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Patented Nov. 5, 1946
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UNITED STATES PATENT
2,410,770!
FFiCE
2,410,170
BENEFICIATION 0F FLUORITE
Robert B. Booth, Springdale, and Joseph E.
Carpenter, Greenwich, Conn., assignors to
' American
Cyanamid
Company,
New‘ York,‘ _
N. Y., a corporationof Maine
Nov Drawing. . Application August 23, 1943,
Serial No. 499,693
8 Claims. '
(Cl. 209—166)
This invention relates to'the bene?ciation of
non-siliceous minerals. More particularly, the
invention relates to an improved'method of con
2
only will. permit carrying out the operation with
out heating, but which will produce an equally
good or‘better bene?ciation at low temperatures
than that previously obtainablewith comparable
centrating ?uorite by ‘froth ?otation from ores
containing ?uorite, barite, calcite and other like 5 amounts of 'the usual reagents, even when the lat
ter are used in a heated pulp.
non-siliceous minerals, as well as siliceous min
erals.
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_
.
In general, the objects of the present inven
~
tion are accomplished by the use of a ?otation
Concentration of ?uorite » from ?uorite-con
taining ores in which the remaining constituents
reagent comprising sulfonated vpetroleum hydro
are principally non-metallic, non-siliceous min
carbons of the green acid type obtained in the re
fining of petroleum lubricating oils or salts or
soaps of such acids. In addition, a suitable de
erals constitutes an industrially important oper- _
ation. Extensive installations for carrying out
this operation by froth ?otation are in regular
, pressant for the calcite and the like mineralsis
ordinarily used. In order to obtain optimum
ores by frothv ?otation should be quite simple since 15 results, certain ores are preferably conditioned
with the reagents at high solids prior to the actual
the pure mineral itself is readily ?oated by the
use.
Theoretically, the bene?ciation ‘of ?uorite
froth ?otationl
use of so-called “anionic” ?otation reagents such -
as for example the fatty acids, talloel and the
like as well as the various soaps thereof.
Un
Sulfonated petroleum hydrocarbons, such as
I‘ those which constitute the principal reagent in
fortunately however, the gangue constituents of 20 carrying out the novel process of the present in
many ?uorite-containing ores are also readily
collected by the same reagents. As a consequence,
vention, are commercially available in a number
' of different ~forms. However, as shown, for exam
ple, in U. S. Patent 2,331,049, their principal
considerable work has been done to develop sat
source is as by-products from the re?ning of pe
isfactory methods of carrying out the operation.
_A number of such processes have been proposed. 25 troleum lubricating oil fractions in the‘ course of
treatment with fuming sulfuric acids‘ or sulfuric
Some have been} practically useful, others have
acids, When so produced, these by-products are
not.
generally found to be salts of the sulfonated hy-l
Of these proposed methods, those which have
drocarbons. Most commonly, the metallic radi
produced acceptable results have usually in
volved heating the ore-pulp which "is to be sub 30 cal of the salt is sodium. However, salts of other
metals such as. the alkaline earth metals, alu
jected to froth ?otation. Heating the pulp ap
parently serves the double purpose of aiding in ' minum and the like are encountered. In some
procuring proper dispersion of the ?otation re
agents and in improving. their selectivity. 'In
cases, no attempt has been made to neutralize the
_ acid product. Even after neutralization. free
35 sulfonates and/or sulfates are often found.
So far as the present invention is concerned,
it makes little difference whether the sulfonated
out heating, an acceptable concentration is not
petroleum hydrocarbon is used per se or as a
only verydi?lcult to obtain, but at the same time,
salt; whether or notlthe sulfur is present in a
the reagent consumption is usually excessive.
sulfate or a sulfonate group, there usually be
Limiting a process to elevated temperatures in
common practice, the pulp is heated to a tem
perature in therange of about 80-101}° F. With
z
ing some of both present; or whether the com
this way is a serious drawback, both from the
point of view‘ of ‘added expense and from the
pounds-are used as salts of sodium, potassium,
calcium, barium, aluminum and the like. Nor
point of view of ease in operation. The objec
need the materials be puri?ed, since mixtures of '
tionable features of the practice are particularly
aggravated during cold weather, when the wa 45 compounds produce wholly satisfactory results.
As used in the present case, the term ‘,‘sulfonated .
ter supply is necessarily at a low temperature.
petroleum hydrocarbons” is therefore intended to
Despite the obvious inconveniences of heating, it
include such mixtures as'are found in the com
has continued to be regarded as necessary for
‘
, successful operation.
mercial
products.
'
'
There remains therefore an unsatis?ed de-' 50 Petroleum sulfonates, or derivatives thereof,
which are suitable for use according to the'proc
mand for a process of bene?ciating ?uorite which
ess of the present invention are commercially
is not subjected to these dimcultles, i. e., one
available under a variety of designations. Among
which is not particularly sensitive as to the
these found to be useful are “Petronate” and
amounts of reagents used and does not require
heating-the pulp in order to obtain sucessful bene 55 “O-Emulsi?er,” obtainable from L. Sonneborn'
sons; “Eldrol” and “Petrosul,” obtainable from
Pennsylvania Oil Products Re?ning (30.; Sherwood “Reagent 407,” obtainable from Sherwood
present invention to provide one such process.
Re?ning C0,; “Ultranate #2,” obtainable from
It is also an object of the present invention to
00.; and “SP-1,” “SP—302,” and
provide a novel reagent combination which not 60 Atlantic
?ciation.
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'
'
It is, therefore, the principal object of the
' 2,410,770
1
3
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4
“SP-312," obtainable from ~Stanco ‘Distributors,
making successful concentration. In the process
Inc.
of the presentinvention, this di?iculty is readily
>
'
However, the vcommercially-available, sulfo- I
nated petroleum hydrocarbons may be divided
on a functional basis into two distinct groups.
One of these is the group variously known as
“mahogany” acids, “mahogany” soaps and the
like. This group is characterized in that itscon
stituents are generally oil-soluble but water-dis
persible. Usually, but not necessarily, these com
overcome by the addition of an amount of a more '
hydrophobic material. This may be done by
adding an oil in suitable quantity or by mixing
some of the oil-soluble petroleum sulfonates with
the water-soluble type. Any of the commercially
available oils of animal, vegetable or mineral
origin may be used for this purpose. Unsulfo
10 nated petroleum derivatives such as crude oil,
‘ pounds have a deep mahogany color when in
kerosene or fuel oil are very suitable. Saponi?
able oils, such as cocoanut oil, cotton seed oil and
tion as “mahogany" compounds‘.
'
'
other glyceride oils may be used. Anionic ma
The other group is generally, but not neces
terials such as the fatty acids and the lilee'also
sarily, ‘characterized .by a green coloration in 15 may be used, provided the gangue constituents
solution. Hence, compounds of this group are
are such as not to ‘be ?oated by these materials.
. usually referred to as ,“green-sulfonic’? acids or
Talloel, in view of its low cost, is especially
solution which gives rise to the generic designa
“green” soaps. More important than the color
' distinction'however, is the fact that the so-called
useful.
.
_
Amounts of these materials used will obviously
“green”. compounds are characterized by being 20 vary with the particular circumstances.
water-soluble.
Despite their other similarities _
the two groups of compounds are by no means
The
~m'ost pronounced variations in demand are
caused by the nature of the ore‘ and the particu
necessarily equivalents each to the other. Par
lar' water-soluble petroleum sulfonates being
used. No general rule can therefore be empirical
. when they are applied to ore dressing problems. 25 ly established for all cases; In general, however,
The instant applicationlis primarily concerned
the amounts required have been found to fall
with the use of the water-soluble petroleum sul
within the range of about 0.1-2.5 lbs/ton of ore
fonates, i. e., the green sulfonic acids and salts
treated. Ordinarily however, the amounts used
or soaps thereof, which require considerably dif
will be between about 0.5 and 1.5 lbs/ton. Vari
ferent treatment-than those of the “mahogany? 30 ations in the temperature. at which the ?otation
ticularly is this true as in the present invention,
or oil-soluble type.
r
‘ In general, the process of the present inven
is carried out'ha've also been found to have an
effect on the amount of these hydrophobic ma
tion comprises the steps of reducing the ore to a
terials required.
vsize suitable for feed to ‘a froth ?otation opera
Similarly, the nature of the ore, the tempera
tioni desliming the ore, if necessary; making a 35 ture, the pulp density, the water used. the source
pulp of the ore with water: adding the reagents
of the water-soluble petroleum sulfonates and the
thereto; subjecting the pulped ore to froth ?ota
amount of slimes present, all have been found to
tion andl?nally collecting the froth concentrate . have a direct bearing on the‘amount of water
in the usual manner.
soluble petroleum hydrocarbons required. to bring
Where it is desirable to use a desliming opera 40 about an effective concentration of the mineral
tion, it has been found well in some cases to carry
out this operation in the presence of ‘soda ash or
some equivalent alkaline material to assist inv
freeing the slimes. If a depressant for the gangue
is to be used in the subsequent operations, it is
- also well to add a, small amount of the depressant
value. Therefore, as in the case of the hydro
~ phobic materials, nofixed rule applicable to all
instances can be laid down as to the amount of
collecting agent required. In general, however, it
has been found that amounts of water-soluble
petroleum hydrocarbons ranging from about 0.1
during desliming. ‘Wherev a, depressant for the
to 5.0 lbs/ton will take care of all but the most
gangue' minerals is to be used in carrying out the '
extraordinary cases. With the ores most com
process or the present invention, quebracho was
monly encountered, this range can be substan-.
50
found to give excellent results. Other depres
tially halved, since most of the ores may be read
sants such as dextrin, particularly yellow com
ily bene?ciated using an amount of reagent in
dextrin, and the alkali phosphates'and polyphos- '
the range from about 0.2 to 2.5 lbs/ton.
‘
phates may bev used with highly satisfactory re
As has been shown, the water-soluble. petroleum
sulfonates have generally proved to be satisfac
It was also found desirable in certain cases to 55 tory when used. as the principal promoter for the
condition the ore-pulp with the ?otation reagents
?uorite minerals. However, certain external cir
.prior to the actual ?otation step. Pulp densities
cumstances may require that the actual froth ?o
of about 60-65% solids were found to give ex
tation operation be carried out in the presence of
cellentresults and to be ordinarily preferable.
other substances such as oleic acid, talloel and the
sults. In some cases no depressant is necessary.
-
However, if so desired, lower pulp densitieseven 00 like which are themselves we'll known anionic
down to densities such as those commonly used
type reagents. This condition may be brought
in ?otation operations per se may be used. The ' about by the nature of the ?ow scheme employed,
‘invention is not necessarily limited to any par
the presence of these additional agents being due
ticular mode of admixture, and the reagents
to other operations which are'being carried out in
may be added- directly to the ?otation cell if so
the same plant. 7 For example, these reagents are
desired and still obtain acceptable results;
frequently carried along in reusing process water.
‘ The green type, of petroleum sulfonates and/or
It has been found that the water-soluble petro
their derivatives which are used in the present
leum sulfonates are perfectly effective in, the
process are characterized, as noted above,.by their
presence of these ‘extraneous reagents. In fact,
solubility in water. While this solubility is not 70 as has _ been noted above under some circum
always complete, it is sumciently high so that
stances, these agents may be added deliberately
when used alone the reagent may ‘not always
in order to replace all or part of the oil normally
produce the optimum concentration of ?uorite.
used to overcome any di?iculty which may arise
These green compounds appear to lack certain
due to the solubility of the sulfonated petroleum
water-repellent. properties "which are helpful in 75 hydrocarbons. Similarly, the presence {of small
' 2,410,770
10 toi. 'll'hisv conditioned pulp was subjected to
froth flotation in the Fagergren Flotation Ma=
fonates has been frequently found to increase the ~
chine at room temperature as inmample 1.
e?ectiveness of these additional reagents in their ’ Illustrative results are shown in Table H.
intended applications.
I
Table If '.
There is, however, a marked advantage ofthe
present invention in that equally good or better
Hydroil R. ‘lb/ton _____________________ .. 2.02
results can be obtained at low- temperatures than _ Gleaner cone-per cent Car's assay _____ __ 0%.2'?
amounts of the watersoluble petroleum sul
are normally obtained in prior practice at high ‘ . Cleaner conc.—per cent CaCOa assay_'__-.. 5.02
temperatures. This ‘feature of the invention wili
Cleaner conc.--per cent Cali‘: distribution.-. 68.96
be more fully illustrated in connection with the 10 Cleaner tailing-per cent CaFr assay‘. ____ -_ 63.81
following examples which are meant to be illu‘s
trative only and not by way of limitation. All
parts are by weight unless otherwise noted.
‘"Ibns” as used in the following examples refer to
Rougher tailing-per cent Cali‘: assay_____ 2%.81 ‘
We claim:
'
1. A process of bene?ciating ?uorite-contain?
'15 ing ores, which comprises subjecting an aqueous
pulp of such ores to froth ?otation in'the presence
of from about 0.2 to 5.0 lbs/ton of ore of a collec
An Illinois ?uorite ore, containing chie?y ?uor»
tor comprising a water-soluble product selected
short tons-
'
'
ExArsrLE 1
ite (about 72% CaFr) and limestone (about 18.5%
from the group consisting of sulfonates of the
CaCOs), was ground to minus 65 mesh and de
green acid type obtained ' in the re?ning of
slimed using 2 lbs/ton of soda ash and 0.1 lbJton 20 petroleum
lubricating oils and soaps and water
of quebracho. The deslimed pulp was then-made
soluble
salts
of such sulfonates.
up to 22% solids and conditioned for 1 minute
2. A process of bene?ciating fluorite-containing
with about 0.1 lb./ton of quebracho and varying
ores in which a majorjportion of the gangue is
amounts of green acids. In different'tests the
pulp was treated at di?erent temperatures.
comprised of non-silicious minerals, which corn»v
prises subjecting an aqueous pulp of the ore to
The conditioned pulp was subjected to froth
froth ?otation in the presence of an effective
flotation in a Fagergren Flotation Machine. The
t of a depressant for the non-silicious
concentrate was cleaned once using 0.25 lb./ton
. game, about 0.2 to 5.0-lbs./ton of ore of a water- _
of quebracho. It was found that acceptable re
sults could be obtained using green acids in 80 soluble product selected from the group consist
ing of sulfonates of the'sgreen acid type obtained
amounts varying from 0.5-2.0 lbs./ton over a
in the re?ning of petroleumglubricating oils and
temperature range of from 32-100" F. vAt the
lower temperatures it was found that slightly , soaps‘ and water-soluble salts of'such sulfonates,
and an amount of a compatible oiling agent e?ec- >
more reagent was required, that the recovery was
slightly less but that the concentrate in general 35 tive to increase the water-repellent‘properties of
the, water-soluble sulfonated product.
_
was of higher grade and contained less objection
3. A process of bene?ciating ?uorite-containing
‘able non-metallic gangue'. Illustrative results
ores which comprises subjecting an unheated
are shown in Table I.
.
-
aqueous pulp of such ores to froth ?otation in
Table I
.
40 ‘the presence of from about 0.2-5.0 lbsJton of
ore of a collector selected from the group consist- I
32
'
.
Temperature, °F ______________ __
86
LbJton-green acids __________ __
1.00
' 1.50
ing of the water-soluble sulfonates of the green
LbJton-fuel oil.._._.._.. ________ _.
1.00
1.50
acid-type obtained in the re?ning of petroleum
lubricating oils and soaps and wateresoluble salts
~Cleaner conc.—per cent, CaFa
assay .__________________..___.... 98.58
94.78 45.
Cleaner conc.-p'er cent cacos
Cleaner tailing-:per cent Calla
assay _______ __' ______________ -0158
4. A process of bene?ciating ?uorite-containing
_ores in which a major portion of the gangue is
ease
comprised of non-silicious minerals which _c0m-=
assay __________________ _4_---__
Cleaner conc.—per cent Cali‘: disI
tribution __________________ _; ‘11.33
of ‘ such sulfonates.
3.96
ram
Rough tailing-—per cent CaFr as
say _______________________ _. 14.60
prises subjecting an unheated aqueous pulp of
v50 the ore to froth ?otation in the presence of an
42.00
effective amount of a depressant for the non
silicious gangue and about 0.2-5.0 lbs./ton of ore
of a collector selected from the group cons
~_
of the water-soluble sulfonat'es 'of- the green acid
As was noted'above the presence of mahogany
soap in addition to the green type oi’ compounds 56 type obtained in the re?ning of petroleum lubri
eating oils and soaps and water-soluble salts of
permitted excellent beneficiation operations to be carried out using none of the oil or fatty acid
which was found to be important when green
acids alone were used. An illustration ‘of this
such sulfonates.’
I
.
.
5. A method according to claim 2 in which the
voiling-agent is present in amounts of from about
type of operation is shown in the following ex
0.2 to 2.5 lbs. per ton of ore.
ample.
oiling-agent is an unsulfonated petroleum ,hy
-
Exam“ 2
,
-
An additional sample of the same ore treated in.
» Example 1 was ground and deemed in-the same “5
~. manner. Portions of the 'deslimed' ore were then
subjected to the conditioning operation at about '
65% solids with varying amounts of Hydroil R
(a commercial mixture of water-soluble and oil
soluble; petroleumv sulfonates ‘obtainable tram 70
Emery Industries Inc.) which was diluted with
secondary butyl alcohol ‘in the proportion'of
.
.
_
6. A method according to claim 2 in which the
drocarbon.
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'
V
"7. A methodaccording to claim 2 in which the
felling-agent comprises an unsulfonated glyceride
8. A method according toclaim 2 in which the
oiling-agent comprises a fatty-acid.
ROBERT E. BOOTH.
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