Патент USA US2105807код для вставки
2,105,807 Patented Jan. 18, 1938 UNITED STATES PATENT OFFICE 2.105.807 DIITERENTIAL CONCENTRATION OI." NON ~ METALLIC MINERALS Arthur Crago, Mulberry, Fla., aalignor to Phos phate Recovery Corporatiom-New York, N. Y., a corporation of Delaware I No Drawing. Application February 15, 1933, Serial No. 656,887 5 Claims. - (Cl. 209-167) The present invention relates in general to a concentration of non-metallic minerals from their ores, and more particularly to a process of differential concentration applicable to ores ' of the class consisting of phosphate-calcite-silica ores, ?uorspar-calcite-silica ores, and ?uorspar barite-silica ores. In accordance with the invention, a pulp of the ore to undergo treatment is agitated in the 9 presence of a fraction of one per cent of a free fatty acid and a fraction of one per cent of a substantially insoluble and unsaponi?able 011, without added agents capable of substantially affecting its pH value, the desired concentrate 5 being subsequently separated by froth ?otation or other manner known in the art. By this procedure omitting the use of alkali or other pH-affecting substance, it has been found possi ble to differentially concentrate one non-metallic ‘0 mineral with- respect to both another non-metal lic mineral and siliceous gangue. Either phos phate or ?uorspar can thus be separated from both calcite and silica; and ?uorspar can be separated from both barite and calcite. It has 35 also been found possible to separate calcite from silica by the process of the present invention. In order that the best results may be obtained agitation being conducted in a subaeration-?o tation laboratory testing machine, and the slimes removed by decantation. The deslimed pulp was thickened to contain 72% solids, and then there was added during further agitation- 0.28 pound of a solution of ?sh-oil fatty acids in an equal weight of fuel oil, enough more fuel oil to make a total of one pound of fuel oil, and 0.14 pound of a frothing agent consisting of three parts of 10 crude rosin residue dissolved in one part of ker osene oil, all per ton of dry material present. The pulp showed a pH value of 7.4. After three minutes agitation the thick pulp was then diluted and agitated in the machine 15 for the production of a froth over a period of three minutes, a rougher ?oat concentrate being separated. The tailing was discarded and the rougher concentrate cleaned four times by re agitation without added agents. The tailing 20 from each cleaning was assayed separately, but constituted a middling which, in commercial operations, could be returned to the ?otation cells for additional recovery of values therefrom. The results are shown in the foliowingtable: ‘ Percent Percent Percent CaF: sic, Percent :égoF’ 02.0 0. ered"' ______ _ by the process of the present invention, it has been found advisable to limit rather narrowly 30 the size of the ore particles subjected to the con centrating operation, as well as to largely de Feed __________ -_ 100. 0 52. 76 9. 11 37. 37 Finished cone. __ 32. 3 98. 38 0. l8 0. 88 4th midd ...... __ 2. 4 94. 48 0. 16 slime the ore pulp prior to its admixture with 3rd m1dd__-____._ 1st and 2d mldd- 3. 5 l6. 4 87. 54 51. 60 0. 00 0. 51 12.24 47. 48 '5; 7 16. the reagents. Tails __________ -. Slimes ________ -- 35. 10. 4 10.02 34. 64 23. 42 7. 45 65. 57 55. 29 6. 8 6. 8 In preparing the ore for treatment by the 35 process of the present invention, it is ordinarily ?rst subjected to a preliminary grinding opera tion and is thereafter screened or classi?ed to remove all particles other than those desired. The undersize may then he deslimed and the 40 oversize reground, deslimed, and added to the deslimed undersize; or the oversize may be re ground, added to the undeslimed undersize, and the whole then deslimed. The procedures herein described in detail are 45 ?otation procedures, but in many cases parallel results may be obtained by effecting the concen trating operation on a shaking table, the concen trate coming off at the side of the table as if it were the lighter material and the tailing at the 50 end as if it were the heavier material. Other features and advantages will appear in connection with the examples described below. Ground crude ?uorspar ore from Hillside Fiuorspar Mines, Rosiclare, Illinois, with a 55 gangue principally of calcium carbonate, but containing some silica, was screened through 35 mesh‘, the oversize being ground to pass 35-mesh and added to the undersize; The resulting mix ture was agitated in a relatively large amount of 69 water to facilitate removal of the slimes, the 5.05 \ 30 60. 4 4. 3 35 Other fatty acids, such as oleic acid, have also been found useful as reagents. Fluorspar carrying more than 2% of silica yields so much ?uosilicic acid as to be useless 40 for. the production of hydro?uoric acid. As a result of this and other reasons, ?uorspar con taining upwards of 98% of calcium ?uoride com mands at least double the price of the spar car rying only 96% of calcium ?uoride. It has 45 hitherto proved impossible to produce a 98% ?uorspar from the relatively impure material generally mined. According'to the present in vention, by a suitable choice of, reagents it has proved possible to obtain a satisfactory so-called 50 acid spar, as shown by the example given above. A phosphate ore from North Africa,pknown as Constantine rock, with a gangue largely of cal cium carbonate, was raised from uncommercial grade to commercial grade by ?otation with fuel 55 oil and a soap-forming fatty acid. The ore was ground to pass a 35-mesh sieve, and deslimed by agitation with water and decanting the slimes. ' The wet deslimed material, in a pulp containing ‘72% of solids, was mixed with one pound of fuel 60 2 9,105,807 oil, one pound of crude oleic acid (red oil) and 0.14 pound of the kerosene-rosin solution above identified. all per ton of. dry material present. The thick pulp was diluted and agitated in the Thedetailedresultsandasaayar ‘ arelhcwnln, the following table: Per- ?otation machine, and a rougher froth concen trate was separated. Upon removal of the tall ing, the rougher concentrate was put back into . 00. 3.11.. B.P.L. Ins. 004 m 20:;_ the machine and reagitated without added agents for two minutes, and thereafter a finished or cleaned concentrate was separated. The re sults are shown in the following ‘table. in which the tailing from the cleaning operation is‘desig nated as a middling. ' - ' use 141 11.51 .............. .. 10.67 1.21 00.40 1.00 as“ 11114 sass 1am sass an 11.10 11.00 1.s 70.1 a4 1111 1a: an a1 40.4 oass- an 0.11: 042 40.0 can an; 7.0a 112.4 41.4 A lot of phosphate ore from Consolidated Inn ing and melting Co., of Trail, 3. 0., had to be 15 cent Wt. B. P. L. 00004 Ins. ' ' ' mm recov cry ground to pass ZOO-mesh to free the silica gangue. The ore was then treated to remove part of a 56. I8 26. 8 O. 70 68. 56 17.66 E. 92 14. 8 I. 7 66. 2 40. 6 s. 26 ................ -. 0. 99 l. 42 15.6! 19. 3 72. 0 18.8 1.0 12. 2 82. 9 18. 0 15.4 8S. 1 It was found that better results were some; times obtained when solid fatty acids of ?sh oil. dissolved in part of the fuel oil, were sub stituted for the oleic acid. By slightly varying conditions, it was found possible to float limestone away from silica. A mixture consisting of one part Ocala limestone, largely calcite, and about three parts of the tail ings from a mill of the Phosphate Recovery Cor poration treating Florida pebble phosphate, was screened through 24-rnesh, and the oversize ground to the same mesh and added to the under size. The rmulting material was deslimed by agitation with water and decantation, and thick ened to contain 70% solids. The thick pulp was calcium carbonate gangue, whereupon a phos phate concentrate was separated. To eifeet these results the ground ore was deslimed by agitation with water and decantation. The deslimed ma terial in the state of a thick pulp was agitated with 2.5 pounds of fuel oil, 0.84 pound of crude oleic acid, and 0.28 pound of Tarol No. 2 (a mix ture of 75% steam distilled pine oil and 25% rosin oil by volume), all per ton of deslimed solids. The material thus conditioned was diluted and frothed to separate a small weight concentrate. richer in the carbonate and poorer in the phos phate. The remaining pulp was thickened and 30 agitated with 0.2 pound of caustic soda, 4 pounds of fuel 011, 0.84 pound of crude oleic acid, and 0.14 pound of the frothing agent above referred to as Tarol No. 2, all per ton of solids, whereupon it was diluted, and a phosphate ?oat concentrate separated. Thedetailedresultsandassaysareshownin' the following table: agitated for three minutes with 2 pounds of fuel oil and 0.53 pound of crude oleic acid, both per ton of dry material present, the pH value of the at? pulp being 7.8. No bubble-forming‘ agent or other added ?otation agent was found necessary. The oiled pulp was diluted and frothed in the ?otation machine for one minute, during which a calcium carbonate ?oat was separated. The results are shown in the following table: Percent wt. 100 22 78 Area 4 O9 $35%? ? $28 ! sway-9 883823 5 0 E 88 ee C 001 0008' In" reohvery 23. 04 90. 64 B. P. L. 4. 10 86. 6 18. 6 The foregoing procedure raised the B. P. L. con tent to a grade of commercial utility. By a somewhat modified procedure ?uorspar has been separated from barite. A table feed ?uorspar ore carrying calcium carbonate, from d5 Hillside Fluorspar Mines, Rosiclare, 111., was . The tailings were evidentlymostly silica, which was the principal ingredient of the phosphate tailings put into the original mixture. Another lot of the same Constantine ore was mixed with an equal weight of deslimed barite ore from Paga Mining Co., Cartersville, 6a., and the mixture ground to pass 35-mesl1. The ground material was deslimed by agitation for a three around to pass 65-mesh, and deslimed by agita-' minute period with water and decantation until tion with water and decantatlon. The deslimed all the slimes seemed to have been removed. The coarse material in a dilute pulp was. agitated results of the desliming operation are shown in with 1.20 pounds of sodium oleate and 0.1 pound the following table:’ of pine oil, both per ton of solids, and a carbon ate ?oat concentrate was ?rst removed. The so dium oleate was of course a’ soap, produced from fatty acid and alkali. The tailing remaining was 70 thickened and in this state agitatedwith 1 pound of fuel oil, 0.5 pound of crude oleic acid, and 0.14 pound of the kerosene-rosin solution above iden tl?ed, all per ton of original solids in the deslimed pulp, whereupon it was diluted and a phosphate II ?oat‘concentrate removed. Pub Pceantreoovty cent . . "i- cm s10. 0.00. peso. Cal‘; “04 2am 20.00 10.11 2.41 I 10a "5132s" an 0am 2010 . . Zl'esd.__.--..- 10o. 1a70 21. 4s Slime...... .. 12.2 14.40 21.00 2114 211.11 us 1.2 1011. 111 110 pulp of deslimed material was thickened 70 3 2,100,001 to 72% solids and‘ agitated with 0.5 pound of fuel 011, 0.19 pound of ?sh-oil fatty acids, and 0.14 pound of the kerosene-rosin solution'above iden ti?ed, all per ton of ?otation feed, whereupon it was diluted and a ?uorspar ?oat concentrate separated. The ?uorspar rougher concentrate thus obtained was re?oated four times, in each instance without the addition of further agents, to yield a ?nished concentrate of over 98% pm'ity, 10 four cleaner tailings constituting middlings be barite-silica ores, in the presence of a fraction of one per cent of a free fatty acid and a fracion of one per cent of a substantially insoluble and un saponi?able oil, without added alkali or other agent capable of substantially aifecting its pH value; and separating by froth ?otation in the case of a phosphate-calcite-silica ore a concen ing obtained which, in commercial practice, trate relatively rich in phosphate and relatively would be retreated to yield further recoveries. The ?uorspar ?nished concentrate contained over poor in calcite-silica, in the case of a ?uorspar~ calcite-silica ore a concentrate relatively rich in 86% of the ?uorspar in the original material. 15 The rougher tailing resulting from the ?rst ?oat was rethickened, agitated with 0.32 pound of caustic soda, 2 pounds of fuel oil, 0.45 pound of ' ?sh-oil fatty acid, and 0.14 pound of the kero sene-rosin solution above identi?ed, all per ton 20 of solids present, whereupon it was diluted and agitated to yield a barite rougher concentrate, a ?nal tailing being also obtained. The barite rougher concentrate was re?oated twice without added agents to yield a ?nished concentrate, as 25 well as two cleaner tallings constituting mid dlings. The results are shown in the following table: 30 am Pay. Product Percent of ya NOOVGI'Y :tnt ' 85 slimes, of suitably divided particles of an ore of the class consisting of phosphate-calcite-silica ores, ?uorspar-calciteesilica ores, and ?uorspar Cal‘, 010, 00001 1311804 car, B01804 0011100110--.. 20.0 0020 Midd . 0.4 00.01 Midd . 1.0 0010 10.10 21.40 1000 ?uorspar and relatively poor in calcite-silica, and in the case of a ?uorspar-barite-silica ore a con 3. A process of di?erential concentration which I comprises agitating a pulp, nearly free from slimes, of suitably divided particles of an ore of the class consisting of phosphate-calcite-sillca ores, ?uorspar-calcite-silica ores, and ?uorspar barite-silica ores, in the presence of a fraction of one per cent of a free fatty 0010 and a frac tion of one per cent of a substantiallynnsoluble and unsaponl?able oil. without added 'alkali or other agent capable of substantially affecting its pH value, the fatty acid being carried in at least a part of the oil; and separating in the case of a phosphate-calcite—siiica ore a concentrate rel 100.0 0.00 - 1.00 0.42 21.01 0.00 00.00 0.10 4.04 10.40 02.0 1.0 1.0 0.1 01 01 calcite-silica, in the case of a ?uorspar-calcite silica ore a concentrate relatively rich in ?uor spar and relatively poor in calcite-silica, and in the case of a ?uorspar-barite-silica ore a con centrate relatively rich in ?uorspar and relatively poor in barite-silica. _ MidcL?- 2.0 21.10 1.00 41.01 04.42 22 01 MiddJl- 0.0 4.10 41.00 40.00 1.0 10.0 _ 30001103111105. 04.0 000 14.00 #2__.'- 0.4 000 01.00 01.04 0.02 40.00 0.10 00 01 14.2 0.0 prising agitating a pulp, nearly free from slimes, of suitably divided particles of a phosphate-cal cite-silica ore in the presence of, a fraction of one per cent of a fatty acid soap and a fraction 40 M100. #1--.- 4.00 . 00 020 00.04 Tall ......... .. 10.0 0.40 0012 000 004 00 00 002 0.00 0.0 0.0 The barite concentrate thus obtained maybe further treated to raise its grade. It will be noted 45 that 86.1% of the original ?uorspar was re covered in the form of a concentrate carrying 98.28% of ?uorspar and conforming to the most exacting commercial demands. Having thus described certain embodiments 50 of the invention, what is claimed is: 1. A process of differential concentration which comprises agitating a pulp, nearly free from of one per cent of a substantially insoluble and unsaponiflable oil ; separating a ?oat concentrate relatively rich in calcite and relatively poor in phosphate-silica: dewatering the remaining pulp; agitating the dewatered pulp in the presence of a ' fraction of one per cent of a free fatty acid and a fraction of one per cent‘of a substantially in slimes, of suitably divided particles of an ore of the class consisting of phosphate-calcite-silica ores, ?uorspar-calcite-silica ores, and ?uorspar barite-silica ores, in the presence of a fraction of prising agitating a pulp, nearly free from slimes, of suitably divided particles of a phosphate-cal one per cent of a free fatty acid and a fraction of one per cent of a substantially insoluble and unsaponi?able oil, without added alkali or other 60 agent capable of substantially a?ecting its pH 5. A process of differential concentration com cite-silicaore in the presence of a fraction of one per cent of a free fatty acid and a fraction of one per cent of a substantially insoluble and unsa poni?able oil, without added alkali or other agent value; and separating in the case of a phosphate capable of substantially affecting its pH value: calcite-silica ore a concentrate relatively rich in separating a small-weight ?oat concentrate richer phosphate'and relatively poor in calcite~sllica, in calcite and poorer in phosphate; dewatering the remaining pulp; agitating the dewatered pulp in the case of a ?uorspar-calcite-silica ore a con centrate'relatively rich in ?uorspar and relatively poor in calcite-silica, and in the case of a ?uor spar-barite-silica on a concentrate relatively rich in ?uorspar and relatively poor in barite 70 4. A process of di?erential concentration com soluble and unsaponi?able oil, without added alkali or other agent capable of substantially af fecting its pH value; and separating a ?oat con centrate relatively rich in phosphate and rela tively poor in calcite-silica. silica. 15 centrate relatively rich in ?uorspar and rela tively poor in barite-silica. atively rich in phosphate and relatively poor in ’ r000 ......... .- 100.0 20.10 20.10 10 - 2. A process of differential concentration which comprises agitating a pulp, nearly free from in the presence of a fraction of one per cent of a fatty acid soap and a fraction of one per cent of a substantially insoluble and unsaponi?able oil: and separating a ?oat concentrate relatively rich in phosphate and relatively poor in calcite- 7o silica. 1 ARTHUR CRAGO.