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Патент USA US2410376

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2,41%,376
Patented Oct. 29, 1946
: - omrso ‘ STATES PATENT f OFFICE
BENEFICIATION OF IRON ORES
' Robert Ben Booth, Springdalaand Earl Conrad
Herkenhoff, Stamford, Conn.,
assignors
to I ’
American Cyanamid Company, New York, N. Y., ‘
a corporation of Maine
No Drawing. Application April 5, 1943,
.
Serial No. 481,906
8 Claims.
-
_
,
‘
.
,
I
,
.,
(01. 209—166_) ‘ 7
1
may be used in unlimited quantities. With every
acid and’ everyore the effect generally increases‘
This invention relates to the bene?ciation of
iron ores by froth ?otation processes.
ous beneficiation problem'because the unit value
at?rst with the addition of more acid, reaches a
maximum, and then may decline when more acid
of’ iron concentrates is not high and flotation
procedures in the pasthave not given commer
cially useful results. Iron ores containing hem
constitute the range of best? operation, with an
Low grade iron ores have presented a very seri
is used. In general, with sulfuric acid, amounts
of acid froml1/2to 5'lbs. per ton of, ?otation feed"
optimumldepending on the ore and other condi
tions of about 21/2 to 3 lbs. per ton, These ?gures
subjected to frothflotation in the presence of
the typical fatty acid collectors used with oxide 10 apply ‘to processes in" which the pulp is condie
tion'ed at' high-"solids. Where vconditioning at
ores, but, while some bene?ciation takes place,
low‘ solidsis} employed, such as for example, at
the grade obtained and recovery are not su?i
atite, magnetite, or similar iron minerals can be
?otation pulp density, acceptable results can be}
obtained, but the vamount of "acid- required is
greatly increased-ranging from‘ 5 ‘to 10 lbs. vper
ciently high to make the process commercially
feasible,
v
-
‘
H
'
jIt’has been'propo‘se'd to ?oat oxide ores with
ton-"of ‘feed. Adcommercially acceptable prod
water-insoluble reaction‘products of sulfuric acid
and petroleum, hydrocarbons from lubricating oil
stock obtainedasa waste product from the re?n
ing lubricating oil ‘stock with strong sulfuric acid,
oleum, chlorosulfo'nic or other sulfonating‘ agents
uct is obtained, ‘but, because of'thebetter re
sults and smaller reagent consumption, it is pre
ferred to condition at highsolids, although‘ the
20 invention is not limited ‘thereto;
_
‘
The tremendous improvement obtained by
and referred to in the trade as mahogany soaps.
means o-f-rthe present ‘invention is vall the. more
surprising because oxide 'ore ?otation in the pres
fatty acids, but the results are not commercial,
ence of anionic collectors such‘ as‘fatty ‘acids
particularly when iron ores are treated. '
v‘According to the present invention iron? ore 25 frequently proceeds best in a neutral-‘or slight
ly alkaline circuit." In fact, the addition'of any
pulps'are treated with an inorganic acid such as
These reagents give somewhat better results than
sulfuric acid, phosphoric acid and the like, and
the acid-treatedv pulp can be ?oated with ma
hogany soaps, used alone, or dispersed in petro
considerable‘amounts of sulfuric acid with a fatty
waste products from‘ washers, and other low
because when ore pulp is treated with an acid
such as sulfuric acid and'then floated in a cir-'
acid collector will-kill the ?oat altogether. Un
doub’tedly the acid operates ‘in a different man
leum hydrocarbons, alcohols, 'or other oily sol 30 ner with the mahogany soaps. 7' They action does
not appear’ to be one due solely to pH of the cir
vents, to give high grades and good recoveries
cuit, ‘although this may be a contributing factor,
which ‘permit transforming rejected tailings,
grade ores into commercially acceptable con
cuit in which the pH is raised by'the addition of
an‘ alkali, such as sodium carbonate, the improved
results of the present‘ invention are still re
nature which permits easy dewatering, so that
tained.- This is an added reason for believing
concentrates can be shipped to central locations
that at least one factor in the process is some
for sintering. vThe process is also advantageous
'
in that the reagents used are cheap and in nor 40 surface effect of the acid on the ‘ore particles.
* Water-insoluble‘ reaction products of sulfuric
mal times'readily obtainable in large quantities.
acid andpetroleum hydrocarbons from lubri
The mechanism of the present invention is not
eating oil stock vary duite widely‘ with different
completely known, and it is not desired to limit
crude‘ oils and different refining procedures. The
it to any particular theory of operation. Within
centrates. An outstanding advantage of the con
35
centrates obtained is their generally granular
I compositions are somewhat inde?nite and are
wide limits the nature of the acidic anion does
ordinarily considered to be mixtures containing
not appear to play a great role. Almost any
both sulfonate and sulfate esters. We have found
reasonably well dissociated inorganic acid can be
that practically all ‘of ‘these products can be
used. In fact, it is not necessary to add a free acid.
used in the present invention, although there is
Certain acid salts such as sodium or potassium
bisulfate and sodium chlorosulfonate work as 50 some difference in‘ effectiveness between ma‘
hoga'ny soaps of different petroleum companies.
well as sulfuric acid. There is some difference
When‘ no‘acid is used in treating the pulp, there
in the action of different acids. This leads us
is 'a very wide.di?‘erence between mahogany
to believe that probably one'factor of the present
soaps of'different' origins. It is a surprising effect
55 of the present‘ invention, however, that the acid
treatment‘ of the ore‘to a very great extent ad
tor may be action on stained gangue such as
invention is the action of the acid on the‘ parti
cles of iron ore. It is possible that another fac
. justs differences between mahogany-soaps of dif
iron-stained quartz.
ferent origins. They‘ all give improved results
i. It is an advantage of the present invention
that the amount of inorganic acid to be used is
not critical. This does not mean that the-acids
with acid and the difference between various ones
60
isv de?nitely lessened; This curiously‘ different
2,410,876
3
4
behaviourgwith and without acid .of various mar
hogany soaps is an additional reason for believe
ing that one factor of the present invention is a
surface alteration of the iron ore and possibly;
of the gangue. It seems reasonable to believe that‘
the acid treatment may so alter the surface‘of
bracho and other dispersing agents. The con
centrate with collector removed is then subjected
to a cleaning operation using a cationic ?otation
reagent to ?oat out silica or siliceous gangue.
This double ?oat presents a more expensive pro
cedure, but with some highly refractory ores it
.is an economically attractive procedure.
iron mineral particles that good adherence is
obtained with almost any mahoganysulfonate. 1 , » It is an advantage of the present invention that
It is necessary to coat the mineral particles with
itimay be used in such various manners so as to
the active mahogany soap. This makes it neces 10 obtain the best results economically with various
sary to use some precautions in mixing the pro-_.
ores, taking into consideration the nature of the
moter with the ore. We have found that it :is de-.
ore and the economic factors at the mines, such
sira'ble to have the active ingredients in solution
or dispersion in organic solvents. Commercial
as availability of fuel, shipping costs and the like.
In every case the present invention will be used
mahogany soaps are sold as an oil solution or 15 to obtain the best economic results with any par—
dispersion of the sulfuric acid reaction products
ticular ore, and the wide latitude given to‘the
and, therefore, are already dispersed in av hydro
ore dressing engineer by the non-critical charac
carbon solvent. These commercial products may
ter of the present invention is of real advantage
be mixed with the ores directly or they may be
in permitting optimum results with a wide variety
further diluted with other organic solvents. The
nature of the solvent does not appearto be critical.
Excellent results are obtained with hydrocarbon
solvents, such as petroleum hydrocarbons which
are naturally present inthe commercial mahog
any soaps, the latter‘being normally sold in the
form of a solution in petroleum hydrocarbons.
Glyoeride oils, of which cocoanut oil is a typical
example, also give good results and it is possible
to get good feeding with solutions in various al
cohols and other organic materials. This leads
usto believe that the main, if not only, function
of the solvent is to effect more uniform distribu
tion in the ore pulp, but it may also have other
.
of iron ores. i
The, problem of slime is not greatly different in
the process of the present invention than in the
general run of ?otation processes. Here, as else
where, slime is never desirable. However, it is
an advantagev of the present invention that it is
not peculiarly critical as far as slime is concerned
and it is possible to operate with undeslimed ore
or, which is more important, with ore which has
been only partially deslimed, thus permitting
more economical desliming procedures. The ef
fect of slime is normal and manifests itself pri
marily in added consumption of reagent. As the
reagents are fairly cheap it is sometimes desirable
to use relatively economical desliming procedures
which do not remove the slime completely and
such procedures are permissible by reason of the
relative lack of sensitivity of the present process
to the presence of small amounts of slime. More
effects. because when it ‘is attempted to feed the
active constituents of themahogany soaps in the
form ofv hot water dispersions the results are not
as good. Therefore, it is preferred to introduce
the collector in solution in an organic solvent
without limiting the invention broadly to this
involved desliming procedures, such as those em
4-0 ploying a polishing or scrubbing of the ore parti
preferred modi?cation.
' The question of froth is present as in any froth
?otation process, and various mahogany soaps
show different frothing powers. Where adequate
frothing can be obtained they may be used alone.
However, in many cases it is desirable to use one
or more frothers, for which the standard types of’
frothers such as pine oil, cresylic acid, mixtures
of higher‘ paraffin alcohols from 7 to '10 carbon
atoms and synthetic frothers prepared from mix
cle followed by desliming, are not normally neces
sary although they may be used and do effect
some economy of reagent. The extent to which
the desliming is to be effected is largely one of
economic compromise and the degree of desliming
to produce optimum results with minimum costs
will be determined in the case of each ore.
As has been pointed out above, the nature of
the acid to be used in treating the ore‘ is not criti
tures of these higher alcohols with hydrocarbons, 50 cal, For most practical purposes sulfuric acid is
may be used. We have also found that water
preferred because of its cheapness. It is also one
soluble reaction products of sulfuric acid with pe
of the best acids. Other acids such as sulfurous
troleum hydrocarbons from lubricating oil stock,
acid, phosphoric acid and the like may also be
the so-called green acids, may also be used as
used and in some cases, where waste gases con
frothers and also show some promoting effect.
taining S02 are available, they constitute a very
When‘ used alone with acid treatment, fair re
cheap source of acid usable in the present in
sults are obtained. but not as good as with the
vention. Within wide limits the purity of the
mahogany soaps or acids of the present invention.
acid does not seem to play any decisive result in
The technique of froth ?otation is not mate
the present invention, which'permits the use of
rially changed by the use of the present invention,
lower purity acids which are sometimes available
and this is an advantage because the operator does
not have to learn new techniques, and standard
?ow-sheets and equipment may be used in most
cases. Examples of typical ?otation procedures
are the/use of the process of the present invention
in rougher ?oats, cleaner ?oats, and the like.
*It is also possible to utilize the principles of
the‘ present invention in a. so-called double
?otation process in which a rougher ?oat is ef
fected with the mahogany soaps or acids on acid
at considerably reduced prices and the possibility
of using cheap material in the present invention
constitutes a further economic advantage.
It is an advantage of the present invention that
the addition of acid-"may take place at various
points in the ?otation procedure. Thus it may be
added in the conditioner and in many cases this
is preferable, or it may be used in desliming, or
added directly to the ?otation circuit. Obviously,
recovery at some slight sacri?ce of grade. The
concentrate is then'treated with chemicals or
agents to remove the collector from the surface
of course, the acid may be added in portions at
various points in the ?otation operation. The
fact that the acid addition is not critical permits
a great deal of ?exibility in setting up a ?ow sheet
for any given iron ore.
of the. particles. Typical of such agents are. due.
Th4? Present invention will be described in
treatedpulp, adjusting conditions for maximum
2,410,376
6
greater detail in conjunction‘withthefollowing
out above; better, results‘ are obtainediby‘ condi-
speci?c examples, which are typical of, the in-,
tioning the pulp with promoter at high solids.
vention, and which have been chosen to illustrate
certain of the ranges within which the invention
The signi?cance of the results in Section 3 in the
table as compared to Section 1 is, therefore, pri
gives good results. The parts are by weight.
Example 1
marily comparative;
Minnesota iron ore having an iron content of
about 30.5% Fe was deslimed and divided into
a large number of portions. Some of these were
conditioned at 22% solids with mahogany soaps
from various sources and ?oated in a Fagergren
?otation machine. Further tests were made in
-
Y'
‘‘
It was attempted to use the various mahogany
soaps by feeding them as a 1%;% dispersion in
hot water directly to the ?otation pulp. The use
of hot dispersions has been recommended in the
past in connection with the use of mahogany
soaps as collectors for ores other than iron ores.
The results of these tests are not tabulated as in
general no ?otation took place. The reason for,
which the pulp temperature was raised to 50° C.
and the mahogany soap fed directly to the ?ota 15 the- peculiar behavior of mahogany soaps with
iron ore when contrasted with their action on
tion cell, these tests being made with and without
other oxide'ores has not been determined, but is
additional sulfuric acid. Finally further amounts
of the ore were treated by conditioning with the
probably a surface phenomenon.
-
promoters and 5 lbs. per ton of sulfuric acid
The amount of acid present in the treated ore
added to the ?otation machine. In all tests the 20 pulp is suf?cient to react with the major portion
mahogany soaps werediluted with 10% secondary
or all of the mahogany soaps to transform them
butanol. The metallurgical results appear in the
partly or wholly into the corresponding free sul
following table which is divided into three sec
fonic acids. It ispossible to use the free sul
tions, the ?rst section being the various mahogany
fonic acids themselves and the results are sub
soaps, the second, tests at higher temperature, 25 stantially the same, but it is preferred to use the
50° C., with and Without sulfuric acid, and the
mahogany soaps, since they are not corrosive and
third, tests made with 5 lbs. per ton of sulfuric
do not present difficulties in shipping or handling
acid at normal temperature.
Petroleum sulfonate used
Concentrate
Tailing
"
Source
Name
Per cent Fe
Lbs/ton Pvsgi‘é‘?t
per cent
Fe assay
Assay
Dist.
Section 1
_
Standard Oil Company of California _______________________ __
2. 27
31. 28
44. 40
46.02
Sonneborn Sons, Inc ________________ _.
2. 27
37. 57
48. 90
59. 97
19. 16
2. 33
2. 40
31. 52
20.01
49.10
51.90
50. 97
35.54
21. 74
.24. 95
2. 66
2. 40
28. 62
‘ 43. 20
44.49
46.09
42. 59
65. 77
24.05
18. 24
2. 20
32. 55
44.09
47. 51
23. 51
4- 40
32. 93
47. 98
50. 28
23. 30
_ __ _
Atlantic Re?ning 00....
Stanco Distrib., Inc.__.D0 ______________ __
Do _____________________ __
1:1 mixture of Oalol and SP-l
__
1 part of above mixture with 1 part of green acids (Sonneborn
_ 23. 70
Sons, Inc.) (water soluble).
Sonneborn Sons __________________________________ .__________ __
2. 67
Atlantic Re?ning 00....
Do ____________________ --
Penna. Oil Prod. Refn’g O0-
11. 31
(2)
2. 13
Sherwood Re?ning Co ____________ ._
_
Shell Oil Co
_.
Reagent 407 . . _
2. 87
2. 50
2.07
0.92
_ . . .._ _____ -.
2.90
Crude naphtha sulfonlc soap.
1. 80
(2)
O. 83
>
2. 20
2. 20
1. 80
7.03
46.04
10. 60
29. 35
31. 34
44. 34
46.14
23. 63
1.42 ........................ __
Section 2
1:1 mixture of Oalol and SP-l ______________________________ __
Do.l
' ‘
Shell Oil Co
Do.1
1.80
6. 77
Section 3
12. 78
28. 33
7
Standard Oil Co, of California
____ __
Sonneborn Sons ______________________________ __
l 1 mixture of Calol and SP-L
Atlantic Re?ning Co.-.
_
C210]
Petronate. .
........... --
Ultranate #3
2. 27
2. 27
2. 20 ~
51. 39
36. 15
53. 98
34. 47
48. 84
39.74
58. 53
58. 51
71.17
25. 82
19. 61
18.88
2. 30
55. 89
40.19
74. 12
17. 78
Sonneborn Sons ...... ._
O-Emulsi?er.
2. 67
38. 23
52. 9B
68. 93
15. 71
Atlantic Re?ning Co--Penna. Oil Prod. Rein’g Co...
Ultranate #l-....
2. 50
2.13
42. 34
28. 38
43. 97
56.03
61. 77
51. 90
19. 98
20. 58
1 2% lbs. per ton of sulfuric acid added to the ?otation.
2 No promotion.
-
It will be noted that mahogany soaps or peExample 2
troleum sulfonates vary considerably in their pro
A further portion of the Minnesota iron ore.
moting power. Some show no promotion at ‘all
used in Example 1 was deslimed and conditioned
and others, such as, for example, Petronate and 6’I) at high solids (about 67%) with 2 lbs. per ton of
SP-l show considerable promotion, although not
Ultranate No. 3, diluted to 22% solids and ?oated
sui?cient to produce a commercial result. Section
in a Fagergren ?otation machine. In the ?rst
2 shows‘that high temperature, which has been
four tests the sulfonate was prepared as a 12%
recommended, produces poorer results and when
dispersion in hot water, boiled gently for 10 min
sulfuric acid is added the' results, although not
utes and ‘then fed to the conditioner, and in the
next two tests the sulfonate was fed directly to
good, are enormously improved. It will also be
the, conditioner,v in the next test in the form of a
noted that in Section 3 practically all of the ma
dispersion in hot 3% sulfuric acid, and. in the last
hogany soaps give good results with 5 lbs. of sul
test as a dispersion in cold 3% sulfuric acid. I In
furic acid. The results in Section 3 are not under
the optimum conditions for, as ‘has been'pointed 75 some of the tests sulfuric acid was-added and in
2,410,876
othersfuel oil.' The metallurgical results appear
?otation‘ alone is given, as the results of rougher
in the following table.
?otation are commercial.
-
'
Lbs/ton
fsulé
ona e
Concentrate
Tailing
.
used,
lbs/ton‘ H2804
Fuel
on ‘
Per
cent
Per cent Fe
wt‘
Assay
Sulfonate usedl
Por
cent
Fe
Dist.
Tailing
1111
Per Cent
Lbs./ton
wt
Name
assay
_ 2.0
5 go
_ 2.0
7.0
2.5
7.0
2. 0
2. 5
2. u
7. 0
2. o
2. 5
2. 0 '
2. 5
2. 0
2. 5
10 Petronate _______ __
3. 60
Ultranate #2 _____ __
3. 49
SP-3l2 .......... . .
3. 25
Per cent Fe
Assay
Dist.
46.35
54. 78
49.61
84. 70
76.42
91.93
56.46
43.10
56.82
45. 9e
s4. 94
72. a5
55. 07
47. I4
84. 33
Ultranate #s_-_---.
2. 20
37. 74
54. 9s
55. 3e
51-. 7e
67. 91
95. 44
45.25
58.56
87.07
20
39 . 63
58 . 68
76 . 71
c
31 ° 1 an dSP-L.
2.
per cent
Fe
assay
85. 52
53. s1
60. 75
3. 84
1 = 1 1111K
_ t We 0 f
. .
.
The addition
of acid
pro-
5e. 49
4s. 30
s5. 45
Ultranate #1-- _-__
15
It W1_H b e no t e d th a t w h en no aci d was presen t
.
no ?otation
resulted.
Concentrate
5
duced an excellent recovery of a material having
.
a commercially
acceptable grade.
.
.
.
ThlS
is
quite
20
remarkable as the concentrate is a rougher con
1 Allsulfma ts
0 11']In t 9 (1
W1'th
10 (Z'Wm
.
d My
bu t am 1.
Example 5
The effects of various acid concentrations were
centrate only, without any cleaning. The addi
tion of fuel oil alone did not bring about any
tested using the deslimed ore of Example 1 con
improvement, but gave good results when asso
ciated with sulfuric acid. It will be noted that 25 ditioned at high solids with 2.2 lbs. per ton of
an equal mixture of Calol and SP-l diluted with
excellent results were obtained in the last three
10% secondary 1butanol, followed by dilution to ?o
tests regardless of whether the sulfonate and acid
tation density and ?otation in a Fagergren ?ota
were‘ fed directly or the sulfonate dispersed. in the
tion machine. The metallurgical results are as
acid.
follows:
Example 3
A low grade Minnesota iron ore, having about
14.5% Fe chie?y as hematite with a quartz
gangue, was deslimed, conditioned at high solids
(67%) with 2 lbs. per ton of Petronate, diluted to
?otation density and ?oated in a Fagergren ?ota 35
tion machine. In the ?rst two tests the sulfonate
was fed directly to the conditioner, in the third
test the sulfonate was prepared as a 12% dis
persion in hot water, and in the last test this
12% dispersion was boiled gently for 10 minutes 40
prior to feeding. The metallurgical results ap
pear in the following table.
Concentrate
Sulfonate
used,
lbs/ton
Lbs/ton
H280‘ Per cent
w
2. 0
2. 0
2. 0
2. 0
None
2. 5
2. 5
2. 5
Tailing
Per cent Fe
Per gent PH
.
15. 10
20. 33
23. 40
24. 43
Assay
Dist.
assay
52. 50
52. 86
52. 25
50. 43
61. 48
83. 43
92. 90
96. 40
5. 85
2. 68
l. 22
O. 61
6. 9
2. 3
2. 5
2. 5
It will be noted that Petronate gives consider
Rougher concentrate
Tailing
H2804,
lbs/ton
None
0. 50
1. a0
2. 50
Percent
wt.
9. 23
46. 04
42. 95
39. 63
Per cent Fe
Per cent
Fe
Assay ’
Dist.
assay
43. 80
54. 05
58. 32
58. 68
13. 20
81. 39
82. 10
76. 71
29. 28
10. 54
9. 57
11. G9
DH
7. 0
5. 7
3. 1
2. 7
It will be noted that, as the amount of sulfuric
acid increased, the results improved up to about
11/2 lbs. per ton, reaching a maximum at about
45 this point, with some loss in recovery when 21/2
lbs. per ton of sulfuric acid was reached. With
this reagent combination a pH of about 3 gives
best results. It should be noted that in a single
roughing operation, high recovery of a commer~
cia1 grade of concentrate was obtained without
50 any
cleaning.
Example 6
The effect of conditioning time was studied;
using the deslimed ore of Example 1, condition
55
ing being e?’ected at 67% solids, followed by di
sulfuric acid, but the acid greatly increases the
recovery. Under the best conditions with good
dispersion the recovery is increased by about 50%.
While the grade is slightly below commercial
standard, which usually requires about 58% Fe, 60
lution to flotation density and ?otation in a Fa
able bene?ciation even without the presence of
it is su?iciently high so that commercial results
may be obtained by cleaning.
gergren ?otation machine. In each case the re
agent was an equal mixture of Calol and SP-l
in the amount of 2.2 lbs. per ton associated with
2% lbs. per ton of sulfuric acid. The sulfonate
mixture was diluted with 10% secondary butanol.
The metallurgical results appear in the following
table.
Example 4
The ore of Example 1 was used in a series of
Rougher concentrate
tests in which it was conditioned at high solids
(67%) with various mahogany soaps, then di
luted and ?oated using a rougher ?oat and clean
er ?oat. The amount of sulfuric acid was kept 70
constant at 21/2 lbs. .per ton. The metallurgical
results appear in the following table in which the
?rst line for the ?rst 5 mahogany soaps repre
sents rougher ?oats and the second line cleaner
?oats. In the .case of the last reagent, rougher 75
Per cent
Per cent Fe
Tailing
assay, per
cent Fe
Tf
m9? 0 .con'
dimming
wt.
39. 63
41. 32
22. 22
Assay
Dist.
58. 68
59. 29
59. 68
76. 71
81. 77
43. 31
11. 69
9. 50
22. 31
Minutes
2
4
6
2,410,376
contained about 14.3% Fe with a quartz gangue:
was 'deslime’d conditioned at" 65% solids with 2
It will be noted that as the time of condi
tioning increases so does the recovery, but ex
cessive conditioning brings about a drop. The
reason for this phenomenon is not known. How
7
lbs. per ton of an e qual mixture of Calol and SP 1
(diluted with 10% secondary butanol) , together
ever, the change is not sudden and the condi- 5 with 12.5 lbs. per ton of sulfuric acid. The condi
tioned pulp} was then diluted to ?otation de nsity
tioning time is, therefore, not critical.
and ?oated in a Fagergren ?otation machine.
The metallurgical results appear in the following
Example 7
table.
.This test was made to show the results obtain- 10
Rougher con
able with various types of iron ore. In every
Tailing
centrate, per
case the ores were deslimed, conditioned at high
cent Fe
Temp. of
pulp
solids with an equal mixture of Calol and SP-1
‘Per cent
(diluted with 10% secondary butanol) and op
Assay
Dist.
15
Fe assay
timum amounts of sulfuric acid. The conditioned
pulp was then diluted to ?otation density and
tmanna
r.mnawd.eumnand,Tai.an.em. mw
Thdet"eMNahmn.e
e.ntmAawseun.mt.obltacmCsdSwrhiVHQn,M376eaw9”2o.mnmphnmea.hdyste?welao60FV_Wrnrsh6m?ed329ta.m5a0_wmi.popoow5t3u.ha.bnc35.w 68hmas1n.ni0mmpe5mduwnMa,mLMe.mnisaemm.mrhuewoa.vism“tnmwewop.“emn"douhfn, oeIg._wmehsntueo .lmW.mHam0cm?.%1i0StP6w.nmh0v36.;9g.m80sa.m?%lsnm?Pl. 30dWnmV.qS?MmdWnwo5ST.“dvaaI51h.L“oh?1et,mcoa..n9mbhwttncme.""hmew,.aW.ea_v.tey .
nmw.onamwgT m.cwbmnhMaumVlhMedMia2m.wh1W.m“us.dm mrsmnw.mavp.?i.a mhw.imoyzrsn.m ai 2n“4e.am0lAzmeSan05l4.37:95234
0
X.b
S1...6
e
andbmweaows“Whetos
e
1
O.rv
1. . .
_m_
B
a. P.
rP..s
r1
Hb
a
e
p
. ."
. qn
r.e.
60
.nt
C
1.. .
s
mawaas.od3r1m0i60.Fae5w3.csu2mpm0eLiid&r?.mww.emsr1cv.Poma_psw.dsen.N.amm.mwwie. MIL.M1WCmOQtd, kw“mXoe
ma2e1.4e.mMh.,5an.c0.
w.w43m74t..h4793p820t89h..4.e0653. D.F78.91r7
H.1-aaareOTi
. .b I
...
e0
e_
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neeC.vma.fEhamsn.et ,
ha.awmnsvmae.ng.Htnmw?1l.som m 56nedhtn.r0.hunP.aamTam.msmtnirlumon.,_f’ .2gtd.t3145.a0ae9c.ddr6285v2m51.-i13s
.mWuWgmmM.RM3n21 8.05496A82s9l,5a3b.8cn9d?reVta.L z a 4.HerOS0.T2On
w1mhc.et.vanno.1.sr5nctim,.wvdtsz?r.ihctgsh. .m.m“W
inVef
D.neOn0.1
toof,Hm
s551
S
. ..1
. f.
.
,.~t."0r.I7ua.H0b., a .w.esrFdeue
ne.ea
fee.nd._.emum...
..m
.mat
,m
g1
m
c.m,bn.mlnree,w.nrm
rha.nie,usdwpztmvnsc
H.mmesmomv.T.e,%an.nm.w nma m w
.a,wmme.rMF_.m,er ,
aWwnrmmV“H.ubP6lt24n?.187S35a9601. m1.mnasw iu.maovclwmsnieot.
t.1$1.rm4Yuouae.mnav3.m4Laea,ih.ua o
r9I4.7o6219ug3t296
.danthm dw.
vb
ae
t. (.s
SmmRE60O.83l41w6S.bcle
e.fdt_.
..rt_..We.l;i.lb1BIti23123.
1 In absence of acid, froth was excessive, causing much mechanical over?ow into the ?oatiproduets;
Example 9 j
The effect of temperature was studied, using
another low grade Minnesota ore. The ore, which
with 10% secondary butanol) and 2.5 lbs. per ton
of sulfuric acid wase?ected at various pulp-densi
75 ties, followed by dilution to'22‘79 solids and ?ota-v
2,410,378
151
12
tion in a Fagergren jflotation machine; The
It will be apparent that desliming‘is helpful,
metallurgical results ‘appear in the following table.
Concentrate
- -
per cent Fe,
-
Tallmg
Dist.
reagents.‘
Pulp density .
j per cent
Assay
although the presence of slime does not preclude
obtaining fair results but at a higher cost for
57. 86
82.88
9. 62
2.3
67
82. 95
91. 35
ll. 21 .
7. 19
____ __
____ __
>52
36
32. 57
88. 55
19. 64
2. 3
22
-
.
.
The e?ect of various. acids was determinedaby
dltmnmg .
49. 94
43. 12
.
Example 173.
solids income
gggggg; r13
.
5
'
testing with a low grade ore such as that de
scribed in Example '12. Inevery case the ore
was conditioned at high solids with 2.2 lbs. per
ton of an equal mixture ‘of Calol and SP-l diluted
'
‘
with 10% secondary *butanol‘. Rougher ?otation
only was conducted. The metallurgicalresults
are shown in the following table.
The above tests show that optimum ‘grade is
obtained with. high solids conditioning. Condi
tioning at lower solids, while permitting excel
lent recoveries, decreases ‘very markedly the de
15
Acid used '
I Concentrate
gree of concentration.
Per
Example 11
The e?ect of flotation pulp density was studied,
using the .ore of Example 10, conditioning being
Type ;
Concentrate
-
Fe
Per cent
Dist.
>
assay
"
Fe
pH
Dist.
Fe.
30
,, ..
52. 98
58. 60
46. 04
91. 72
Nltric ___________ __
44. O9
92. 31
6. 03 ‘ _6. 8
2. 7
1; 34 2. 7
l. 34
.
________ _.___ _
Boric ____________ -_
Perchloric _______ _Phosphoric ______ __
Sulfllrous ________ __
Carbonic ________ __
solids in
-:
3. 54
22. 52
51. 89
91. 18
1. 46
2. 8
3. 99
23. 01
50. 91
92. 23
1. 22
2. 5
14. 17
26. 57
21.12
19. 93
25. 50
54. 20
43. 20
52. 69
55. 77
43. 92
62. 45
89. 72
88. 74
90.02
89. 74
5.38
1. 79
l. 79
1. 54
1. 72
6. S
2. 7
2. 7
2. 3
6. l
2. 5
2. 5
2. 5
2. 5
(1)
.
1 Saturated.
’ ?otation
assay
Assay
Hydrochloric ____ _ _
48
Pulp density
per cent
~
Per cent
weig
per cent pH
'
25 Hy d r oilucrsilic
10.—(27%—30%)__.
Tailing
-
.
Assay
7
Hydrofluoric-
in a Fagergren ?otation machine ‘at various pulp
densities. The metallurgical results appear in the
‘
,
Per cent Fe
ceni:1t
N'ouefcontrol test. ________ __ 13. 87
2. 5
24'. 39
2. 5
26. 74
e?ected at 67% solids with the same amount of
‘
Lbs/ton
7
20
‘the same reagent and acid, followed by ?otation
following table;
»
Telling
‘
' The acids all show improved recovery, although
60. 29
86. 32
7. 31
2. 4
57. 86
82. 8S 1
9. 62
____ __
' 22
53. 84
89. 15
6. 94
____ __
33
there is considerable variation. A very weak acid,
11
1 such as boric acid, is not 'su?lciently effective
35 for economical operations on a-commercial scale.
In generai,_a dissociation constant between 10-7
and 10-8 represents the lower limit of utility.
Example 14
_ The variation of flotation pulp density causes
a considerable change in grade, the ‘best results
‘being at the very low density of, 11%. At this
density, however, v the capacity of ‘the machine .is 40 4 Various dispersing agents can be used in the
decreased and the particular density t‘obe chosen
present process prior to‘ desliming. "The follow
will be the result of an economic" compromise be;
ing tests; were made.‘ The ore used was that of
‘tween output oandvgr'adeu V
V
Example '1 and the dispersing agents were added
prior to deslirriing.vv III-each case conditioning
'
’ fEmampZe '12 _~_
_
i I
.
The effect or slime. was determined,' using a low 45 was effected at high solids'with 2.2 lbs. of the
secondary butanol mixture of Calol and SP-l and
grade Minnesota iron ore. ‘This ore was divided .
2.5 lbs. per ton of‘sulfuric acid (except in the
into three'portions, ,the ?rst ‘of which: "was de
case of sodium hydroxide, where 3.5 pounds of
’
sliined thoroughly,’ the Ssecond was not 'deslimed
sulfuric acid per ton were used in order to neu
at all; and'the-third was'partially deslimed. Con 50 tralize the alkalinity). Thepulp was diluted to
diti'oning was e?'ected at high solids with the
secondary butanol mixture of Calol and SP-l and .
sulfuric acid, the optimum amounts oi reagent
and acid being used in each case. The metal
lurgical results appear in the following table.
55
. flotation density, and ?oated in a Fagergren flo
"tation machine with a single cleaning. The fol
lowing metallurgical results were obtained.
V Additionalreagents h
Concentrate
Tailing
'
cent
Product
P
'
_
er
~
.P
'
gisttri'
or
cent
cent
Fe
vinsol.
n 1011
Fe
*
Name ;
._
Lbs/ton
'
8'22"‘
jHiSO‘ 60
sodium silicate___.'..
Sodium dioctyl s
\
Calc. head _________ __
14. 53
_____ ._
40. 92> '
___-,.__
Clean. cone ________ __
60.17
Clean. tail..Rough. taiL.
11.57. '
0.85 '
Rough. cone.
'
losvll'ccinaten?
Slime__._
2.50
Calcium lignin sul-
6-5
14.55’
Como. No
41.53 '
Clean. conc No
55.115
Clean. ta
15.47
_________ __
Rough. tail
'
assay
Assay
fonate (crude).____
Dist.
3.00
42. 5e
60. 25
84.35
0. 50
37. 77
61. 41
'68. 71
' 11. 54
2. 00'
42.14
60.77
85.05
’ s13
2.00
39. 97
61. 41
81. 26
6. 67
'
5.26
'
Itwill be noted that the use of the‘ dispersing
l
Calc. head_
‘ Fe
wt‘
-
.;
Sodiuin hydroxide.“
53. 49.‘ >
N o desliming: '
per cent
>
Substantially complete
desliming:
Per cent Fe
'Percent
. '5 agents does not adversely a?ect the ?otation op
‘ Y er‘ation, which is an added advantage of the pres
invention as it permits
.170 exit
‘which aid in desliming.
4. ()2
the use of agents
.
Rough. cone. No. 2... 36.61.
Partial deslimingz-
>
“Gale. 1;
“ ‘Slime-
_ ~
' '
Rough. con
Tallinn" '
'»
~
"
'
~14. 22. -
.
‘35.93vv
.
56.52
4.02
Example 15
‘
" Anumber of tests were runwith the deslimed
.- i
22.10
__
----- -_
75
ore of Example 1 to determine the effects'oi vary
2,410,376
13‘
It will be apparent that the present invention
ing amounts of fuel oil and reagents. In every
case the deslimed ore was conditioned at high
is not at all critical with respectto the organic
solids with the reagent and 2.5 lbs. per ton of
sulfuric acid were used in the conditioning. The
?rst four tests used a constant amount of re—.
agent, 2.2 lbs. per ton of an equal mixture; of 1.
both from the standpoint of grade and recovery
being obtained in each case.
solvent used, commercially acceptable results
Calol and SP—1, diluted with 10% secondary
"
Example 1'7 '
butanol, and the second four tests used a con
stant amount of fuel oil, 1.12 lbs. per ton,'and
A further series of tests was made on the ‘ore
varying amounts of the alcoholic mixture of 10
used in Example 16, but a different" petroleum
Calol and SP-l. The metallurgical results are
shown in the following table.
_
Lbs/ton
Concentrate
.
1
2. 20
y
acid
- oil
Tailing
Per cent Fe
Sulfuric Fuel Per cent
weight
aisgzl't
98 Fee
Assay
Dist.
56.52
20
‘2. 50
None
84. 26
~ 8. 77
2. 20
2. 50
0. 56
47. 32
56. 88
89. 54
. V5. 97
2. 20
I 2. 20
2.50
2.50
1.12
2. 24
47.09
32. 50
58.83
v 58. 83
90.07
62. 79
5.77 » r
16. 79
V
,
45. 38
In each case the reagent consisted of 3 parts'of
Ultranate No. 3 to 1 part of the organic solvent.
15 The amount of sulfuric acid used was 2.5 lbs. per
ton as in the preceding example. A rougher con-J
centrate only was taken. The metallurgical re
sults appear in the following table.
,
‘
Sulfonate
used,
lbs/ton
sulfonate, namely Ultranate No. 3, was employed.
‘
7' 1. 65 .
2. 50
1. 12
28. 34
57. 82
53. 98
19. 49
-~ 2. 20 -
2. 50
1.12
47. 09
58.83
90. 07
5. 77
2. 75
2. 50
1. 12
50. 09
57. 31
94. 53
3. 33
51. 94
48. 58
56. 44
59. 61
3. 30
2. 50
1. 12
After one c_eaning operation
_
_
'.
Concentrate
. Reagent
Organic solvent
I
' 96. 60
2. 15
95. 42 ______ __
gigging‘
use
s./ton
Per
‘
y’t
per can
2. 06
2. 50
2.42
Fe
Wt’
Assay Dist.
42. 28
46. 13
46.12
59. 54
59. 16
58.90
25
It" will be noted that there is an optimum
amount of'fuel oil» and an optimum'amount of
Per cent Fe
cent
83. 31
89.35
90.32’ v
8. 74
6. 04
5.40
reagent. These “amounts will’ vary- somewhat .30
from ore to ore and from reagent to reagent.
Example 18
'''The following tests were made to compare
various‘ organic solvents ‘andrmaterials'used in
combination with mahogany-soap. Theore and
The use of acid salts instead of acids'wa's illuse
trated by the following tests‘in which a deslimed
conditioning procedure was the‘ same as in the
preceding example. In each case 2.2 lbs. per ton
ore similar to that in Examplel was used, being
step, at which time the additional reagent was
also introduced. After dilution to ?otation
density the pulp was ?oated in a Fagergren ?ota
by a single cleaning was used and ‘in the second
conditioned at high solids with varying, amounts
of the'secondary'butanol mixture of Calol and
of an equal mixture of. Calol and SP-l; diluted
SP-l and acid salts. After dilution to‘?otation
with 10% secondary butanol, and 2.5 lbs.’ per ton
of sulfuric acid were used in the conditioning 40 density in the ?rst test a roughing float followed
test a rougher concentrate only was'taken. The
metallurgical results appear in the following table.
_
>
‘
Acid salt a
Sulfogate
use ,
5
lbs'lton
> 4. 40
2.20
,
.
7 Name
Potassium blsulfate_-__
Sodium
Per
Lbs/ton
P er cen t F e
cent
Tailing'
Assay
-
per cent I pH
wt‘
Assay Dist.
10.0
44.00
60. 96
88. 64
4. 89
2. 4
6. 0
42. 78
59. 28
83. 12
9. 00
2. 4
chlorosulfon-
ate ________________ -_
Concentrate
Fe
.
‘
tion ‘machine and cleaned fence. The metal
lurgical results appear
in the following table.
'
‘
V “ Additional reagent
60
~Concentrate
_
Tailing
'
.
‘Name
,
_
‘
‘ 19
2 Example
.
.
Per
'
assay
'1)“ cent Fe
_7
per cent
Lbs/ton
cent
> _
wt
Assay ‘Dist.
Fe 7
0.75
49.81
57.82
94. 12
j 0. 75
51. 10
57. 05
95. 09
0. 68
0.70
43. 39
45. 09
59.36
60. 25
84. 30.
88. 42
47. 53
42. 57
35.41
58. 97 92. 65 .
60.38 ‘83. 15
59. 87' 69. 61 ‘
6. l5
2. 31
. 6. 28
11. 15
45. 72
39. 26
45.01
47. 09;
60. 90
,59. 23
3. 85
10. 26
65
Oleic acid.
Talloel‘u'?
_--
Naphthenlc acid.
Cottonseed oi1____-_-.__
‘
0. 50
0. 68
. 0.67
' 1. 00
.
__
Chlorinated kerosene-.Fuel oil ‘No; 2 l.__.-._._‘. ,
[-1Bougherrllotationonlym
0. 74
0.83
0. 53
1.12
42. 49
..
60. 25
83. 35
90.15
75. 77
v59. 74 87. 47
5s. 83: 90.071
, 2. 69
r
2. 44
.
6. 79
. 3. 72
3.- 33
7, _5. 77
The double flotation of Minnesota iron ore con-3
taining about 29% Fe was carried out by deslim
ing' the ore, conditioning with 2.2 lbs. per ton of
an equal mixture of Calol and SP-l (diluted with
10% secondary butanoll andf2.5 lbs. per ton of
sulfuric acid. The conditioning ltook place at
67% ‘solids. The conditioned pulp was then di
luted, subjected to flotation, conditioned with ad->
70 ditional 1.1_ lbs. per ton of the sulfonate. mixture
and again ?oated, followed by treatment of the
‘concentrate with quebracho and soda lash and
desliming.v Cationic ?otation with pinejoil and
75 laurylaminehydrochloride was‘ then EconductedLE
2,41 0,376
15
The ?otation procedure and metallurgical results
16.
tion because it permits obtaining good results with
are tabulated in the following table.
Flotation
Operation
‘
per cent
‘
‘i
many iron ores _in a ?otationcircuit which is sub
‘.
'
.
Laurylamine
Qnebraclio, Soda ash, Pine oil,
solids
lbsJton
lbs./ton
hydrochlw .
'
lbs/ton ride-‘wing! I
Deslime ____________ __
Conditioner _________ __
Elotation—anionic.
Condition the cone.._..
Deslime.____________ __
wli‘lotation-cationic - _
stantially neutral, and, therefore, does not pre
15 sent a serious corrosion problem, making it un
.
necessary to use acid-proof material except in
the conditioner which is ‘a type of apparatus more
Percent Assay per Dist. per
Pmduct
wt.
> _cent Fe
cent "Fe
Head.._-_._ _______________________ __
100.00
28.98
100.00
Primary slime _____________________ ..
5. 14
22. 89
. 4. 06
Rougher tailing ___________________ __
39. 70
Secondary slime.
2. 57
3. 52
__._
4. 06
15. 69
2. 20
__
4, 45
24. 18
3. 71
Iron tailing"!_________________ _-
46. 65
53. 75
86. 51
Silica conc ___________ __
readily acid-proofed than ?otation machines.
Any of the ordinary alkalies, such as caustic soda
20 or ammonia, may be used.
Alkalies which form
insoluble compounds, such aslime, ,do not give
quite as good results. Because of its relatively
low- cost and excellent results, soda ash is nor
mally preferred.
Example 20
25
_In the examples the invention has been de
scribed in connection with the use of a Fagergren
subjected to conditioning at high solids with an
?otation machine. This machine gives excellent
equal mixture of Calol and SP-l, diluted with
results in the process of the present invention and
10% secondary butanol, and various tests were
run; ?rst with 2.5 lbs. of sulfuric acid, then with 30 is ‘preferred. However, theprocess of the present
invention is inrno sense limited to any particu
no acid but soda ash in the conditioning, and
lar ?otation machine andkany of the ordinary
?nally acid treatments followed by neutralization
types of ?otation machines may be employed.
of the acidity with soda ash in the ?otation cir
A deslimed ore suchas used in Example 1 was
. All of, the oil soluble petroleum sulfonates re
cuit. The Various samples of ore were then di
luted to ?otation density, ?oated in a Fagergren 35 ferred to in the examples under the trade names
are typicalpetroleum sulionates of the mahog
?otation machine to produce a rougher'concen- I
any soap or acid type as commercially obtained
trate and, following the addition of more resul
from the treatment of .petroleum lubricating oil
fonate a scavenger concentrate, the scavenger
fractions with sulfonating: agents, such as sul
concentrate being intended to be treated as a
furic acid, oleum and .the like.
middling and recycled in the circuit. ' The metal
lurgical results appear in the following table in
which the scavenger concentrate appears in the
second linev of eachsuccessful test.
Concentrate
'
_
'Per cent Fe
' ‘lbs/ton
acid,
'
'
'
‘ ‘
lbs mm
lbs/ton
‘
‘
Assay
2.20
1. 10‘
- 2.20
2. 5
None
_..
None '
None
5. 0
'
Assay,
Dist.
58. 68
76.71
39. 28
15.1)6
per cent
Fe
No useful ?oat V
produced
pH
___.
_.__
5.12
' 2. 6
___.
10.0
'
,
2. 20.
2-5
3.0
57.43.
79. 49
___.
___.
1. 10
___
Noll
27. 69
13. 05
5. 26
6.8
2:20
‘2:5
~65. 95'
_;-_-
_-_V_. a
1. 10
___
23. 21
6. 92
7. 3
'
4. 0' ' -
None
59. 10'
39. 49
We claim:
1. A method of vbene?ciating oxidized iron ores
by froth ?otation of the cm in the form of an
aqueous pulp, which comprises conditioning the
Final tailing
Sulfonate Sulfuric Soda ash";
used,
40
The results clearly show that, in the absence of
acid, soda ash prevents any useful ?oat, whereas
ore with an inorganic acid substance, the anion
not which is a constituent of an inorganic acid
having a dissociation constant of at least 10-", the
amount of said acid substance being such that
on dilution to froth ?otation density and ?oating.
the rougher tailing in the absence of added alkali
50
shows a pH in the range of 2 to 6, and subjecting
' the-aqueous pulp of said treated ore to froth ?ota
tion in the presence of a collector for oxidized iron
minerals, the major constituent of which is an
oil soluble petroleum sulfonate obtained in the
re?ning of petroleum lubricating oils and remov
ing a. concentrate/relatively rich in iron‘ and a
tailing. relatively'poor in iron.
7
j
‘ ‘
2. Amethod' o‘flb'ene?ciating oxidized 'iron ores
if the ore has been treated with acid, a consid
by froth ?otation of the ‘ore 'in'the form of an
erable amount of _soda ash, :up to :the, amount v60 aqueous pulp, which comprises conditioning the
which results in an almost neutral. circuit,-does
ore ‘with sulfuric'acid, the amount of said sul
not adversely a?ect the recovery and ‘grade.
When the amount of_ soda ash is increased still
further some falling o? in recovery is to~be noted;
but in this case the vgradeoflthe scavenger con
centrate is much higher and, therefore, ;a cone,
siderable portion of the iron values‘ would :be
recoverable therefromj This‘results in an overall
iron ‘recovery when recyclingiof ‘the ,middlings is
employed, which is not substantially "poorer than
with' smaller amounts ofv soda ash. The vreason.
forthe curious behaviour of acid-treated ore is
not known, but it indicates that the pH. .oithe
?otation circuit is not _thef‘coiitrolling factor;
This is an added advantage of the present inven- ‘7
furic acid being such: that ondilution to froth
?otation density and ?oating, the rougher tail
ing in the absence of added alkali shows a pH
in the range of_2 to 6, and subjecting the aqueous
pulp of said treated ore togfroth ?otation in the
presenceot a collector :foroxidized iron minerals,
the major'constituentof which ‘is an'oil soluble
petroleumsulfonate 1 obtained in the‘ re?ning of
petroleum ‘lubricating :oils and removingv ‘a con
centraterelativelyrich‘ in iron and atailing rela
ti-vely poorvin iron.
"
'
‘
"
Y
‘
‘i? 3. A method according to claim. 14in which
conditioning is effected at high solids with both
collector and acid substance and the thus condi~
2,410,376
17
tioned pulp is then diluted to ?otation density
before froth ?otation.
4. A method according to claim 2 in which
conditioning is effected at high solids with both
collector and sulfuric acid and the thus condi
tioned pulp is then diluted to ?otation density;
before froth ?otation.
5. A method according to claim 1 in which
the conditioning is with a mixture of petroleum
10
sulfonate and an unsulfonated oil.
6. A method according to claim 2 in which
a
18
the conditioning is with a mixture of petroleum
sulfonate and an unsulfonated oil.
7. A method according to claim 1 in which the
conditioning is at high solids with the ‘acid sub
stance, petroleum sulfonate and unsulfonated oil.
8. A method according to claim 2 in which the
conditioning is at high solids with sulfuric acid,
petroleum sulfonate and unsulfonated oil.
ROBERT BEN BOOTH.
EARL CONRAD HERKENHOFF'.
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