Note: Descriptions are shown in the official language in which they were submitted.
0~)7~;
--1--
NOVEL COLLECTORS FOR
THE SELECTIVE FROTH FLOTATION OF
SULFIDE MINERALS
This invention concerns novel collectors for
the recovery of metal containing sulfide minerals and
sulfidized metal containing oxide minerals from ores
by froth flotation.
Flotation is a process of treating a mixture
of finely divided mineral solids, e.g., a pulverulent
ore, suspended in a liquid whereby a portion of such
solids is separated from other finely divided solids,
e.g., clays and other like materials present in the
ore, by introducing a gas (or providing a gas in situ)
in the liquid to produce a frothy mass containing
certain of the solids on the top of the liquid, and
leaving suspended (unfrothed) other solid components of
the ore. Flotation is based on the principle that
introducing a gas into a liquid containing solid par-
ticles of different materials suspended therein causes
a &erence of some gas to certain suspended solids and
not to others and makes the particles having the gas
33,740-F -1-
~;~70~)76
thus adhered thereto lighter than the liquid. Accord-
ingly, these particles rise to the top of the liquid to
form a froth.
Various flotation agents have been admixed
with the suspension to improve the frothing process.
Such added agents are classed according to the function
to be performed: collectors, for sulfide minerals
including xanthates, thionocarbamates and the like;
frothers which impart the property of forming a stable
froth, e.g., natural oils such as pine oil and eucalyp-
tus oil; modifiers such as activators to induce flota-
tion in the presence of a collector, e.g., copper
sulfate; depressants, e.g., sodium cyanide, which tend
to prevent a collector from functioning as such on a
mineral which it is desired to retain in the liquid,
and thereby discourage a substance from being carried
up and forming a part of the froth; pH regulators to
produce optimum metallurgical results, e.g., lime, soda
ash and the like.
It is of importance to bear in mind that
additives of the hereinbefore described types are
selected for use according to the nature of the ore,
the mineral(s) sought to be recovered, and the other
additaments which are to be used in combination
therewith.
An understanding of the phenomena which makes
flotation a particularly valuable industrial operation
is not essential to the practice of the present inven-
tion. The phenomena appear, however, to be largely
associated with selective affinity of the surface of
partiGulated solids, suspended in a liguid containing
33,740-F -2-
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1~70~76
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entrapped gas, for the liquid on the one hand, the gas
on the other.
The flotation principle is applied in a
number of mineral separation processes among which is
the selective separation of such metal sulfide minerals
as those containing copper, zinc, lead, nickel, molyb-
denum, and other metals from iron containing sulfide
minerals such as pyrite and pyrrhotite.
Among collectors commonly used for the recov-
ery of metal containing sulfide minerals or sulfidizedmetal containing oxide minerals are xanthates, dithio-
phosphates, and thionocarbamates. Other collectors
commonly recognized as useful in the recovery of metal
containing sulfide minerals or sulfidized metal con-
taining oxide minerals are mercaptans, disulfides(R-SS-R) and polysulfides [R-(S)n-R], wherein n is 3 or
greater.
The conversion of metal containing sulfide
minerals or sulfidized metal containing oxide minerals
to the more useful pure metal state, is often achieved
by smelting processes. Such smelting processes can
result in the formation of volatile sulfur compounds.
These volatile sulfur compounds are often released to
the atmosphere through smokestacks, or are removed from
such smokestacks by expensive and elaborate scrubbing
equipment. Many nonferrous metal containing sulfide
minerals or metal containing oxide minerals are found
naturally in the presence of iron containing sulfide
minerals such as pyrite and pyrrhotite. When the iron
containing sulfide minerals are recovered in flotation
processes along with the nonferrous metal containing
33,740-F -3~
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sulfide minerals and sulfidized metal containing oxide
minerals, there is excess sulfur present which is
released in the smelting processes resulting in an
undesirably high amount of sulfur present during the
smelting operations. What is needed is a process for
selectively recovering the nonferrous metal containing
sulfide minerals and sulfidized metal containing oxide
minerals, without recovering the iron containing sulfide
minerals such as pyrite and pyrrhotite.
Of the commercial collectors, the xanthates,
thionocarbamates, and dithiophosphates do not selec-
tively recover nonferrous metal containing sulfide
minerals in the presence of iron containing sulfide
minerals. On the contrary, such collectors collect and
recover all metal containing sulfide minerals. The
mercaptan collectors have an environmentally undesir-
able odor and are very slow kinetically in the flota-
tion of metal containing sulfide minerals. The disul-
fides and polysulfides, when used as collectors, give
low recoveries with slow kinetics. Therefore, the
mercaptans, disulfides, and polysulfides are not gener-
ally used commercially. Furthermore, the mercaptans,
disulfides and polysulfides do not selectively recover
nonferrous metal containing sulfide minerals in the
presence of iron containing sulfide minerals.
What is needed is a flotation collector which
will selectively recover the nonferrous metal con-
taining sulfide minerals or sulfidized metal containing
oxide minerals in the presence of iron containing
sulfide minerals such as pyrite and pyrrhotite.
33,740-F ~4~
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This invention concerns a froth flotation
process for selectively recovering nonferrous metal
containing sulfide minerals or sulfidized metal con-
taining oxide minerals from ores. More particularly,
this in~ention concerns a process for recovering metal
containing sulfide minerals or sulfidized metal con-
taining oxide minerals from an ore which comprises
subjecting the ore, in the form of an aqueous pulp, to
a froth flotation process in the presence of a flota-
ting amount of a flotation collector wherein the col-
lector has a hydrocarbon containing one or more mono-
sulfide units, wherein the carbon atoms to which the
sulfur atom(s) are bound are aliphatic or cycloali-
phatic carbon atoms, and the total carbon content of
the hydrocarbon portion of the collector is such that
the collector has sufficient hydrophobic character to
cause the metal containing sulfide mineral or sulfidized
metal containing oxide mineral particles to be driven
to the air/bubble interface, under conditions such that
the metal containing sulfide mineral or sulfidized
metal containing oxide mineral is recovered in the
froth.
The novel collectors of this invention result
in surprisingly high recovery of nonferrous metal
containing sulfide minerals or sulfidized metal con-
taining oxide minerals, and a surprisingly high selec-
tivity toward such nonferrous metal containing sulfide
minerals and sulfidized metal containing oxide minerals
when such metal containing sulfide minerals or sulfi-
dized metal containing oxide minerals are found in thepresence of iron containing sulfide minerals. These
collectors demonstrate good recovery and good kinetics.
33,740-F ~5~
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The novel collector of this invention is a hydrocarbon
which contains one or more monosulfide units wherein the sulfur
atoms of the sulfide units are bound to non-aromatic carbon atoms,
i.e., aliphatic or cycloaliphatic carbon atoms. Monosulfide unit
refers herein to a unit wherein a sulfur atom is bound to two car-
bon atoms of a hydrocarbon moiety only. Such hydrocarbon compounds
containing one or more monosulfide units, as used herein, include
such compounds which are substituted with hydroxy, cyano, halo,
ether, hydrocarbyloxy and hydrocarbyl thioether moieties. Non-
aromatic carbon atom refers herein to a carbon atom which is notpart of an aromatic ring.
Preferred hydrocarbons containing monosulfide units
include those corresponding to the formula
R -S-R
wherein
Rl is a methyl or ethyl group or a hydrocarbyl
radical or a hydrocarbyl radical substituted with one or more
hydroxy, cyano, halo, ether, hydrocarbyloxy or hydrocarbyl thio-
ether moieties;
R2 is an aliphatic, cycloaliphatic or aromatic group
or combination thereof, having from 5 to 11 carbon atoms;
wherein Rl and R2 may combine to form a heterocyclic ring structure
with S; with the proviso that S is bound to an aliphatic or
cycloaliphatic carbon atom; with the further proviso that the
total carbon content of the sulfide collector be such that the
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sulfide collector has sufficient hydrophobic character
to cause the metal sulfide particles to be driven to the
air/bubble interface.
The invention, in particular, resides in a
method for recovering metal-containing sulfide minerals
or sulfidized metal-containing oxide minerals from an
ore which comprises subjecting the ore, in the form ofan
aqueous pulp, to a froth flotation process in the
presence of a flotating amount of an organic compound of
the formula:
Rl -S-R2
wherein Rl is a methyl, ethyl, epoxy (i.e.
--C _ C--)
o
group or R3-S-R4 wherein R3 is a hydrocarbyl group and
R4 i5 a hydrocarbylene group; and R2 is an aliphatic,
cycloaliphatic, aromatic group or combination thereof
having from 5 to 8 carbon atoms and under conditions
such that the metal-containing sulfide or sulfidized
metal-containing oxide is recovered in the froth.
The invention also resides in a method of
recovering metal-containing sulfide minerals or
sulfidized metal-containing oxide minerals from an ore
33,740-F -6a-
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~270~'76
-6b-
which comprises subjecting the ore, in the form of an
aqueous pulp, to a froth flotation process in the
presence of a flotating amount of an organic compound of
the general structural formula:
(R)2--c --C--Rl)2
.,
wherein each R and each Rl is independently hydrogen, an
aliphatic, cycloaliphatic, aromatic or combination
thereof, unsubstituted or substituted with one or more
hydroxy, ether, cyanogen, halogen orthioether moieties,
provided at least one R or Rl is not hydrogen and the
epithio collector has at least 6 and less than 20 carbon
atoms, under conditions such that the metal-containing
sulfide mineral or sulfidized metal-containing oxide
mineral is recovered in the froth.
33,740-F -6b-
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Preferably, Rl and R2 are independently an
aliphatic, cycloaliphatic or aralkyl moiety, unsub-
stituted or substituted with one or more hydroxy,
cyano, halo, oR3, or SR3 moieties, wherein R3 is a
hydrocarbyl radical; wherein Rl and R2 may combine to
form a heterocyclic ring with S. Rl and R2 are more
preferably an aliphatic or cycloaliphatic moiety,
unsubstituted or substituted with one or more hydroxy,
cyano, halo, oR3/ or SR3 moieties; wherein R1 and R2
may combine to form a heterocyclic ring with S. In a
more preferred embodiment, Rl and R2 do not combine to
form a heterocyclic ring with S, and R1 and R2 are
alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl,
unsubstituted or substituted with one or more hydroxy,
halo, cyano, oR3 or SR3 moieties, wherein R3 is ali-
phatic or cycloaliphatic. In a most preferred embodi-
ment, R1 and R2 are independently alkyl or alkenyl,
particularly R1 is methyl or ethyl and R2 is a C6 11
alkyl or C6 1~alkenyl group. In the most preferred
embodiment, R and R are not the same hydrocarbon
moiety, that is, the monosulfide is asymmetrical. R3
is preferably aliphatic or cycloaliphatic. R3 is more
preferably alkyl, alkenyl, cycloalkyl or cycloalkenyl.
The total carbon content of the hydrocarbon
portion of the hydrocarbon monosulfide collector must
be such that the sulfide collector has sufficient
hydrophobic character to cause the metal containing
sulfide mineral or sulfidized metal containing oxide
mineral particles to be driven to the air/bubble inter-
face. Preferably, the total carbon content of thehydrocarbon monosulfide collector is such that the
minimum carbon number is 4, more preferably 6, and most
preferably 8. The maximum carbon content is preferably
20, more preferably 16, and most preferably 12.
33,740-F -7_
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Examples of cyclic compounds useful in this invention
include the following structures.
(R ) 2 ~ c\-/c (R ) 2 and R ~ S
wherein R1 and R4 are independently hydrogen, aryl, alkaryl, ara-
lkyl, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, hydroxy,
cyano, halo, oR3 or SR , wherein the aryl, alkaryl, aralkyl, alkyl,
alkenyl, alkynyl, cycloalkyl, cycloalkenyl may optionally be
substituted with a hydroxy, cyano, oR3 or SR3 moiety, and the like;
and R5 is a straight- or branched-alkylene, -alkenylene, or
-alkynylene, unsubstituted or substituted with a hydroxy, cyano,
halo, oR3 or SR3 moiety, provided that at least one Rl is not
hydrogen.
In another preferred embodiment of this invention, the
collectors of this invention correspond to the formula
(R )3_nC(H)n-S-c(H)n(R )3-n
wherein
R6 is independently hydrocarbyl, or hydrocarbyl
substituted with a hydroxy, cyano, halo, ether, hydrocarbyloxy or
hydrocarbyl thioether moiety; wherein two R6 moieties may combine
to form a cyclic ring or heterocyclic ring with the sulfur atom.
n is an integer of 0, 1, 2 or 3; with the proviso that
the total carbon content of the hydrocarbon portion of the collec-
tor is such that the collector has sufficient hydrophobic
character
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70~)76
g
to cause the metal containing sulfide mineral or
sulfidized metal containing oxide mineral particles
to be driven to the air/bubble interface.
Preferably, R6 is aliphatic, cycloaliphatic,
aryl, alkaryl or aralkyl, unsubstituted or substituted
with a cyano, hydroxy, halo, oR3 or SR3 moiety, wherein
R3 is as hereinbefore defined. More preferably, R6 is
an aliphatic or cycloaliphatic moiety, unsubstituted or
substituted with a hydroxy, cyano, halo, aliphatic
ether, cycloaliphatic ether, aliphatic thioether or
cycloaliphatic thioether moiety. Even more preferably,
R6 is an alkyl, alkenyl, cycloalkyl or cycloalkenyl
moiety. Most preferably, one -C(H)n(R6)3 n is a methyl
or ethyl moiety, and the other is a C6 11 alkyl or
C6_11 alkenyl moiety. Preferably, n is 1, 2 or 3, and
more preferably 2 or 3.
The preferred hydrocarbon co~taining mono-
sulfide units of the formula Rl-S-R2, wherein R1 and R2
are defined as above, are prepared by standard methods
known in the art, e.g. reacting R2-H with Rl-SH, where
R1 and R2 are defined as above.
Examples of compounds within the scope of
this invention include methylbutyl sulfide, methyl-
pentyl sulfide, methylhexyl sulfide, methylheptyl
sulfide, methyloctyl sulfide, methylnonyl sulfide,
methyldecyl sulfide, methylundecyl sulfide, methyl-
dodecyl sulfide, methylcyclopentyl sulfide, methyl-
cyclohexyl sulfide, methylcycloheptyl sulfide, methyl-
cyclooctyl sulfide, ethylbutyl sulfide, ethylpentyl
sulfide, ethylhexyl sulfide, ethylheptyl sulfide,
ethyloctyl sulfide, ethylnonyl sulfide, ethyldecyl
33,740-F -9-
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sulfide, ethylundecyl sulfide, ethyldodecyl sulfide,
ethylcyclopentyl sulfide, ethylcyclohexyl sulfide,
ethylcycloheptyl sulfide, ethylcyclooctyl sulfide,
propylbutyl sulfide, propylpentyl sulfide, propylhexyl
sulfide, propylheptyl sulfide, propyloctyl sulfide,
propylnonyl sulfide, propyldecyl sulfide, propyl-
undecyl sulfide, propyldodecyl sulfide, propylcy-
clopentyl sulfide, propylcyclohexyl sulfide, pro-
pylcycloheptyl sulfide, propylcyclooctyl sulfide,
dibutyl sulfide, butylpentyl sulfide, butylhexyl
sulfide, butylheptyl sulfide, butyloctyl sulfide,
butylnonyl sulfide, butyldecyl sulfide, butylun-
decyl sulfide, butyldodecyl sulfide, butylcyclo-
pentyl sulfide, butylcyclohexyl sulfide, butylcy-
cloheptyl sulfide, butylcyclooctyl sulfide, dipen-
tyl sulfide, pentylhexyl sulfide, pentylheptyl
sulfide, pentyloctyl sulfide, pentylnonyl sulfide,
pentyldecyl sulfide, pentylundecyl sulfide, pentyl-
dodecyl sulfide, pentylcyclopentyl sulfide, pentyl-
cyclohexyl sulfide, pentylcycloheptyl sulfide, pen-
tylcyclooctyl sulfide, dihexyl sulfide, hexylheptyl
sulfide, hexyloctyl sulfide, hexylnonyl sulfide,
hexyldecyl sulfide, hexylundecyl sulfide, hexyldo-
decyl sulfide, hexylcyclopentyl sulfide, hexylcy-
clohexyl sulfide, hexylcycloheptyl sulfide, hexyl-
cyclooctyl sulfide, diheptyl sulfide, heptyloctyl
sulfide, heptylnonyl sulfide, heptyldecyl sulfide,
heptylundecyl sulfide, heptyldodecyl sulfide, hep-
tylcyclopentyl sulfide, heptylcyclohexyl sulfide,
heptylcycloheptyl sulfide, heptylcyclooctyl sul-
fide, dioctyl sulfide, octylnonyl sulfide, octyl-
decyl sulfide, octylundecyl sulfide, octyldodecyl
sulfide, octylcyclopentyl sulfide, octylcyclohexyl
sulfide, octylcycloheptyl sulfide, octylcyclooctyl
sulfide, octylcyclodecyl sulfide, dinonyl sulfide,
, 33,740-F -10-
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~z~o~76
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nonyldecyl sulfide, nonylundecyl sulfide, nonyldo-
decyl sulfide, nonylcyclopentyl sulfide, nonylcy-
clohexyl sulfide, nonylcycloheptyl sulfide, nonyl-
cyclooctyl sulfide, didecyl sulfide, decylundecyl
sulfide, decyldodecyl sulfide, decylcyclopentyl
sulfide, decylcyclohexyl sulfide, decylcyclohep-
tyl sulfide, and decylcyclooctyl sulfide. More
preferred sulfides include methylhexyl sulfide,
methylheptyl sulfide, methyloctyl sulfide, methyl-
nonyl sulfide, methyldecyl sulfide, ethylhexylsulfide, ethylheptyl sulfide, ethyloctyl sulfide,
ethylnonyl sulfide, ethyldecyl sulfide, dibutyl
sulfide, dipentyl sulfide, dihexyl sulfide, dihep-
tyl sulfide, and dioctyl sulfide.
Hydrocarbon means herein an organic
compound containing carbon and hydrogen atoms. The
term hydrocarbon includes the following organic com-
pounds: alkanes, alkenes, alkynes, cycloalkanes,
cycloalkenes, cycloalkynes, aromatics, aliphatic
and cycloaliphatic aralkanes and alkyl-substituted
aromatics.
Aliphatic refers herein to straight-
and branched-chain, and saturated and unsaturated,
hydrocarbon compounds, that is, alkanes, alkenes
or alkynes. Cycloaliphatic refers herein to satu-
rated and unsaturated cyclic hydrocarbons, that
is, cycloalkenes and cycloalkanes.
Cycloalkane refers to an alkane contain-
ing one, two, three or more cyclic rings. Cycloal-
kene refers to mono-, di- and polycyclic groups
containing one or more double bonds.
33,740-F -11-
~z~o~7G
Hydrocarbyl means herein an organic
radical containing carbon and hydrogen atoms. The
term hydrocarbyl includes the following organic
radicals: alkyl, alkenyl, alkynyl, cycloalkyl, cyclo-
alkenyl, aryl, aliphatic and cycloaliphatic aralkyl andalkaryl. The term aryl refers herein to biaryl,
biphenylyl, phenyl, naphthyl, phenanthrenyl, anthra-
cenyl and two aryl groups bridged by an alkylene group.
Alkaryl refers herein to an alkyl-, alkenyl- or alkynyl-
-substituted aryl substituent, wherein aryl is as defined
hereinbefore. Aralkyl means herein an alkyl group,
wherein aryl is as defined hereinbefore.
Cl 20 alkyl includes straight- and branched-
-chain methyl, ethyl, propyl, butyl, pentyl, hexyl,
heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,
tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
nonadecyl and eicosyl groups.
Halo means herein a chloro, bromo, or iodo
group.
The process of this invention is useful for
the recovery, by froth flotation, of metal containing
sulfide minerals and sulfidized metal containing oxide
minerals from ores. An ore refers herein to the mater-
ial as it is taken out of the ground and includes the
desired metal containing minerals in admixture with the
gangue. Gangue refers herein to that portion of the
material which is of no value and needs to be separated
from the desired metal containing minerals.
33,740-F -12-
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-13-
In a preferred embodiment, metal containing
sulfide minerals are recovered. In a more preferred
embodiment of this invention metal sulfide containing
minerals containing copper, nickel, lead, zinc, or
molybdenum are recovered. In an even more preferred
embodiment, sulfide minerals containing copper are
recovered. Also preferred metal sulfide containing
minerals are those which have high natural hydropho-
bicity in the unoxidized state. The term "hydropho-
bicity in the unoxidized state" applies to a freshlyground mineral or a mineral having a fresh surface
which demonstrates a tendency to float without col-
lector addition.
Ores for which these compounds are useful
include sulfide mineral ores containing copper, zinc,
molybdenum, cobalt, nickel, lead, arsenic, silver,
chromium, gold, platinum, uranium and mixtures thereof.
Examples of metal containing sulfide minerals which may
be concentrated by froth flotation using the process of
this invention include copper-bearing minerals such as,
for example, covellite (CuS), chalcocite (Cu2S), chal-
copyrite (CuFeS2), valleriite (Cu2Fe4S7 or Cu3Fe4S7),
bornite (Cu5FeS4~, cubanite (Cu2SFe4S5), enargite
[Cu3(AslSb)S43, tetrahedrite (Cu3SbS2), tennantite
25 (Cu12As4S13), brochantite [Cu4(OH)6S04], antlerite
[Cu3S04(0H)4], famatinite [Cu3(SbAs)S4], and bournonite
(PbCuSbS3); lead-bearing minerals such as, for example,
galena (PbS); antimony-bearing minerals such as, for
example, stibnite (Sb2S3); zinc-bearing minerals such
as, for example, sphalerite (ZnS); silver-bearing
minerals such as, for example, stephanite (Ag5SbS4),
and argentite (Ag2S); chromium-bearing minerals such
as, for example, daubreelite (FeSCrS3); nickel-bearing
minerals such as, for example, pentlandite [(FeNi)gS8];
33,740-F -13-
..
~Z70076
-14-
molybdenum-bearing minerals such as for example, molyb-
denite (MoS2); and platinum- and palladium-bearing
minerals such as, for example, cooperite [Pt(asS)2]-
Preferred metal containing sulfide minerals include
molybdenite (MoS2), chalcopyrite (CuFeS2), galena
(PbS), sphalerite (ZnS), bornite (Cu5FeS4), and pent-
landite [(FeNi)gS8].
Sulfidized metal containing oxide minerals
are minerals which are treated with a sulfidization
chemical, so as to give such minerals sulfide mineral
characteristics, so the minerals can be recovered in
froth flotation using collectors which recover sulfide
minerals. Sulfidization results in oxide minerals
having sulfide characteristics. Oxide minerals are
sulfidized by contact with compounds which react with
the minerals to form a sulfur bond or affinity. Such
methods are well-known in the art. Such compounds
include sodium hydrosulfide, sulfuric acid and related
sulfur containing salts, such as sodium sulfide.
Sulfidized metal containing oxide minerals
for which this process is useful include oxide minerals
containing copper, aluminum, iron, tungsten, molybdenum,
magnesium, chromium nickel, titanium, manganese, tin,
uranium, and mixtures thereof. Examples of metal
containing oxide minerals which may be concentrated by
froth flotation using the process of this invention
include copper-bearing minerals, such as cuprite (Cu2O),
tenorite (CuO), malachite [(Cu2OH)2CO3], azurite
[Cu3(OH)2(CO3)2], atacamite [Cu2Cl(OH)3], chrysocolla
(CuSiO3); aluminum-bearing minerals, such as corundum;
zinc-containing minerals, such as zincite (ZnO), and
smithsonite (ZnCO3); tungsten-bearing minerals such as
33,740-F -14-
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~7 6
-15-
wolframite (Fe,Mn)WO4; nickel-bearing minerals such as
bunsenite ~Nio)i molybdenum-bearing minerals such as
wulfenite (PbMoO4), and powellite (CaMoO4); iron-con-
taining minerals, such as hematite and magnetite;
chromium-containing minerals,-such as chromite
(FeOCr203); iron- and titanium-containing minerals,
such as ilmenite; magnesium- and aluminum-containing
minerals, such as spinel; iron-chromium-containing
minerals, such as chromite; titanium-containing miner-
als, such as rutile; manganese-containing minerals,
such as pyrolusite; tin-containing minerals, such as
cassiterite; and uranium-containing minerals, such as
uraninite; and uranium-bearing minerals such as, for
example, pitchblende [U2O5(U3O8)] and gummite (UO3nH20).
The collectors of this invention can be used
in any concentration which gives the desired recovery
of the desired minerals. In particular, the concen-
tration used is dependent upon the particular mineral(s)
to be recovered, the grade of the ore to be subjected
to the froth flotation process, the desired quality of
the mineral to be recovered, and the particular mineral
which is being recovered. Preferably, the collectors
of this invention are used in concentrations of 0.001
kg to 1.0 kg per metric ton of ore, more preferably
between about 0.010 kg and 0.2 kg of collector per
metric ton of ore to be subjected to froth flotation.
Frothers are preferably used in the froth
flotation process of this invention. Any frother
well-known in the art, which results in the recovery of
the desired mineral is suitable.
33,740-F -15-
~Z~0{)76
--16--
Frothers useful in this invention include any
frothers known in the art which give the recovery of
the desired mineral. Examples of such frothers include
C5 8 alcohols, pine oils, cresols, Cl 4 alkyl ethers of
polypropylene glycols, dihydroxylates of polypropylene
glycols, glycols, fatty acids, soaps, alkylaryl sul-
fonates, and the like. Furthermore, blends of such
frothers may also be used. All frothers which are
suitable for beneficiation of ores by froth flotation
can be used in this invention.
Further, in the process of this invention it
is contemplated that collectors of this invention can
be used in mixtures with other collectors well-known in
the art. Collectors, known in the art, which may be
lS used in admixture with the collectors of this invention
are those which will give the desired recovery of the
desired mineral. Examples of collectors useful in this
invention include alkyl monothiocarbonates, alkyl
dithiocarbonates, alkyl trithiocarbonates, dialkyl
dithiocarbonates, alkyl thionocarbamates, dialkyl
thioureas, monoalkyl dithiophosphates, dialkyl and
diaryl dithiophosphates, dialkyl monothiophosphates,
dialkyl and diaryl thiophosphonyl chlorides, dialkyl
and diaryl dithiophosphonates, alkyl mercaptans, xan-
thogen formates, xanthate esters, mercapto benzothiazoles,fatty acids and salts of fatty acids, alkyl sulfuric
acids and salts thereof, alkyl and alkaryl sulfonic
acids and salts thereof, alkyl phosphoric acids and
salts thereof, alkyl and aryl phosphoric acids and
salts thereof, sulfosuccinates, sulfosuccinamates,
primary amines, secondary amines, tertiary amines,
quaternary ammonium salts, alkyl pyridinium salts,
guanidine, and alkyl propylene diamines.
~, 33,740-F -16-
~71~)7 Ei
-17-
Specific Embodiments
The following examples are included for
illustration and are not intended to limit the scope of
the invention. Unless otherwise indicated, all parts
and fractions are by weight.
In the following examples, the performance o
the frothing processes described is shown by giving the
rate constant of flotation and the amount of recovery
at infinite time. These numbers are calculated by
using the formula
1 -kt
y = R~ [1 - kt ]
wherein: y is the fractional amount of mineral recov-
ered at time t, k is the rate constant for the rate of
recovery and R~ is the calculated fractural amount of
the mineral which would be recovered at infinite time.
The amount recovered at various times is determined
experimentally and the series of values are substituted
into the equation to obtain the R~ and k. The above
formula is explained in Klimpel, "Selection of Chemical
Reagents for Flotation", Chapter 45, pp. 907-934,
Mineral Processing Plant Desiqn, 2nd Ed., 1980, AIME
(Denver).
Example 1 - Froth Flotation of a Copper Contain-
ing Sulfide Mineral
In this example several of the collectors of
this invention were tested for flotation of copper
containing sulfide minerals. A 500 g quantity of Western
Canada copper ore, a relatively high grade chalcopyrite
, 33,740-F -17-
.. , ~ .
.
. . .
' '
' .,
-
~Z70~76
-18-
containing ore with little pyrite, was placed in a rod
mill having one-inch (2.5 cm) rods, with 257 g of deion-
ized water and ground for 420 revolutions at a speed of
60 rpm to produce a size distribution of 25 percent
less than 100 mesh. A quantity of lime was also added
to the rod mill, based on the desired pH for the sub-
sequent flotation. The ground slurry was transferred
to a 1500 ml cell of an Agitair Flotation machine. The
float cell was agitated at 1150 rpm and the pH was
adjusted to 8.5 by the addition of further lime.
The collector was added to the float cell
(8 g/metric ton), followed by a conditioning time of
one minute, at which time the frother, DOWFROTH~ 250,
was added (18 g/metric ton). After an additional
one-minute conditioning time, the air to the float cell
was turned on at a rate of 4.5 liters per minute and
the automatic froth removal paddle was started. The
froth samples were taken off at 0.5, 1.5, 3, 5 and 8
minutes. The froth samples were dried overnight in an
oven, along with the flotation tailings. The dried
samples were weighed, divided into suitable samples for
analysis, pulverized to insure suitable fineness, and
dissolved in acid for analysis. The samples were
analyzed using a DC Plasma Spectrograph. The results
are compiled in Table I.
33,740-F -18-
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tl~ ........... . .......
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~t O ~1 U~ N ~ l X O D ~ U~ t~ 0 r~ O 0 ~ CD r~ U) d~
a~ o ~ 7 ~ r~ r~ ) o
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~ a a~ x ~ x ~ ~ x
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U Ul r~ r-l r~t U O X ~ U ~ ~rl I ~ 0 ~ t ~ ~C r~t ~ O El a) ~1 0 ~
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00000000 0 0 0 0 0000
a ~ 0 D ~ ~ d1 ~ ~ U~ O ~ O ~1 ~
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........ . . ......
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~:; P ~ a~ ~ 0 (~ ~ 0 0
........ . . . . ....
00000000 0 0 0 0 0000
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at ~ ~ 0 0
r~ 0 ~ ~ 0
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rl ,~ ~1 ~ ~-~-rl ~1 ~ O ~ O I O rl ~ ~ rl S
~o S ~O ~ O ~ X~ Ll S ~ ~ ~ ~
~1 ~ u o a) r~ ~ ~ o ~ s ~ o x
u ~ a) O ~ O :1 O ~ O Q,-~l ~ N O
~1 I o ~ I I I I S I SSS I 1 05 0 :~
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U ~ ~ ~ E~ u ~ * N
33, 740-F -20-
~70~)76
--21--
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.~ 0 o
~0 ~ 0 0 ~
C I,~,1 ,1 ,1
o o o o
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_It` I` N N ~
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a~ ~ 0
C ~ U~ 0
,, u~ ~ h ~'
o
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~ o o o o
<~1 O ~ N ,~ ~
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g
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o ~ ~
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- ~ ~ x ~ u~ o
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U _I N N N --~ C~
33, 740-F -21-
.,
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.- . . - .
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The collectors of this invention demonstrate
better rates and equilibrium recovery than mercaptan
and polysulfide collectors.
Exam~le 2 - Froth Flotation of a Copper/Molybdenum
Ore
Bags of homogeneous ore containing chal-
copyrite and molybdenite minerals were prepared with
each bag containing 1200 g. The rougher flotation
procedure was to grind a 1200 g charge with 800 ml of
tap water for 14 minutes in a ball mill having a mixed
ball charge (to produce approximately a 13 percent plus
100 mesh grind). This pulp was transferred to an
Agitair 1500 ml flotation cell outfitted with an auto-
mated paddle removal system. The slurry pH was adjusted
to 10.2 using lime. No further pH adjustments were made
during the test. The standard frother was methyl iso-
butyl carbinol (MIBC). A four-stage rougher flotation
scheme was then followed.
STAGE 1: Collector - 0.0042 kg/metric ton
MIBC - 0.015 kg/metric ton
- condition - 1 minute
- float - collect concentrate
for l minute
STAGE 2: Collector - 0.0021 kg/metric ton
MIBC - 0.005 kg/metric ton
- condition - 0.5 minute
- float - collect concentrate
for 1.5 minutes
33,740-F -22-
. ,
~o~
-23-
STAGE 3: Collector - 0.0016 kg/metric ton
MIBC - 0.005 kg/metric ton
- condition - 0.5 minute
- float - collect concentrate
for 2.0 minutes
STAGE 4: Collector - 0.0033 kg/metric ton
MIBC - 0.005 kg/metric ton
- condition - 0.5 minute
- float - collect concentrate
for 2.5 minutes
The results are compiled in Table II,
TABLE II
Copper/Molybdenum Ore
from Western Canada
15 Col- Dosage Ave Ave Ave
lec- g/metric Cu Molyb Cu Mo Fe
torton R-71 R-71 Grade2 Grade2 Grade2
A11.2 0.776 0.7250.0560.001810.254
B11.2 0.710 0.6910.0930.003250.149
B6.7 0.730 0.7030.1180~003900.155
B22.4 0.756 0.7600.1050.003460.161
C11.2 0.699 0.6970.1070.003860.164
C22.4 0.723 0.7230.1120.003920.142
A - potassium amyl xanthate, not an example of this
invention
B - 1,2-epithiooctane
C - hexylmethyl sulfide
_ R-7 is the experimental fractional recovery
after 7 minutes
2 _ Grade is the fractional content of the specified metal
in total weight collected in the froth
33,740-F -23-
,.,
,
.. . ...
- :
~,2~0076
-24-
The use of the collectors of this invention
has a significant influence both on improving the
overall concentrate grade (the fraction of desired
metal containing sulfide mineral in the final flotation
product) as well as a significant lowering of pyrite in
the concentrate as measured by the lowering of the Fe
assay of the product. This is true regardless of the
dosage being used. This means less mass being fed to
smelters and less sulfur emissions per unit of metal
being produced.
Exam~le 3 - Froth Flotation of Copper/Nickel
Ore from Eastern Canada Containing
Very High Amounts of Iron Sulfide
Mineral in the Form of Pyrrhotite
A series of samples were drawn from the
feeders to plant rougher bank and placed in buckets to
give approximately 1200 g of solid. The slurry con-
tained chalcopyrite and pentlandite minerals. The
contents of each bucket were then used to perform a
time-recovery profile on a Denver cell using an auto-
mated paddle and constant pulp level device with indivi-
dual concentrates selected at 1.0, 3.0, 6.0 and 12.0
minutes. The collectors were added once with a con-
dition time of one minute before froth removal was
started. The dosage of the collectors was 0.028 kg/-
metric ton of flotation feed. Individual concentrates
were dried, weighed, ground and statistically represen-
tative samples prepared for assay. Time-related recover-
ies and overall head grades are calculated using standard
mass balance equations.
33,740-F -24-
:' ',. ~.. ,
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: ' " ' - ' ' , . .
. - ... . .~. .
~27~)~76
--25--
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U~ ~ .
N ~7 t` O
h ~ -1 a~ ~ ~
h~,l I ~ ~ ,1
o o o
O
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~: O O O
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h O o O ~
O ~ h ~1
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h O O o
U~
h ~: tr~ O O
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h ~ $
v ~
g O O O O
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u~
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U O r~ I V O O
a~
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33, 740-F -25-
.
.: :- . .
.
007~;
-26-
The collectors of this invention give a
copper recovery comparable to sodium amyl xanthate; the
collectors of this invention result in much higher
rates of flotation. The collectors of this invention
result in a lower nickel recovery than sodium amyl
xanthate, but also provide a much lower recovery of
undesired iron sulfide pyrrhotite. This is indicated
by the R12 value of pyrrhotite and the about 50 percent
increase in sel~ctivity of nickel sulfide mineral
over the undesired iron sulfide mineral pyrrhotite.
ExamPle 4 - Froth Flotation of A complex
Pb/Zn/Cu/Ag Ore from Central
Canada
Uniform 1000 g samples of ore were jrepared.
The ore contained galena, sphalenite, chalcopynite, and
argentite minerals. For each flotation run, a sample
was added to a rod mill along with 500 ml of tap water
and 7.5 ml of SO2 solution. six and one-half minwtes
of mill time were used to prepare a feed of 90 percent
less than 200 mesh (75 microns). After grinding, the
contents were transferred to a cell fitted with an
automated paddle for froth removal, and the cell was
attached to a standard Denve~flotation mechanism.
A two-stage flotation was then performed. In
Stage I, a copper/lead/silver rougher float was carried
out, and in Stage II, a zinc rougher float was carried
out. To start the Stage I flotation, 1.5 g/kg Na2CO3
was added (pH of 9 to 9.5), followed by the addition of
collector(s). The pulp was then conditioned for 5
minutes with air and agitation. This was followed by
a 2-minute condition period with agitation only. MIBC
frother was then added (standard dose of 0.015 ml/kg).
33,740-F -26-
.,~ ,
:~
~7 ~ ~7 6
-27-
Concentrate was collected for 5 minutes of flotation and
labeled as copper/lead rougher concentrate.
The Stage II flotation consisted of adding
0.5 kg/metric ton of CuS04 to the cell remains of Stage
I. The pH was then adjusted to 10.5 with lime addition.
This was followed by a condition period of 5 minutes
with agitation only. pH was then rechecked and
adjusted back to 10.5 with lime. At this point, the
collector(s) were added, followed by a 5-minute con-
dition period with agitation only. MIBC frother wasthen added (standard dose of 0.020 ml/kg). Concentrate
was collected for 5 minutes and labeled as zinc rougher
concentrate.
Concentrate samples were dried, weighed, and
appropriate samples prepared for assay using X-ray
technigues. Using the assay data, recoveries and
grades were calculated using standard mass balance
formulae.
In addition to the above procedure, tests
were also run at lower pH in Stage I (no Na2C03 was
added, giving a pH of 8.5) and in Stage II only enough
lime was added to give a pH of 9.5. Also with the
lower pH, 0.3 kg/metric ton of CUSO4 was added.
33,740-F -27-
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--28--
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C~ o o o o
c
oo ~
u~ O ~-- O r~ 0
l C~
P~ o o o o o o o o
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U~
o , o, o, o
C~ o o o o
,, t~ o~ o~ ~ oo ~ CO U~
U~ CO oo o U~ ~ ~ ~ U~
~ o o oo oo o o
C`l
C~l ~o
~ ~ I ~ I ~ I _1 1
C~ o o o o
~ ~ ,r)03 o o~
r~ ~ ~ ~ ~ ~ ~ ~ c~
o o~ o o~ o o~ o
o o o o o o o o
, C~, ~,CO ,
c Q o ~ o o
E~: ~ ~ ~D ~ ,~ ~ ~ O
Llu~ ~0 0 X O ~ O 00 ~
~ O o O o o O O o
O ~ U'~
~~: o o o~ o Cl~ O oo
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o ~ . ~ ~
~ E
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I o
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33, 740-F -28-
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29
_,
~ 1~ 1~, s
o o
U~ U~ 0~
l _l ~o ~ oo V
~:; O o O O
_~ o '~
~ 01 01
D ~ o O U
L~
u~ C~
u, ~ ~n ~ u
00 oo
C`~
'l o~
n~ ~ I ~ I jt
C~ O O _l
oo o In J-
C l ~0 CO
~:; O O O O
'C -~
~1 ~ ". ,~
~; O O O O O U
OU'7 U~
:~ x a~ x ~
-- ~c~o o
~ ~ u~ o ~
0 2 _, ~C O
_ ~ a
1.~ ~ X~ ~,1 h O
o U ~ ~ ~ ~ X
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u)~ 3 ~ 3~ ~
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m U~
, 33, 740-F -29-
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This is a complicated flotation which shows
the rather remarkable result that the collectors of
this invention can be substituted for a complex mixture
of 3 commercially optimized collectors and essentially
match the metal recoveries and grades at the normal pH
and CUS~4 selected as optimal for the commercial col-
lectors (tests 1, 2, 3). The corresponding tests (4,
5, 6) at lower pH and CUSO4 also show that the collec-
tors of this invention are capable of giving signifi-
cantly improved metal grades over the 3 commercial col-
lectors. This result can represent significant savings
in lime and CuS04 costs to a plant operation. (The
main reason pH was controlled to 10.5 in Stage I and
9.5 in Stage II was to improve selectivity. The main
reason for adding CuS04 was to improve Zn recovery
while maintaining grade.) Note that at the lower CUSO4
runs (5, 6) the collectors of this invention actually
increased Zn recovery and maintain good grade.
Exam~le 5 - Froth Floatation of a Copper/
Molybdenum Ore
A 500 g quantity of a copper/molybdenum ore
from South America was placed in a rod mill having
one-inch (2.5 cm) rods along with 257 g of deionized
water and a quantity of lime. The mixture was ground
25 for 360 revolutions at a speed of 60 rpm to produce a
size distribution of suitable finess (about 25 percent
less than 100 mesh). The ground slurry, containing
various copper containing sulfide minerls and molyb-
denite, was transferred to a 1500 ml cell of an Agitair
Flotation machine. The float cell was agitated at 1150
rpm and the pH was adjusted to 8.5 by the addition of
either lime or hydrochloric acid.
33,740-F -30-
,,
~0~)7~
-31-
The collector was added to the float cell
(45 g/metric ton), followed by a conditioning time of
one minute, at which time the frother, DOWFROTH~ 250,
was added (36.4 g/metric ton). After an additional
conditioning time of one minute, the air to the float
cell was turned on at a rate of 4.5 liters per minute
and the automatic froth removal paddle was started.
Samples of the froth were collected at 0.5, 1.5,
3, 5, and 8 minutes. The froth samples were dried
overnight in an over along with the flotation tailings.
The dried samples were weighed, divided into suitable
samples for analysis, pulverized to insure suitable
fineness, and dissolved in acid for analysis on a DC
Plasma Spectrograph. The results are compiled in
Table V.
33,740-F -31-
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--3 2--
0GO N d~
C`~ ~ t` t~
co~tNe~l
O I
~4 ~ O o O O
O ~ ~
~`1d~ ~ 00 NO
CDt`t~t~ OD tau~
O I. . ~ ~ ~
O O O o ~10
~ ~ CD
,X
e
c. a~ 1 0
C~00 CD a~ oo 3
:~ I . . .. ~U
C.~ o o oo 3 0
o O
m o o
~ U U
In ~ , O ~ ~
o o ~ 0 ~
~ " o~
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o~
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a~
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~
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~ ~ X ~ X
o
Uo ~ ~o,,~
o ~ o Z
c~ X o x o ,, a~ ~
33, 740-F -32-
.~,
~'70076
--33--
The collectors of this invention show a
significant increase in molybdenum recovery over the
standard reagent; however, there is a decrease in
the copper recovery. Also a very significant desired
decrease is shown in the recovery of iron-bearing
sulfide minerals.
Example 6 - Froth Flotation of a Copper Ore
When the procedure of Example 1 was repeated
using a relatively high grade chalcopyrite containing
ore with little pyrite from a different location in
the same mine as Example 1, the following results
were obtained as compiled in Table VI.
33,740-F ~33~
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--3d~--
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i
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o ~ C5~ ~1 ~ C~
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U~
a~
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~
,1 ~o ~ r~
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h
n a~ a~ in in~ a~
D ~ O ~1 ~I h ~1,
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"p a~ r~l N ~i ~i o t~5 R
U ~ ~
s~ ~1 ~ ln
g ~
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S~ o~ ~ ~ ~ o .
O i-n a~ !~ ~ U
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U
~t ,~ ,~ N 5: ~ ~ I V~ ~ O
O ~ U~ O ~ Z
u a) a~
33, 740--F -34-
1 ~70~7~i
-35-
This example illustrates two fractors: 1)
the influence of the hydrophobic portion of the collector;
2) the comparison of the compounds of this invention
to a simple inorganic sulfide (Na2S).
33,740-F _35_
~:
.
.
..
. .
.
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