US3590998A - Flotation of sulfide ores - Google Patents
Flotation of sulfide ores Download PDFInfo
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- US3590998A US3590998A US796158A US3590998DA US3590998A US 3590998 A US3590998 A US 3590998A US 796158 A US796158 A US 796158A US 3590998D A US3590998D A US 3590998DA US 3590998 A US3590998 A US 3590998A
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- United States
- Prior art keywords
- flotation
- sulfide
- compound
- collector
- formula
- Prior art date
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000005188 flotation Methods 0.000 title abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 24
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 8
- 229910052569 sulfide mineral Inorganic materials 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 125000002947 alkylene group Chemical group 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 229910052745 lead Inorganic materials 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 235000001014 amino acid Nutrition 0.000 description 7
- -1 amino ester Chemical class 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 241000894007 species Species 0.000 description 3
- FUOOLUPWFVMBKG-UHFFFAOYSA-N 2-Aminoisobutyric acid Chemical compound CC(C)(N)C(O)=O FUOOLUPWFVMBKG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 150000002332 glycine derivatives Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010665 pine oil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012991 xanthate Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- TXTWXQXDMWILOF-UHFFFAOYSA-N (2-ethoxy-2-oxoethyl)azanium;chloride Chemical compound [Cl-].CCOC(=O)C[NH3+] TXTWXQXDMWILOF-UHFFFAOYSA-N 0.000 description 1
- QHDHNVFIKWGRJR-UHFFFAOYSA-N 1-cyclohexenol Chemical compound OC1=CCCCC1 QHDHNVFIKWGRJR-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- WVRLAHTVGOLBEB-UHFFFAOYSA-N 4-chlorobut-2-en-1-ol Chemical compound OCC=CCCl WVRLAHTVGOLBEB-UHFFFAOYSA-N 0.000 description 1
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- PQANGXXSEABURG-UHFFFAOYSA-N cyclohexenol Natural products OC1CCCC=C1 PQANGXXSEABURG-UHFFFAOYSA-N 0.000 description 1
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010642 eucalyptus oil Substances 0.000 description 1
- 229940044949 eucalyptus oil Drugs 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical class NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910001656 zinc mineral Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S209/00—Classifying, separating, and assorting solids
- Y10S209/901—Froth flotation; copper
Definitions
- FLOTATION OF SULFIDE ORES BACKGROUND 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 are separated from other finely divided mineral solids by introducing a gas (or providing a gas in situ) into the liquid to produce a frothy mass containing certain desired solids on the top of the liquid, and leaving suspended (unfrothed) solids in the liquid.
- a gas or providing a gas in situ
- Flotation is based on the principle that introducing a gas into a liquid containing solid particles of difierent materials suspended therein causes adherence of some gas to certain suspended solids and not to others and makes the particles having the gas thus adhered thereto lighter than the liquid. Accordingly, they rise to the top of the liquid to form a froth.
- collectors e.g., high carbon chain compounds such as 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 eucalyptus oil
- modifiers such as activators to induce flotation 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.
- additaments of the above type are selected for use according to the nature of the ore, the mineral sought to be recovered, and the other additaments which are to be used in combination therewith.
- the flotation principle is applied in a number of mineral separation processes among which is the selective separation of such minerals as sulfide copper minerals, sulfide zinc minerals, sulfide molybdenum minerals and others from sulfide iron minerals.
- the present invention concerns the use ofa unique class of compounds as collection agents in a flotation process. With some of these collectors better recoveries are realized and with others improved selectivity is achieved. Certain of these agents produce improvement in both aspects.
- the present invention concerns an improved method of flotation separation of sulfide minerals which comprises subjecting a sulfide ore to a flotation process in the presence of a compound corresponding to the formula wherein R is a hydrocarbyl group, other than an aryl or alkaryl; R is an alkylene group, and R, is a hydrocarbyl group other than aryl or alkaryl; said compounds acting as flotation collectors in the concentration of sulfide minerals of copper, zinc, molybdenum, cobalt, nickel, lead, arsenic and others from ores in preference to other minerals.
- the present compounds are employed as flotation collectors using standard flotation techniques.
- Preferable compounds correspond to the formula Q H 3 wherein R represents a hydrocarbyl group selected from the group consisting of a branched or straight chain alkyl or alkenyl group or an cycloalkyl or cycloalkenyl group, preferably containing from 1 to 10 carbon atoms, or an aralkyl group; R, represents an alkylene group, preferably containing from 1 to 6 carbon atoms, and R represents a hydrocarbyl group selected from the group consisting of an alkyl, alkenyl, cycloalkyl or cycloalkenyl group, preferably containing from 1 to 8 carbon atoms, an aralkyl or aralkenyl group.
- the flotation collector compounds as defined herein can be prepared by the interaction of an ester of a primary amino acid with a compound corresponding to the general formula wherein M represents a metal cation and R, is the same as defined hereinbefore, the desired product being obtained with coformation of the metal acetate through cleavage of the bond.
- the flotation collector compounds as defined herein are particularly suitable for use in standard flotation processes to concentrate copper sulfide and other like minerals from sulfide ores.
- a pulp is first prepared by wet grinding the ore to a suitable size with or without a pH modifier.
- a suitable frothing agent is then added, e.g., pine oil, cresylic acid, polyalkoxyparaffin and the like.
- An effective quantity of the flotation collector compound as defined herein is then added usually ranging from about 0.01 lb. to about 0.25 lb. per ton of pulp and the pulp usually agitated and.
- EXAMPLE 1 Various species of flotation collector compounds within the scope of the present invention were employed in the flotation recovery of copper from a sulfide ore obtained from Southwestern United States employing the following procedure. A sample of ore was ground for 4 minutes at a pulp density of 645 percent by weight solids with 2.0 lbs/ton of lime. The pulp was then conditioned for 2 minutes at a pH of 10.3 with a collector compound and 0.05 lbs/ton of a frother. The pulp was then floated for 4 minutes. A standard flotation collector compound consisting of a thionocarbamate compound corresponding to the formula was employed as a control. The specific collector compounds, concentrations of collectors, and analysis of the concentrates and tailings for copper are set forth in the following Table I.
- noaH.-0-ccmf -o-ocH oH3 was successfully employed as a flotation collector in the separation of copper sulfide from an ore.
- H H3CCH2OCCHT NHC 0 CH was prepared in the following manner:
- the structure of the compound was confirmed by infrared and NMR analysis. Calculated analysis for the compound is C 49.29 percent, H-7.82 percent and No.39 percent. Actual partial analysis was 649.39 percent. H-7.72 percent and N- 6.38 percent.
- R can represent, ethyl, chloroethyl, propyl, isopropyl, butyl, isobutyl, n-amyl, isoamyl, hexyl, octyl, dodecyl and other like groups.
- esters of such amino acids are made by standard procedures for the esterification of carboxylic acids, such as by heating the hydrochloride of the amino acid with alcohol in the presence of a catalytic amount of free HCl and then neutralizing to spring the free amino acid ester.
- Amino acids which can be used as their esters include for example, 2, or 4- aminobutanoic acids, 6-amino caproic, 2-amino-2-methyl propanoic acid, a and [3 alanine and other like amino acids.
- Amino acid esters of the following exemplary alcohols can be employed: 3-hexanol, 2, 3, S-trimethyl; 2-hexanol, 2, 3, 4, trimethyl; ethylene cyanohydrin; benzyl alcohol, cyclohexanol, cyclohexenol, cyclohexylmethyl alcohol, 4-chlorobutanol, 3-chloro-2-methyl-butyl alcohol, crotyl alcohol, 4- chlorocrotyl alcohol and other such alcohols.
- collector compounds hereinbefore defined as suitable for the practice of the instant invention can be derived from such of the above alcohols as do not comprise reactive halogen substituents.
- a flotation collector comprising a compound corresponding to the formula wherein R corresponds to a hydrocarbyl group selected from the group consisting of a alkyl or alkenyl group containing from 1 to 10 carbon atoms, a cycloalkyl, cycloalkenyl or an aralkyl group; R corresponds to an alkylene group, containing from 1 to 6 carbon atoms, and R corresponds to a hydrocarbyl group selected from the group consisting of an alkyl, cycloalkyl, cycloakenyl or alkenyl group containing from i to 8 carbon atoms, or an aralkyl or aralkenyl group.
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
An improvement in the concentration of ores by flotation which comprises subjecting a sulfide ore in the form of a pulp to a flotation process in the presence of an effective quantity of a flotation collector comprising a compound corresponding to the formula WHEREIN R and R2 are hydrocarbon groups and R1 is an alkylene group. Certain of the indicated compounds provide enhanced recovery of and/or selectivity of sulfide minerals of Cu, Zn, Mo, Co, Ni, Pb and As over iron sulfide.
Description
United States Patent David J. Collins Walnut Creek;
Guy H. Harris, Concord, both of, Calif. [21] Appl. No. 796,158
[72] Inventors [22] Filed Feb. 3, 1969 [45] Patented July 6, 1971 [73] Assignee The Dow Chemical Company Midland, Mich.
[54] FLOTATION OF SULFIDE ORES 6 Claims, No Drawings [52] 1.1.8. Cl 209/166, 260/455 [51] 1nt.C1 803d 1/02, C07c 153/07 [50] Field 01' Search 209/166,
3,290,351 12/1966 McKay 260/455 2.835.625 5/1958 Lo 260/455 X FOREIGN PATENTS 750,568 6/1956 Great Britain.... 260/455 1,179,312 12/1958 France 260/455 Primary Examiner- Frank W. Lutter Assistant Examiner-Robert Halper Attorneys-Griswold and Burdick, Bruce M. Kanuch and William R. Norris ABSTRACT: An improvement in the concentration of ores by flotation which comprises subjecting a sulfide ore in the form of a pulp to a flotation process in the presence of an effective quantity of a flotation collector comprising a compound corresponding to the formula wherein R and R are hydrocarbon groups and R, is an alkylene group. Certain of the indicated compounds provide enhanced recovery of and/or selectivity of sulfide minerals of Cu, Zn, Mo, Co, Ni, Pb and As over iron sulfide.
FLOTATION OF SULFIDE ORES BACKGROUND 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 are separated from other finely divided mineral solids by introducing a gas (or providing a gas in situ) into the liquid to produce a frothy mass containing certain desired solids on the top of the liquid, and leaving suspended (unfrothed) solids in the liquid.
Flotation is based on the principle that introducing a gas into a liquid containing solid particles of difierent materials suspended therein causes adherence of some gas to certain suspended solids and not to others and makes the particles having the gas thus adhered thereto lighter than the liquid. Accordingly, they 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, e.g., high carbon chain compounds such as 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 eucalyptus oil; modifiers such as activators to induce flotation 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 additaments of the above type are selected for use according to the nature of the ore, the mineral 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 invention. They appear, however, to be largely associated with selective afi'mity of the surface of particulated solids, suspended in a liquid containing entrapped gas, for the liquid on 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 minerals as sulfide copper minerals, sulfide zinc minerals, sulfide molybdenum minerals and others from sulfide iron minerals. The present invention concerns the use ofa unique class of compounds as collection agents in a flotation process. With some of these collectors better recoveries are realized and with others improved selectivity is achieved. Certain of these agents produce improvement in both aspects.
SUMMARY The present invention concerns an improved method of flotation separation of sulfide minerals which comprises subjecting a sulfide ore to a flotation process in the presence of a compound corresponding to the formula wherein R is a hydrocarbyl group, other than an aryl or alkaryl; R is an alkylene group, and R, is a hydrocarbyl group other than aryl or alkaryl; said compounds acting as flotation collectors in the concentration of sulfide minerals of copper, zinc, molybdenum, cobalt, nickel, lead, arsenic and others from ores in preference to other minerals.
PREFERRED EMBODIMENTS In the practice of the present invention the present compounds are employed as flotation collectors using standard flotation techniques. Preferable compounds correspond to the formula Q H 3 wherein R represents a hydrocarbyl group selected from the group consisting of a branched or straight chain alkyl or alkenyl group or an cycloalkyl or cycloalkenyl group, preferably containing from 1 to 10 carbon atoms, or an aralkyl group; R, represents an alkylene group, preferably containing from 1 to 6 carbon atoms, and R represents a hydrocarbyl group selected from the group consisting of an alkyl, alkenyl, cycloalkyl or cycloalkenyl group, preferably containing from 1 to 8 carbon atoms, an aralkyl or aralkenyl group.
The flotation collector compounds as defined herein can be prepared by the interaction of an ester of a primary amino acid with a compound corresponding to the general formula wherein M represents a metal cation and R, is the same as defined hereinbefore, the desired product being obtained with coformation of the metal acetate through cleavage of the bond.
The flotation collector compounds as defined herein are particularly suitable for use in standard flotation processes to concentrate copper sulfide and other like minerals from sulfide ores. In such processes, a pulp is first prepared by wet grinding the ore to a suitable size with or without a pH modifier. A suitable frothing agent is then added, e.g., pine oil, cresylic acid, polyalkoxyparaffin and the like. An effective quantity of the flotation collector compound as defined herein is then added usually ranging from about 0.01 lb. to about 0.25 lb. per ton of pulp and the pulp usually agitated and.
areated. The copper sulfide minerals and other like sulfide minerals, except iron sulfide, collect as a froth which is readily overflowed or skimmed off from the residual gangue and other nondesired materials and the metal values therein recovered.
The following Examples will facilitate a more complete understanding of the present invention but they are not meant to limit the scope of the invention to the specific embodiments incorporated therein.
EXAMPLE 1 Various species of flotation collector compounds within the scope of the present invention were employed in the flotation recovery of copper from a sulfide ore obtained from Southwestern United States employing the following procedure. A sample of ore was ground for 4 minutes at a pulp density of 645 percent by weight solids with 2.0 lbs/ton of lime. The pulp was then conditioned for 2 minutes at a pH of 10.3 with a collector compound and 0.05 lbs/ton of a frother. The pulp was then floated for 4 minutes. A standard flotation collector compound consisting of a thionocarbamate compound corresponding to the formula was employed as a control. The specific collector compounds, concentrations of collectors, and analysis of the concentrates and tailings for copper are set forth in the following Table I.
'1 .u; LE l Run Lb./ton Cu in Percent Cu Number (ollcctor compound added tails recovered (ontroL ('ontrul H, 01 .389 51. 8
o n r! l C:lI50C-Cli2.\'*'O-Cli(ClI3); 0.01 0. 272 55.0
free amine was then added to an aqueous solution containing a EXAMPLE 2 compound corresponding to the formula Other compounds, within the scope of the present invention, were employed as flotation collectors in a flotation process to separate copper from a different copper sulfide ore obtained from the Southwestern United States.
A sample of the ore was wet ground for 3 minutes at a pulp density of 62.5 percent by weight solids with 0.8 lb./ton of lime to provide a concentrate. The pulp was then conditioned with the quantity of a collector compound as shown in Table ll and 0.l3 lb./ton of a frother. The pulp was then floated for 5 minutes. A standard flotation collector compound consisting of a thionocarbamate compound corresponding to the formula was employed as a control. The specific collector compounds, quantities of addition, and results obtained are set forth in Table ll.
the corresponding butyl ester of the substituted glycine was TABLE II Concentrate Tail assay, assay, Percent percent percent recoveries LbJton Run No. Collector compound added Cu Fe Cu Fe Cu Fe 1 Control ,.032 12.4 17.9 .081 1.22 85.8 36.8
r e r 2 CzH OC-CHzCH-NCOC:H .032 14.4 17.6 .080 1.48 86.0 28.8
it r r 3 CzH 0C-CH2CHNC0CH(CH3)2 .032 175 22.4 .079 1.46 86.6 34.5
4 Control .078 11.6 20.5 .072 1.03 87.4 45.1 5-- SameasRunNo.2 .078 14.3 18.4 .076 1.38 86.8 31.8 6 ..San1easRunNo.3 .078 11.2 17.8 .076 1.28 86.8 38.5
noaH.-0-ccmf -o-ocH oH3 was successfully employed as a flotation collector in the separation of copper sulfide from an ore.
One species of a flotation collector compound within the scope of the present invention, corresponding to the formula 0 S OH;
H H3CCH2OCCHT NHC 0 CH was prepared in the following manner:
An aqueous solution containing 21 grams of glycine ethyl ester hydrochloride was neutralized with an aqueous solution containing 6 grams of NaOH. The so-prepared solution of the employed and a product corresponding to the formula was obtained in about an percent yield.
Another species of a flotation collection compound within the scope of the present invention, corresponding to the formula was prepared in the following manner.
In a flask was placed 13.1 grams (0.l mole) of CH3CHCHC O O C2Hs and 13.6 grams (0.1 mole) of C H5-O- The mixture was heated to 55 C. and maintained at 5560 C. until CH SH was no longer observed to be evolved. The last of the CH SH was removed by heating to 55--60 under a reduced pressure of about 30 mm Hg. There was a 95 percent yield of an oily product.
The structure of the compound was confirmed by infrared and NMR analysis. Calculated analysis for the compound is C 49.29 percent, H-7.82 percent and No.39 percent. Actual partial analysis was 649.39 percent. H-7.72 percent and N- 6.38 percent.
In a manner similar to that employed in preparing the previous three compounds the amino ester was reacted with a technical grade xanthate ester corresponding to the formula cg, H s
cH-cm-o-o-c-som CH3 CH2 to give a product corresponding to the formula All of these compounds possess collector activity in the flotation separation of sulfide containing ores.
Other glycine esters corresponding to the general formula NH CH COOR, wherein R is the same as defined hereinbefore, can be employed in the processes previously defined to prepare flotation collector compounds for use within the scope of the present invention. For example R can represent, ethyl, chloroethyl, propyl, isopropyl, butyl, isobutyl, n-amyl, isoamyl, hexyl, octyl, dodecyl and other like groups.
The esters of such amino acids are made by standard procedures for the esterification of carboxylic acids, such as by heating the hydrochloride of the amino acid with alcohol in the presence of a catalytic amount of free HCl and then neutralizing to spring the free amino acid ester. Amino acids which can be used as their esters include for example, 2, or 4- aminobutanoic acids, 6-amino caproic, 2-amino-2-methyl propanoic acid, a and [3 alanine and other like amino acids. Amino acid esters of the following exemplary alcohols can be employed: 3-hexanol, 2, 3, S-trimethyl; 2-hexanol, 2, 3, 4, trimethyl; ethylene cyanohydrin; benzyl alcohol, cyclohexanol, cyclohexenol, cyclohexylmethyl alcohol, 4-chlorobutanol, 3-chloro-2-methyl-butyl alcohol, crotyl alcohol, 4- chlorocrotyl alcohol and other such alcohols.
Similarly, the -OR moiety in collector compounds hereinbefore defined as suitable for the practice of the instant invention can be derived from such of the above alcohols as do not comprise reactive halogen substituents.
Various modifications may be made in the present invention without departing from the spirit or scope thereof for it is understood that we are limited only as defined in the appended claims.
We claim:
1. In the process of concentrating sulfide ores by froth flotation in the presence of a flotation collector the improvement which comprises:
a. subjecting the sulfide ore in the form of a pulp to a flotation collector comprising a compound corresponding to the formula wherein R corresponds to a hydrocarbyl group selected from the group consisting of a alkyl or alkenyl group containing from 1 to 10 carbon atoms, a cycloalkyl, cycloalkenyl or an aralkyl group; R corresponds to an alkylene group, containing from 1 to 6 carbon atoms, and R corresponds to a hydrocarbyl group selected from the group consisting of an alkyl, cycloalkyl, cycloakenyl or alkenyl group containing from i to 8 carbon atoms, or an aralkyl or aralkenyl group.
2. The process as defined in claim 1 wherein from about 0.01 to about 0.25 pounds of said compound per ton of said sulfide ore pulp is employed.
3. The process as defined in claim 1 wherein said compound consists of 4. The process as defined in claim 1 wherein said compound consists of 5. The process as defined in claim 1 wherein said compound consists of 6. The process as defined in claim 1 wherein said compound consists of $1) CH H S OH:
Claims (5)
- 2. The process as defined in claim 1 wherein from about 0.01 to about 0.25 pounds of said compound per ton of said sulfide ore pulp is employed.
- 3. The process as defined in claim 1 wherein said compound consists of
- 4. The process as defined in claim 1 wherein said compound consists of
- 5. The process as defined in claim 1 wherein said compound consists of
- 6. The process as defined in claim 1 wherein said compound consists of
Applications Claiming Priority (1)
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US79615869A | 1969-02-03 | 1969-02-03 |
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US3590998A true US3590998A (en) | 1971-07-06 |
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US796158A Expired - Lifetime US3590998A (en) | 1969-02-03 | 1969-02-03 | Flotation of sulfide ores |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4387034A (en) * | 1981-10-23 | 1983-06-07 | Thiotech, Inc. | Mixed alkylthionocarbamates flotation collectors and ore dressing methods in which the collectors are employed |
US4584097A (en) * | 1984-08-17 | 1986-04-22 | American Cyanamid Company | Neutral hydrocarboxycarbonyl thionocarbamate sulfide collectors |
US4595493A (en) * | 1984-08-17 | 1986-06-17 | American Cyanamid Company | Process for the flotation of base metal sulfide minerals in acid, neutral or mildly alkaline circuits |
US4618461A (en) * | 1983-07-25 | 1986-10-21 | The Dow Chemical Company | O,O'-, O,S'- or S,S'-dithiodialkylene-bis(mono- or dihydrocarbyl carbamothioates) and S,S'-dithiodialkylene-bis(mono- or dihydrocarbyl carbamodithioates) and method of preparation thereof |
US4657688A (en) * | 1984-08-17 | 1987-04-14 | American Cyanamid Company | Neutral hydrocarboxycarbonyl thionocarbamate sulfide collectors |
US4702822A (en) * | 1985-07-12 | 1987-10-27 | The Dow Chemical Company | Novel collector composition for froth flotation |
AU570131B2 (en) * | 1984-08-17 | 1988-03-03 | American Cyanamid Company | Hydrocarboxycarbonyl thionocarbamate collectors |
USRE32827E (en) * | 1984-08-17 | 1989-01-10 | American Cyanamid | Neutral hydrocarboxycarbonyl thionocarbamate sulfide collectors |
CN112973970A (en) * | 2021-03-02 | 2021-06-18 | 驰宏科技工程股份有限公司 | Method for removing arsenic in lead concentrate |
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US4387034A (en) * | 1981-10-23 | 1983-06-07 | Thiotech, Inc. | Mixed alkylthionocarbamates flotation collectors and ore dressing methods in which the collectors are employed |
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