????? ??
?????????????? ????? ??????????????? ????? ???????? ?????????? [3-6].
? ????????? ?????? ?? ??????? ????????????? ? ???????????????? ???? ???? ??????????? ???????? ????????? ?? ??????-?????????? ????????????? ? ??????????? ?? ????????? ????????: ??????? ????????????????? ?????????, ??????? ???????????, ?????????
??????????: ??????????? ?????????? ??, ????????????-?????????????????? ??????????
(???), ???????? ?????????????????? S, ???????????? ????????????? ????????? (???).
????? ????, ???? ???????? ????? ?????????? ?????????? ????? ????????? ??????????
???? ? ??????????? ????? ????????. ?????????? ????????? ???????????? ????????????????? ????????? ? ????????????? ???????? ????????? ??? ????????? ???? ? ???????????
????????????????.
????????? ???? ????????????? ? ????????????? ???????? ????????? ???? ? ?????????
???????????????? 1 ???; ??????? ??????? ?????? 2,5?10 ?4 ?3; ? ?????? ????????? ? = 0,05. ?????????? ???????????????? ???? ??????? ?????????????? ????????? ?????? ???????? ?????
???????? ?????? ? ????????? 0?15·103 ??/???. ????????? ???? ??????? 1 ? ????????? ? ??????? ??????????????????? ?????? ?? ?????????? ???????????: ???????? ????????????????
4 ???, ????? ??????? ?????? 3·10 -3 ?3; ???????? ???????? ????????????????? ????????????
?????????? 2880 ??/??? ? ?????? ????????? ? = 0,01.
?????????? ? ?? ??????????
??????-?????????? ????????? ????????????????
? ????????????? ????
??? ??????? ???????????? ??????? ?????????????? ??????????? ?? ???????? ???? ????
?????????? ?? ????????? ?????????: ???, ?????????????????? ? ??. ????????, ??? ? ? ???????????????? ???? ????? ?? ?????????, ? ? ????????????? ????? ?? ?????? ?????????? ?????????? ???? ??????????. ??? ???????????? ??????????? ????????????? ????????? ??????????
???????????? ????????????????? ????, ??? ??? ????????? ???????? ???, ??????????????????
? ?? ????? ???????? ? ????????????? ???????????. ? ??????? [7-8] ????? ?????????? ? ??????? «????????» ???? (????? ????? ????????? ??????????, ??? ?????? ????????????? ????) ??
???????????? ?????????? ?????????????????? ??? ??????????? ??????????? ?????????? ????,
????????????????? ???? ? ???????????? ?????????.
# 606 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
?? ??????? 1?,? ???????????? ?????????? ????????? ???, ?????????????????? ? ?? ???????????????? ???? ? ??????? ????? ????? ????? ?? ?????????; ?? ???. 1?,? ? ?????????? ????????? ????????????? ???? ? ??????? ???? ????? ????? ?? ?????????. ??????? ??????????????
??????? ???? ?????????? ????????? ??????????? ???? ?????????? ?? ???????. ?? ????????-
???????????????? ????
????????????? ????
?) ? = -380,83???(-?/0,66) + 211,20
?) ? = 113,57 + 21,26? ? 2,22?2
?)
?) ? = 128,55 ? 1,93? ? 0,28?2 + 0,13?3
?) ? = 5,23 ? 0,63???(-?/0,90)
?) ? = 7,44 + 0,36? ? 0,04?2
???. 1. ????????? ??????-?????????? ?????????? ???????????????? ???? ? ??????? ????? ????? ?????
?? ????????? ? ????????????? ???? ? ??????? ???? ????? ????? ?? ??????
# 607 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
?????? ???????? ?????, ??? ? ?????? ?????? ??? ?????????? ?????????? ????????, ????? ????
????????? ????? ?????????? (??????????????) ?????????.
????? ???????, ??? ???????????? ??????? ????????? ?? ??????-?????????? ???????? ????
?????????? ????????? «???????» ????, ?.?. ? ?????? ?????? ???????????? ????????????????
???? ?? ????????? ????? ????? ?? ?????????, ? ????????????? ? ?? ????? ????? ????? ?? ??????.
??????-?????????? ????????? ????????????-??????????????
???????????????? ????
? ??????? [2, 3] ???? ???????????, ??? ??????????? ????????? ????????? ???????????????? ???? ????????????? ?????? ????????? ? = 0,05. ??????? ? ?????? ????????? ????????????? ? ?????? ?????????????? (? = 0,05) ??? ?????????? ??????? ???????? ??????
n = 10 000 ??/???. ?????????????? ????? ???? ??? ????? 100 ??. ?? ???????? 2 ? 3 ???????????? ?????????? ????????? ? ???? ??????????? ???????????? ??????-?????????? ???????
???????????????? ???? ?? ??????? ????????????? ?????????.
?) ? = 24,99 + 0,04?
?) ? = 8,35 ? 0,01?
?)
???. 2. ????????? ??? ???????????????? ???? ? ??????????? ?? ??????? ????????????? ????????? ?
??????? ??????????
# 608 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
????? ????????????? ?????????, ???????
?) ? = 1,08???(-?/57,12) + 5,95
????? ????????????? ?????????, ???????
?) ? = 15,34???(-?/106,36) + 149,24???(-?/21,28) + 141,43
????? ????????????? ?????????, ???????
?)
???. 3. ????????? ??????-?????????? ?????????? ???????????????? ???? ? ??????????? ?? ???????
????????????? ?????????
??? ????????? ? ??????????? ??????? ????????? ??????????? ????????? ???????????
???? ????? ??? ?? 40 %. ??? ??????? ? ?????????? ? ??????????? ????????? ????????????? ????????? [1, 2]. ??????????? ??????????? ?? ??????? ????????? ????????, ????????????? ????????? ??????????? ??????????????? ????????? ???? ??????? ?????? tg? = 0,04
(???. 2?). ?????????? ????????????????? ?????? ????? ?????? ??????????? ? ????????????
?????? [2, 3].
????????????????? ??????????? ????????? ??? ???? ?? ??????? ?????????????? ??????????? ???????????? ?? ???. 2?. ?????? ????? ????????? ?? ???????????? ???????? ????
?????????. ????????????? ?????? ??????????? ??? ? 2,5 %. ???????????? ????????? ? ????
??????? ??????????? ??? ?????????? ??????? ??????????? ?????????. ????????????? ????????? ??? ??????????????? ????????? ???? ??????? ?????? tg? = 0,01.
????????? ???????? ??? ?????????????? ???? ? ??????? ~ 200 ??? ? ????? ? 5 ??? ??
???????? ?? ???????? ????????? 30, 60, 90 ? 300 ? ????????, ??? ????????? ???????? ??? ??
????????? ??????? ? ????????? ???????????????? ????, ??????????? ? ??????? ?????? 100
???, ?? ? ??? 200 ??? ?? ???????? ????????? ???????? ??? (???. 2?).
# 609 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
?? ??????? 3? ???????????? ??????????? pH ?? ??????? ?????????. ?????????? ?????????? pH ????????????? ? ??????????? ??????? ?????????????? ???????????. ??? ??????? ????????? 180 ? ??????? ????? ???????????? ????????? pH ?????????????? ???? ? pH ?????????
?????????? (???max) ????????? 1,1. ???????? ??????????? ????????? pH ????????????? ????????? 3090 ?. ? ???? ????????? pH ?????????? ?? 15 %, ????? ??? ???????????? ????????? pH
?????????? 18 %. ???????? ????????? pH ??? ????????????? ??????????? ? ????????? 3090 ?
????? ? ??? ???? ????????? ???????? ????????? pH ??? ??????????? ? ????????? 90 300 ?.
????? ?????????????? ??????????? ??????????? ????????? ???????? pH ?????????????? ???? ? ??????? ~ 200 ??? ? ????? ? 5 ??? ?? ???????? ?? ???????? ????????? 30, 60, 90
? 300 ?. ? ??????? ????? ??????? ?????????? pH ??? ???? ???????? ?? ????????? ? ??????????????? ????????.
???????? ????????? ??? ? ???????? ????????????? ????????? ???? ???????????? ??
???. 4?. ????????????? ?????? ??????????? ??? ? 2 %. ?? ??????? ??????????? ??????? ???????? ???????????? ????????? ??? ? ????????? 3090 ?. ??? ?????????? ?? 43 %, ????? ???
???????????? ????????? ??? ?????????? 47 %, ?? ?? ????????? ????????????? ????????.
???????? ????????? ??? ??? ????????????? ??????????? ? ????????? 3090 ? ????? ? ??? ????
?)
?)
?)
?)
???. 4. ??????????? ??????-?????????? ?????????? ????????????? ???? ?????????????? ? ????????????
? ??????? 1 ? 5 ??? ?? ??????? ????????????? ?????????
# 610 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
????????? ???????? ????????? ??? ??? ??????????? ? ????????? 90 300 ?. ??????? ????????,
??? ? ?????? [9] ??? ??????????? ???????????? ?? ???? ??????????, ??? ??????????? ????????? pH ???? ??????????? ??? ????????? ? ??????? 1 ???. ??????????? ????????? ????????
??? ?????????????? ???? ? ??????? ~ 200 ??? ? ????? ? 5 ??? ?? ???????? ?? ???????? ????????? 30, 60, 90 ? 300 ?. ????????? ??? ?? ???????? ??????? ? ????????? ????????????????
???? ??????????? ? ?????? 40 ???.
? ????? ????????????? ?? ????????? ??????????? ?? ???????????????? ???? ????????????? ???????? ????????? ????????????????? (30 300 ?) ???? ??????????? ?????????
?????????????????? (???. 3?). ???????? ?????????????????? ????????? ?????????? ??????????
0 ????-1/??, ??? ??????? ? ?????? ????????????????? ???????. ?????????????????? ?????????????? ???? ? ??????? ~ 200 ??? ? ????? ? 5 ??? ?? ???????? ?? ???????? ????????? 30, 60 ?
90 ? ?? ?????????? ? ?????????? ?????? 1 ????-1/?? [10].
??????-?????????? ????????? ?????????????????????????? ????????????? ????
???????????? ??????-?????????? ?????????? ????????????? ???? ????????? ?????????? ????????????? ??? ???????????????? ????: ????? ????????? ? = 0,05; ??????? ????????
?????? n = 10 000 ??/???; ?????????????? ????? ???? ????????? 100 ??. ? ???????????? ????
???????????? ????????????? ???? ? ????????? ???????? ??????????? (????? ????? ?? ??????):
0, 1 ? 5 ???. ?????????? ????????????? ???????????? ?????????? ?? ???. 4, ? ????????? ????????? ????????? ? ????. 1.
??? ????????? ? ??????????? ??????? ????????? ??????????? ????????? ??????????? ???? ???????? ?? 30 % ??? ???? ???????? (???. 4?). ??????????? ?????????? ?? ??????? ????????? ????????, ?? ???? ?????????? ??????? ??????????? ???? ?????????????
????????? ?????????? ???????????: tg? = 0,020,04. ?? ??????????? ???????????? ?????
???????? ????? ????? ??? ???? ?????? ??? ????????????? ??????????? ?? ???? ? ???????
180 ?.
???????? ?????????????????? ???? ??? ????????????? ????????? ????????????? ???
?????????? ??????? ???????? ????????? ? ??????? ???????????. ???????? ??????????? ????????? ?????????????????? ??????????? ??? ?????????????? ???? (???. 4?).
??????? 1. ????????? ?????????, ???????????????? ??????????? ??????-?????????? ??????????
?????????????? ????????????? ???? ?????????????? ? ???????????? ? ??????? 1 ? 5 ???
????? ???????????, ?????
?????????
?????????
0
1
5
?
y = 20,91 + 0,04 ?
y = 24,67 + 0,02?
y = 23,13 + 0,02?
???
y = 155,20 ???(- ?/680,85) +
+ 20,78 ???(- ?/34,46) + 50,81
y = 154,66 - 0,19? - 2,98?2 + 2,81?3
y = 23,11 ???(- ?/30,31) - 994,39 ???(?/24933,15) + 1154,38
S
y =133 + 7654,22 (211,92/(4(? - 280,48)?2+211,922))
y = 125,70+0,23? - 0,004?2 +
+3,67?3 - 1,16?4 + 1,24?5
y = 120,94 + 0,13? - 7,36?2 + 1,69?3
??
y = 7,22+0,02? - 1,7?2 +
+ 7,10?3 -1,01?4
y = - 0,36 ???(- ?/56,90) + 8,07
y = - 0,29 ???(- ?/37,37) + 8,36
# 611 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
???????? ????????? ??? ? ???????? ????????????? ????????? ???? ???????????? ??
???. 4?. ????????????? ?????? ??????????? ??? ????????? 35 %. ?? ??????? ???????????
??????? ???????? ???????????? ????????? ??? ? ????????? 30 220 ? ??? ?????????????? ????
? 3090 ? ??? ???????????? ? ??????? 1 ? 5 ???. ??? ?????????? ?? 23,9 ? 20 % ??????????????,
?? ?? ????????? ????????????? ????????. ???????? ????????? ??? ??? ????????????? ??????????? ? ????????? 3090 ? ????? ? ??? ???? ????????? ???????? ????????? ??? ??? ??????????? ? ????????? 90 300 ? ??? ?????????? ????.
?? ??????? 4? ???????? ??????????? pH ?? ??????? ?????????. ?????????? ??????????
pH ????????????? ? ??????????? ??????? ?????????????? ???????????. ???????? ??????????? ????????? pH, ??? ? ? ?????? ? ???????????????? ?????, ????????????? ????????? 3 090 ?.
? ???? ????????? pH ?????????? ?? 4 %, ??? ????????? ? ??? ???????????? ??????????. ?
????????? 90 300 ? ???????? ?? ????????? ?????????? ????????.
????? ????, ??? ????????????? ???? ???????? ??? ???????????? ?????????? ??? ??????
?????? ?????????: ????? ????????? ? = 0,01; ??????? ???????? ?????? n = 2 880 ??/???; ?????????????? ????? ???? ????????? 1000 ??. ?????????? ????????? ??????-?????????? ???????
????, ?????????? ? ??????? ????? ?????, ???????? ?? ???. 5. ????? ??? ????????? ????????
????????? ??? ???? ??????? ????????? ????????? ??????????? ?????????? ????, ?????????
????. ?? ?????????? ????????? (????. 2) ?????, ??? ???????? ??? ?????????? ??? ? ?? ????? ???????? ????????? ? ?????????? ???? ??????????????. ????? ??????????? ?????????
???? ?????????? ??????????? ??? ?????? ????????? ? ? = 0,01.
??? ?????? ????????? ? = 0,01 ??????????? ????????? ???????? ???, ?? ? ?????????????????? ?????????????? ?????????????? ???? ? ??????? ~ 200 ??? ? ????? ? 5 ??? ? ? ??????? 4 ??? ? ????? 1 ??? ?? ???????? ?? ???????? ????????? 30, 60 ? 150 ?. ??? ???? ???????????
??????????? ????????? ??? ? ??????? 2 ???, ????? ???? ??? ??????? ?????????? ????????.
???????? ?????????????????? ? ?? ? ??????? 12 ??? ????????? ?????????? ????????, ?? ????
? ????? 5 ??? ?? ???????????? ? ???????? ???????? ?? ??????????? ?????????.
??????????
????????? ????????????????? ???????? ??????? ???? ?? ????????????????? ????????????? ??????????? ??? ?????? ????????? ? = 0,05; 0,01 ? ?????? ???????? ??????
n = 10000 ? 2880 ??/??? ? ??????????? ?? ??????? ???????????. ???????? ????????? ???????????????? ??????? ???? (??????????????????, ?????????? ?????????? (pH), ????????????-
??????? 2. ????????? ?????????, ???????????????? ??????????? ??????-?????????? ??????????
?????????????? ????????????? ????, ???????????? ? ??????? 1 ???
?????????
?????????
V = 100 ??.; ? = 0,05
?
y = 25,37 - 0,02? + 2,13?2 + 1,77?3 - 2,23?4
y = 23,69 + 0,22? - 8,25?2
???
y = 154,66 - 0,19? - 2,98? + 2,81?
y = 144,44 - 2,85? + 0,05?2 - 2,07?3
S
y = 125,70 + 0,23? - 0,004?2 + 3,67?3 - 1,16?4 + 1,24?5
y = 122,56 + 0,67? - 0,002?2
??
y = - 0,36 ???(- ?/56,90) + 8,07
y = - 0,58 ???(- ?/40,81) + 7,95
V = 1000 ??.; ? = 0,01
2
3
# 612 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
?)
?)
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???. 5. ??????????? ??????-?????????? ?????????? ????????????? ????, ???????????? ? ??????? 1 ???,
?? ??????? ????????????? ????????? ? ??????????????? ??????
????????????????? ?????????, ??????????????????? ? ??.), ??????????? ???????????? ????????????????? ????????????? ????????? ????. ??? ???? ??????????? ?????????? ?, pH
? ??????????????????, ?????????? ??? ? ???. ??????? ????????? ???????? ? ????????
??????????? ?????????? pH ? ??? ? 3 090 ?. ???????? ????????? ???????? pH ? ??? ?
????????? 3 090 ? ? ??? ? ??? ???? ????, ??? ? ????????? 90 300 ?. ??? ?????????? ??????????
?????? ??????????? ? ???????????? ???????????? ??????? ??????????? (44 ???) ?? ????.
??????????, ??? ???????????? ???????? ?? ??????????? ??? ????????????? ???????????
? ??????? 180 ?. ??????????? ???????? ??? ????????? ??? 300 ? ????????????? ?????????,
?? ???????? ? ??????? ????????????? ????????.
????????, ??? ?? ????? ?????????? ?????????????? ???? ????? ????????? ? ??????? 200
??? ??? ???????????? ??????? ????????????????? ????????????? ????????? ?? ???? ?????????? ?????????? (?, ???, pH, ???, ??????????????????) ?? ???????????? ? ???????? ?????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
?????? ??????????
[1] ??????? ?.?., ??????? ?.?. ?????? ?.?. ????????????? ??????????. ??????????: ???-??
???, 1990. 200 ?.
[2] ????????? ?.?., ??????? ?.?., ????? ?.?. ????????????? ? ?????????????? ?????????? ?????????????? ??????. ???????????: ?????, 2012. 424 ?.
[3] Dubrovskaja O.G., Yevstigneev V.V., Kulagin V.A. // Journal of Siberian Federal University.
Engineering & Technologies, 6 (2013 6) 680?689;
[4] ??????? ?.?., ?????????? ?.?. // ??????? ????????????? ???????? ???? ???????? ?
???????????? ?????????????????. 2009. ?. 14. ? 6. ?. 242?245.
[5] ?????????? ?.?., ??????? ?.?. // ??????? ???????. 2007. ? 2 (17). ?. 146?153.
[6] ?????????? ?.?., ?????????? ?.?., ??????? ?.?. // ???????????? ?????????????????.
2012. ? 3. ?. 26?30.
[7] ???????? ?.?., ????????? ?.?., ???????? ?.?. ? ??. // ?????????. 1999. ?. 44. ???. 2. ?.
197?202.
[8] ????????? ?.?. ??? ????. ?.: ?????, 1979. 254 ?.
[9] ??????? ?.?., ???????? ?.?. // ???????????? ???????. 2010. ? 2. ?. 60?65.
[10] ????????? ?.?., ??????????? ?.?., ??????????? ?.?. // ??????? ?????????? ??????????? ????. ??????????: ??? «?????», 2011. ?. 78?83.
??????????? ??????? ???????? ?????????
?? ??????-?????????? ???????? ???? ? ??????
?.?. ????????, ?.?. ????????????,
?.?. ??????????, ?.?. ????????,
???-?? ?????, ???? ???, ???-???? ???
?
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
?
????? ?????????????? ???? ? ???????
?????????? ??????????????? ????????
?????, 150001, ??????
???????????? ?????????? ???????????? ???????????????? ? ????????????? ???? ?????
??????????? ????????????????? ????????? ??? ????????? ????????? ???????. ????????
????????? ???????????, ??????????????????, ??????????? ??????????, ?????????????????????????????? ??????????, ??????????????????? ? ??????????? ?? ???????
??????????? ?????????. ??????????? ???????????? ????????????????? ?????????????
????????? ??? ????????? ?????????????? ????. ?????????? ????????????? ????????
??????????? ????????????? ?????????? ??? ??????? ??????? ???.
???????? ?????: ????????????? ??????????, ?????????????? ????, ?????, ??????????????,
??????-?????????? ?????????????? ????.
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Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 615-623
~~~
??? [665.63+662.764]:62.50
Numerical Analysis
of Technological Systems
Nikolay D. Demidenkoa and Ludmila V. Kulagina*b
a
FSRI SDTB «Nauka» KSC of SB RAS
50 Akademgorodok, Krasnoyarsk, 660036, Russia
b
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
Received 29.03.2014, received in revised form 18.05.2014, accepted 03.07.2014
The article presents a method of dynamic states analysis and systems for optimal control in complicated
thermotechnical units. Boundary tasks and optimal control parameters were obtained. Necessary
optimality conditions for rectification column control are shown. Numerical analysis of dynamic states
in technological furnaces and optimal control in rectification column, numerical research outcomes
are shown. Research outcomes can be applied for industrial chemical-technological processes
automation.
Key words: mathematical modeling, systems with distributed parameters, optimal control, heat-andmass exchange.
????????
?? ????????????????????? ??????? ??????? ??????????? ????? ? ??????, ???????, ?????,
????????? ?????, ????? ??? ?????????? ? ?.?. ??????????? ?????????????? ? ??????????????? ?????????? ??? ????????? ???????????, ??????????????? ??????????, ???????????????
???????? ? ?.?. ????????? ?????????? ????????? ???????? ????????? ????, ???????????????? ??????? ? ??. ?????? ?????? ???? ????????? ?????????? ???????? ???????????, ??????????? ? ????????????? ????????????????? ???????. ?????? ????????? ? ??????????????
??????????? ??????? ??????????????? ???????? ?????????? ?????????? ??? ???????? ?????????????????? ?????? ???????? ? ?????????? ????????? ????????? ????????? ???????????? ????????????.
?????????????? ?????? ? ?????????????? ???????? ????????? ??????????? ??????? ????????????? ? ??????????? ??????? ??????????????? ?????????, ?????????? ??????????????? ????, ???????????????? ??????? ? ??. ??? ???????? ????? ????????? ???? ?????????
???????? ?????????????? ?????? ???? ???????. ?? ??????? 1 ????????? ?????????????? ????? ???????? ?????????. ???? ???????????? ????????? ????????? ??? ?????????? ????????, ?
???????? ?????? ? ???????????? ????????? ? ?????. ? ?????? ??????????? ??????? ?????????? ?????????? ??????????????? ??? ??????? ? ??????????????? ???????????, ??? ?????*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: klvation@gmail.com
# 615 #
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Nikolay D. Demidenko and Ludmila V. Kulagina. Numerical Analysis of Technological Systems
??? ??????? ??????????? ?????????????? ??????? ???????????????? ????????? ? ???????
???????????. ??? ??????? ??????????? ? ???????????? ??????? ? ??????? ????? ???????????? ?????????? ????????????? ??????????????? ??????? ??????.
???????????????? ????????? ??????? ?? ??????????????? ???? ? ???????????????? ??????. ????????? ???? ?????? ??????????? ?????? ?????????????? ? ?????????????????????????, ??????????????? ? ?????? ???????? ??????????????, ???????? ????????? ??????
?????? ????????? ? ??????????? ? ????????? ??????????????? ????????? (????????? ?????
? ??????, ???????, ?????????????? ???????, ??????? ????? ? ??.). ? ???? ????? ??????????? ??
????????? ??????????? ? ???????? ? ??????? ????? ??????? ??? ?????????? ????? ?? ??????????.
????????? ???? ????? ?????? ???????? ? ????????? (???. 1). ? ?????? ???????? (???????? ??????), ??? ????????? ???????, ????????? ?????????? ??????????? (?????), ???????????
???????? ????? ? ???????? ?? ???? ????????. ? ?????? ????????? ??????????? ????????????? ?????, ?????????????? ????? ??????? ??????? ??? ??????????????? ??????? ????? ?
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Nikolay D. Demidenko and Ludmila V. Kulagina. Numerical Analysis of Technological Systems
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# 617 #
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Nikolay D. Demidenko and Ludmila V. Kulagina. Numerical Analysis of Technological Systems
??? ?????????? ??????? ?????? ?????????? ?????? ??????????? ????????? ? ?????????
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# 618 #
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Nikolay D. Demidenko and Ludmila V. Kulagina. Numerical Analysis of Technological Systems
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Nikolay D. Demidenko and Ludmila V. Kulagina. Numerical Analysis of Technological Systems
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??????????? ???????????? ???????? ???????? ? ??????? ????. D, W ? ????? ???????? ????????
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????????????. ????? ??? ??? ???? ???? ??????????? ??????? ? ???????? ?????????? ?????????? ??????????????? ??????. ??? ?????? ??????????????? ??? ?????? ???????????? ?????????? ? ?????? ???????-??????????? ?????????? ? ????????? ????????.
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Nikolay D. Demidenko and Ludmila V. Kulagina. Numerical Analysis of Technological Systems
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Nikolay D. Demidenko and Ludmila V. Kulagina. Numerical Analysis of Technological Systems
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???????? ??????? ?????? ???????????? ?????????? ???????? ????????? ?????:
1) ???????? ????????? ??????????? ??????????? ??????? F°(t);
2) ???????? ??????? ????????? (10)(13) ? (19)(21);
3) ????? ???????? F(n+1) = F(n) ? ?H;
4) ?????????? ???????? F(n+1) ??? n ? ? ???? ??????????? ??????????.
?? ??????? 6 ????????? ?????????? ???????? ?? ???????????? ?????????? ??? ???????????? ??????? ?-34 [5] ????????? ??????????????? ????????????? ????????? ??????????
(??????????? ????????????????? ????? ??????? ? ????????). ???????? ?????????: D = 27,06
?????/?, W = 76,59 ?????/?, Ld = 45,21 ?????/?, Hxd = 50 ?????, Hxk = 30 ?????.
??????????
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# 622 #
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Nikolay D. Demidenko and Ludmila V. Kulagina. Numerical Analysis of Technological Systems
??????????? ??????? ???????????? ?????????. ?????? ??????????? ? ???????????? ????????????? ???????????? ???????? ????????? ?????????? ???????? ????????? ??????????? ????????? ??????????. ??? ?????? ???????????? ????????????? ?????????? ??????????
???????????????? ?????????? ? ???????? ????????. ??????????? ????????? ??????????
?????????????? ??????? ????????? ? ???????? ??????? ? ??????? ???????? ?????????????
?????????? ?? ???????? ??????? ??????????. ????????????? ??????? ??????? ????????????????? ?? ????????? ???????????????? ? ???????????? ????????.
?????? ??????????
[1] ????????? ?.?. // ??????????, ?????????????? ??????? ? ???????????. ??????? ???????? ???????????????? ????????????. 2012. ? 3(20). ?. 13?21.
[2] ????????? ?.?., ??????? ?.?., ????? ?.?. ????????????? ? ?????????????? ?????????? ?????????????? ??????. ???????????: ?????, 2012. 424 ?.
[3] ????????? ?.?. // ??????? ??????. 2013. ? 3 (49). ?. 182?187.
[4] ????????? ?.?., ???????? ?.?. ????????? ????? ???????????? ???????????? ???????
? ??????????????? ????? // Journal of Siberian Federal University. Engineering & Technologies 1 (2014
7) 55?61.
[5] ????????? ?.?. ????????????? ? ??????????? ?????????????????? ????????? ? ?????????? ??????????. ?.: ?????, 1991. 240 ?.
????????? ??????
???????????????????? ??????
?.?. ??????????, ?.?. ?????????
?
???? ???? «?????» ??? ?? ???
??????, 660036, ??????????, ??. ?????????????, 50
?
????????? ??????????? ???????????
??????, 660041, ??????????, ??. ?????????, 79
? ?????? ??????? ????? ??????? ???????????? ??????? ? ?????? ???????????? ??????????
???????? ????????????????? ???????????. ?????????????? ??????????????? ???????
?????? ? ?????? ???????????? ??????????. ???????? ??????????? ??????? ?????????????
? ?????? ?????????? ???????????????? ????????. ???????? ????????? ?????? ????????????
??????? ??????????????? ?????, ? ?????? ?????? ???????????? ?????????? ????????????????
????????. ????????? ?????????? ?????????? ???????????? ???????? ?????. ??????????
?????????? ????? ???? ???????????? ??? ????????????? ???????????? ????????????????????? ?????????.
???????? ?????: ?????????????? ?????????????, ??????? ? ??????????????? ???????????,
??????????? ??????????, ???????????????.
603 #
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Andrey V. Zhuikov and Anatoliy I. Matyushenko? Decrease of Nitrogen Oxides in the Combustion Process Kansk-Achinsk...
????????????? ?? ?????? ?????? ???????? ?????? ?? ?????? ???????? ???????. ??????? ????????, ??? ?????? ?? ????????? ???????? ? ????????? ??????? ????? ? ????? ???????????
????????????? ???????????? ?????????? ?? ???????????? ??????. ??????????? ???????????
??????????? ???????, ????????? ??????????? ???????? ?????, ?????? ? ???????????? ????????? (q4) ???????? ? ???????? ????? ??? ?????? ?????? ????. ? ??????? [5-7] ?????????
???????????, ??????????? ??????????? ??????????? ???????? ??????-???????? ????? ?
?????? ?????????? ???????? ??????? ?????.
?????? ??????????
[1] ??????????? ?. ?., ?????? ?. ?., ??????? ?. ? . ?????? ?????????? ???????? ? ????
?????????? ??????????? ???????? ???????????? ??????. ? .: ???????????, 1975. 51 ?.
[2] ??????? ?.?. ?????????????? ???????????? ???????? ??????????. ?.: ???????????????, 1986.
[3] ?????? ????????? ?? ???????????? ???????????: ?????. ???.: ? 2-? ?. ???. ? ????./
??? ???. ?. ????????, ?.?. ???????. ?.: ???????????, 1988. 760 ?.
[4] ?????? ?.?., ??????? ?.?., ?????? ?.?. // ???????????? ??????????, 2011, ?8. ?. 911.
[5] ?????? ?? ???????? ?????? ? 109527 ??, ???7 F23C 5/00 ???????????????? ????????
????? / ?. ?. ??????, ?. ?. ???????, ?. ?. ????????, ?. ?. ????????; 2011124187/28; ?????. 15.06.11;
?????. 20.10.2011, ???. ? 29.
[6] ?????? ?? ???????? ?????? ? 104670 ??, ???7 F23C 5/00 ???????????????? ???????? ????? / ?. ?. ??????, ?. ?. ???????, ?. ?. ????????, ?. ?. ??????????; 2010154596/28; ?????.
30.12.10; ?????. 20.05.2011, ???. ? 4.
[7] ?????? ?? ???????? ?????? ? 116203 ??, ???7 F23C 5/00 ???????????????? ????????
????? / ?. ?. ??????; 2011149438/06; ?????. 05.12.11; ?????. 20.05.2012, ???. ? 14.
C??????? ??????? ?????
? ???????? ????????
??????-???????? ?????
?.?. ??????, ?.?. ?????????
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
??????? ??????????? ????????????? ??????? ???????? ??? ??????? ????????????? ???????,
????????? ? ?????????????????? ???????? ????????? ???????? ??????-???????? ????? ?
?????? ???????? ??????? ?????. ???????? ???????? ???????????? ???????? ? ??????,
??????????? ???????? ???????? ? ???? ?????????? ????? ? ??????????? ???????????
???????. ???????? ??????????? ?? ???????? ??????? ???????? ? ??????????? ??????
???????? ? ???????? ????????????? ????????????? ??? ?????? ?? ?????????????.
???????? ?????: ?????? ?????, ????????? ????????,
???????????????? ???????, ??????? ???????? ?????.
# 604 #
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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Engineering & Technologies 5 (2014 7) 605-614
~~~
??? 532.528
Features of Influence of Cavitation Effects
on the Physicochemical Properties
of Water and Wastewater
Vladimir A. Kulagin*a, Ekaterina S. Sapoghnikovaa,
Olesya P. Stebelevaa, Ludmila V. Kashkinaa,
Zhi-Ying Zhengb, Qian Lib and Feng-Chen Lib
a
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
b
School of Energy Science and Engineering
Harbin Institute of Technology
92 West Dachi, Nangang District, Harbin, 150001, China
Received 10.04.2014, received in revised form 21.05.2014, accepted 03.08.2014
The results of studies of distilled and tap water after exposure to hydrodynamic cavitation at
different time regimes. The changes of the temperature, conductivity, pH value, redox potential,
oxygen content depending on the exposure time of cavitation. Rational set duration cavitation
treatment for activated water. The experimental results showed the possibility of using technology
to treat wastewater.
Keywords: cavitation technology, activated water, sewage, supercavitation, physico-chemical
characteristics of water.
????????
???? ?????? ?????????? ???? ? ????????????? ????? ?????? ?? ?????. ??????? ? 1991 ?.
???????? ?? ?????????? ?????????????? ?????????????? ????????? ???? (??????) ?????????? ????????? ?????? ????. ? ????????? ????? ???????????, ???????????? ? ??????? 2011 ?.,
?????????? ???????? ?????? ???????? ?? ????? ??????????????????? ??????? ???????????
? ?????????????? ??? ?????????? ????????? ?????????? ???????? ????, ????????? ????????
??????????? ????????? ?????? ??????? ????? ?????????? ??? ????? ??????????.
? ????????? ????? ?????????? ??????? ??????????????? ???????? ?????????? ??? ?????????????????????? ??????? ???? ?? ????? ????? ??????????? ?? ???? ?????????????????
???????????. ????????????? ????????????? ??????????? ??? ??????????? ??????? ???? ? ???
????? ?????????????, ????????????? ?????????????, ??????????? ????????????? ??????????
[1]. ?? ?????? ????????????? ????????? ??? ???????? ?? ????????????? [2, 3]. ?? ?????? ?????
????????? ???????? ??????, ?????????????? ????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: v.a.kulagin@mail.ru
# 605 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
? ???????? ?????? ????????????????? ??????????? ? ???? ????????? ???????????????????? ??????? (???????? ??????? ??? ?????????), ??????? ?? ?????? ???????????? ???????????
??????? ????, ?? ???????? ? ????????? ?? ?????????, ???????? ??????-?????????? ? ????????????? ??????????. ? ???? ????? ?????????? ???????????? ??????? ?????????? «??????????????» ????, ??????????, ??????????, ????????? ???? ???????? ???????, ?? ?? ?????? ?????????? ????????????? ?????????. ???????????? ?????????????? ???????????? ???????????
??????? ?????? ?????????????????? ?????????? ??? ????????? ?????????????? ????.
?????? ? ?????? ????????????
??? ????? ????????? ?? ?????????? ?????????? ????????????????? ????????? ? ???????? ??????????????? ?????????????? ?????? ??????? ????????? ??????. ?????????? ?????????????????? ?????????? ?? ?????? ?????????????, ?? ? ??????????? ?????? ??????? ??
?????????????? ????? ??????????????? ????? ???????? ?????????? [3-6].
? ????????? ?????? ?? ??????? ????????????? ? ???????????????? ???? ???? ??????????? ???????? ????????? ?? ??????-?????????? ????????????? ? ??????????? ?? ????????? ????????: ??????? ????????????????? ?????????, ??????? ???????????, ?????????
??????????: ??????????? ?????????? ??, ????????????-?????????????????? ??????????
(???), ???????? ?????????????????? S, ???????????? ????????????? ????????? (???).
????? ????, ???? ???????? ????? ?????????? ?????????? ????? ????????? ??????????
???? ? ??????????? ????? ????????. ?????????? ????????? ???????????? ????????????????? ????????? ? ????????????? ???????? ????????? ??? ????????? ???? ? ???????????
????????????????.
????????? ???? ????????????? ? ????????????? ???????? ????????? ???? ? ?????????
???????????????? 1 ???; ??????? ??????? ?????? 2,5?10 ?4 ?3; ? ?????? ????????? ? = 0,05. ?????????? ???????????????? ???? ??????? ?????????????? ????????? ?????? ???????? ?????
???????? ?????? ? ????????? 0?15·103 ??/???. ????????? ???? ??????? 1 ? ????????? ? ??????? ??????????????????? ?????? ?? ?????????? ???????????: ???????? ????????????????
4 ???, ????? ??????? ?????? 3·10 -3 ?3; ???????? ???????? ????????????????? ????????????
?????????? 2880 ??/??? ? ?????? ????????? ? = 0,01.
?????????? ? ?? ??????????
??????-?????????? ????????? ????????????????
? ????????????? ????
??? ??????? ???????????? ??????? ?????????????? ??????????? ?? ???????? ???? ????
?????????? ?? ????????? ?????????: ???, ?????????????????? ? ??. ????????, ??? ? ? ???????????????? ???? ????? ?? ?????????, ? ? ????????????? ????? ?? ?????? ?????????? ?????????? ???? ??????????. ??? ???????????? ??????????? ????????????? ????????? ??????????
???????????? ????????????????? ????, ??? ??? ????????? ???????? ???, ??????????????????
? ?? ????? ???????? ? ????????????? ???????????. ? ??????? [7-8] ????? ?????????? ? ??????? «????????» ???? (????? ????? ????????? ??????????, ??? ?????? ????????????? ????) ??
???????????? ?????????? ?????????????????? ??? ??????????? ??????????? ?????????? ????,
????????????????? ???? ? ???????????? ?????????.
# 606 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
?? ??????? 1?,? ???????????? ?????????? ????????? ???, ?????????????????? ? ?? ???????????????? ???? ? ??????? ????? ????? ????? ?? ?????????; ?? ???. 1?,? ? ?????????? ????????? ????????????? ???? ? ??????? ???? ????? ????? ?? ?????????. ??????? ??????????????
??????? ???? ?????????? ????????? ??????????? ???? ?????????? ?? ???????. ?? ????????-
???????????????? ????
????????????? ????
?) ? = -380,83???(-?/0,66) + 211,20
?) ? = 113,57 + 21,26? ? 2,22?2
?)
?) ? = 128,55 ? 1,93? ? 0,28?2 + 0,13?3
?) ? = 5,23 ? 0,63???(-?/0,90)
?) ? = 7,44 + 0,36? ? 0,04?2
???. 1. ????????? ??????-?????????? ?????????? ???????????????? ???? ? ??????? ????? ????? ?????
?? ????????? ? ????????????? ???? ? ??????? ???? ????? ????? ?? ??????
# 607 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
?????? ???????? ?????, ??? ? ?????? ?????? ??? ?????????? ?????????? ????????, ????? ????
????????? ????? ?????????? (??????????????) ?????????.
????? ???????, ??? ???????????? ??????? ????????? ?? ??????-?????????? ???????? ????
?????????? ????????? «???????» ????, ?.?. ? ?????? ?????? ???????????? ????????????????
???? ?? ????????? ????? ????? ?? ?????????, ? ????????????? ? ?? ????? ????? ????? ?? ??????.
??????-?????????? ????????? ????????????-??????????????
???????????????? ????
? ??????? [2, 3] ???? ???????????, ??? ??????????? ????????? ????????? ???????????????? ???? ????????????? ?????? ????????? ? = 0,05. ??????? ? ?????? ????????? ????????????? ? ?????? ?????????????? (? = 0,05) ??? ?????????? ??????? ???????? ??????
n = 10 000 ??/???. ?????????????? ????? ???? ??? ????? 100 ??. ?? ???????? 2 ? 3 ???????????? ?????????? ????????? ? ???? ??????????? ???????????? ??????-?????????? ???????
???????????????? ???? ?? ??????? ????????????? ?????????.
?) ? = 24,99 + 0,04?
?) ? = 8,35 ? 0,01?
?)
???. 2. ????????? ??? ???????????????? ???? ? ??????????? ?? ??????? ????????????? ????????? ?
??????? ??????????
# 608 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Vladimir A. Kulagin, Ekaterina S. Sapoghnikova? Features of Influence of Cavitation Effects on the Physicochemical?
????? ????????????? ?????????, ???????
?) ? = 1,08???(-?/57,12) + 5,95
???
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