US2185968A - Process of concentrating ores and flotation agents therefor - Google Patents
Process of concentrating ores and flotation agents therefor Download PDFInfo
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- US2185968A US2185968A US172284A US17228437A US2185968A US 2185968 A US2185968 A US 2185968A US 172284 A US172284 A US 172284A US 17228437 A US17228437 A US 17228437A US 2185968 A US2185968 A US 2185968A
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- Prior art keywords
- flotation
- amines
- hydrocarbons
- mixture
- unsaturated
- Prior art date
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- 239000008396 flotation agent Substances 0.000 title description 19
- 238000000034 method Methods 0.000 title description 4
- 230000008569 process Effects 0.000 title description 4
- 239000000203 mixture Substances 0.000 description 47
- 150000002825 nitriles Chemical class 0.000 description 21
- -1 aliphatic nitriles Chemical class 0.000 description 20
- 229920006395 saturated elastomer Polymers 0.000 description 19
- 229930195733 hydrocarbon Natural products 0.000 description 16
- 150000002430 hydrocarbons Chemical class 0.000 description 16
- 150000001412 amines Chemical class 0.000 description 15
- 238000009291 froth flotation Methods 0.000 description 15
- 238000009835 boiling Methods 0.000 description 14
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 238000005188 flotation Methods 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 6
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 229910052949 galena Inorganic materials 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 3
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 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 2
- 239000007788 liquid Substances 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- RHSBIGNQEIPSCT-UHFFFAOYSA-N stearonitrile Chemical compound CCCCCCCCCCCCCCCCCC#N RHSBIGNQEIPSCT-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 241001591024 Samea Species 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- NKKMVIVFRUYPLQ-UHFFFAOYSA-N but-2-enenitrile Chemical compound CC=CC#N NKKMVIVFRUYPLQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052947 chalcocite 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
- 230000001186 cumulative effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- JAIOXBDVPQJCCD-UHFFFAOYSA-N hept-2-enenitrile Chemical compound CCCCC=CC#N JAIOXBDVPQJCCD-UHFFFAOYSA-N 0.000 description 1
- SDAXRHHPNYTELL-UHFFFAOYSA-N heptanenitrile Chemical compound CCCCCCC#N SDAXRHHPNYTELL-UHFFFAOYSA-N 0.000 description 1
- CSAZMTWHVNCILA-UHFFFAOYSA-N hex-2-enenitrile Chemical compound CCCC=CC#N CSAZMTWHVNCILA-UHFFFAOYSA-N 0.000 description 1
- AILKHAQXUAOOFU-UHFFFAOYSA-N hexanenitrile Chemical compound CCCCCC#N AILKHAQXUAOOFU-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000051 modifying 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000012991 xanthate Substances 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
- B03D1/01—Organic compounds containing nitrogen
-
- 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
- B03D1/006—Hydrocarbons
-
- 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
-
- 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
- Y10S209/902—Froth flotation; phosphate
Definitions
- said flotation agent advantageously being prepared by subjecting mixtures of aliphatic nitriles and hydrocarbons to hydrogenation.
- the composition of the nitrile-hydrocarbon mixture will vary somewhat depending upon the kind of higher fatty acid nitriles, or mixtures thereof, used as a starting material, and the conditions during thepyrolysis.
- the predominating nitriles in such reaction mixtures will contain from three to ten carbon atoms, and the predominating hydrocarbons will contain from about flve to fourteen carbon atoms.
- the respective quantitiesof individual nitriles present in the reaction mixture are about the same. There may, for example, be equal quantities of nitriles containing three, four and flve carbon atoms.
- Unsaturated nitriles and unsaturated hydro carbons are also present.
- condensate when stearonitrile is heated at a cracking temperature under pressure the condensate is a pale yellow liquid containing a mixture of saturated and unsaturated nitriles asso- 50 ciated with liquid hydrocarbons.
- This condensate when fractionated, yields the following fractions, assuming the starting mixture to be100 parts of condensate:
- nitrile-hydrocarbon mixtures can be hydrogenated to give mixtures of amines and hydrocarbons which mixu tures are markedly suitable as flotation agents in the froth flotation of ores.
- a mixture of equal parts of proprionitrile, butyronitrile and valeronitrile can be hydrogenated to give a mixture of propyl amine, butyl amine and amyl amine.
- aliphatic nitriles namely those substances having the formula RCN wherein R is an alkyl group are also commonly described as alkyl cyanides.
- Propionitrile corresponds,'for example, to ethyl cyanide
- butyronitrile is the sameas propyl cyanide
- valeronitrile is the same as butylcyanide and yields pentyl amine on reduction.
- unsaturated nitriles (cyanides) in our nitrile-hydrocarbon mixture it will simplify identification of these materials if we refer to them as cyanides and this we do in the specific examples which follow. We shall now give examples of how our invention may be practised.
- Example 1 of 84 per cent hydrogen and 16 per cent ammonia The hydrogenation is continued for two hours in the presence of 2 per cent nickel catalyst.
- This nitrile-hydrocarbon mixture contains propyl cyanide, propenyl cyanide, butyl cyanide and butenyl cyanide, together with heptane, heptene, octane, octene, nonane and nonene. After hydrogenation the boiling point range is100 C. to 152 C.
- the product consists of a solution of about equal parts by weight of butyl, butenyl, pentyl and pentenyl amines in about equal parts by weight of heptane, heptene, octane, octene, nonane and nonene, together with a. small amount of secondary amines.
- the amount of primary amines is approximately 24.9 per cent by weight and secondary amines 3.3 per cent by weight.
- this amine-hydrocarbon mixture in the concentration of 400 parts per million gives essentially quantitative froth flotation of galena.
- concentration of the amine-hydrocarbon mixture is approximately 400 parts per million. Under these conditions we obtain substantial froth flotation of the lead and after activation of zinc by the use of small amounts of copper sulfate an essentially quantitative recovery of zinc results.
- Example 2 A mixture or" unsaturated and saturated nitriles and unsaturated and saturated hydrocarbons, boiling between 140 C. and 180 C., is subjected to hydrogenation under the conditions described in Example 1.
- the original nitrile-hydrocarbon mixture consists essentially of the following substances: Butyl cyanide, butenyl cyanide, pentyl cyanide, pentenyl cyanide, hexyl cyanide and hexenyl cyanide, together with nonane, decane, nonene and decene.
- the amuse boiling point range is 120 C. to 220 C.
- the product consists of a mixture of pentyl, pentenyl, hexyl, hexenyl, heptyl and heptenyl amines in about equal quantities, together with the above named saturated and unsaturated hydrocarbons and a small amount of secondary amines.
- This mixture in the concentration of 425 parts per million produces essentially quantitative froth flotation of galena.
- a concentration of 400 parts per million of this mixture produces essentially complete froth flotation of collophanite.
- Example 3 A fraction of nitrile-hydrocarbons with a boiling point range of 180 C. to 200 C. is subjected to hydrogenating conditions as described under Example 1.
- the boiling point range of the hydrogenated product is 155 C. to 250 0., and .it consists of heptyl, heptenyl, octyl, and octenyl amines, together with decane, decene, undecane, undecene, dodecane and dodecene and a small amount of secondary amines.
- a concentration of 450 parts per million of this mixture gives essentially quantitative flotation of ga1ena. We also use it in a concentration of 450 parts per million for the flotation of rutile and chalcopyrite.
- the composition of the amine-hydrocarbon mixture can vary over rather wide limits depending upon the boiling point range of the nitrilehydrocarbon mixture which is subjected to hydrogenation.
- the product obtained from cracking high molecular weight nitriles may be fractionated so as to give a starting nitrile-hydrocarbon mixture of any boiling point range between the limits of the product; Approximately fifty per cent of the amines and hydrocarbons present will contain one double bond and the remainder will consist of saturated compounds. We believe where the double bond is present that it is in a terminal position.
- Our flotation agents will consist of two or more saturated or unsaturated amines in a mixture of saturated and um saturated hydrocarbons.
- the process of concentrating ores which comprises subjecting the ore to froth flotation separation in the presence of a mixture of saturated and unsaturated aliphatic amines having from three to ten carbon atoms and saturated and unsaturated aliphatic straight-chain hydrocarbons.
- the step comcomprises subjecting an aqueous pulp of the ore' to froth flotation in the presence of a flotation agent comprising a mixture of aliphatic amines containing from three to ten carbon atoms in substantial amounts, together with straightchain aliphatic hydrocarbons.
- a flotation agent comprising an aliphatic hydrocarbon solution of saturated and unsaturated aliphatic amines having from three to ten carbon atoms.
- a flotation agent comprising an aliphatic hydrocarbon solution of at least one unsaturated aliphatic amine having from three to ten carbon atoms.
- a flotation agent comprising a hydrocarbon solution of at least two aliphatic amines chosen from the group consisting of butyl, butenyl, pentyl, pentenyl; hexyl, hexenyl, heptyl and heptenyl amines, one of said chosen amines bein unsaturated.
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
Patented Jan. 2, 1940 PATENT OFFICE PROCESS OF CONCENTRATING OBES AND FLOTATION AGENTS THEREFOR Anderson W. Ralston, William 0. Pool, and James Harwood, Chicago, 111., assignors to Armour and Company, Chicago, 11]., a corporation of Illinois No Drawing.-
60lalms.
l saturatedand unsaturated aliphatic hydrocarbons, said flotation agent advantageously being prepared by subjecting mixtures of aliphatic nitriles and hydrocarbons to hydrogenation.
In the co-pending application of Harwood and II Pool, flled April 28, 1937, Serial No. 139,611, there is described the use of mixtures of aliphatic hydrocarbons and aliphatic nitriles having from about three to ten carbon atoms as flotation agents in the froth flotation of ores. These mixtures of nitriles and hydrocarbons are advantageously made by subjecting relatively high molecular weight fatty acid nitriles, such as stearonitrile, to heat and pressure in the liquid phase, or to heat and a catalyst in the vapor a phase, and condensing a reaction mixture composedof lower molecular weight nitriles and hydrocarbons. Such methcdsflof preparing nitrilehydrocarbon mixtures are described and claimed in the Ralston, Pool and Harwood Patents 2,033,- 536 and 2,033,537.
The composition of the nitrile-hydrocarbon mixture will vary somewhat depending upon the kind of higher fatty acid nitriles, or mixtures thereof, used as a starting material, and the conditions during thepyrolysis. The predominating nitriles in such reaction mixtures ,will contain from three to ten carbon atoms, and the predominating hydrocarbons will contain from about flve to fourteen carbon atoms. Generally the respective quantitiesof individual nitriles present in the reaction mixture are about the same. There may, for example, be equal quantities of nitriles containing three, four and flve carbon atoms.-
Unsaturated nitriles and unsaturated hydro carbons are also present.
For example, when stearonitrile is heated at a cracking temperature under pressure the condensate is a pale yellow liquid containing a mixture of saturated and unsaturated nitriles asso- 50 ciated with liquid hydrocarbons. This condensate, when fractionated, yields the following fractions, assuming the starting mixture to be100 parts of condensate:
25 parts fraction 1 boiling range 40 C.-110 C. ll 25 parts fraction 2 boiling range 110 (IL-175 C.
. molecularweights.
Application November 1, 1937, Serial No. 172,284
25 parts fraction 3 boiling range 175 C.-220 C. 20 parts fraction 4 boiling range 220 C.2'75 C. 5 parts residue boiling range above 275 C.
These fractions consist of saturated and unsaturated nitriles and saturated and unsaturated 5 hydrocarbons falling within the boiling range indicated. The amount of saturated nitriles will roughly equal the amount of unsaturated nitriles, and there will be approximately equal quantities of saturated and unsaturated aliphatic hydrolo carbons.
We have now discovered that such nitrile-hydrocarbon mixtures can be hydrogenated to give mixtures of amines and hydrocarbons which mixu tures are markedly suitable as flotation agents in the froth flotation of ores. For example, a mixture of equal parts of proprionitrile, butyronitrile and valeronitrile can be hydrogenated to give a mixture of propyl amine, butyl amine and amyl amine. We wish to distinguish at this time, however, from the use as flotation agents of amine mixtures, or single amines, having relatively high In certain other co-pending applications in the name of Ralston and Pool there is described the froth flotation of ores in the presence of amines, such as octadecylamine having eighteen carbon atoms. We also wish to distinguish from those flotation processes which use substantially pure aliphatic amines having ten or more carbon. atoms. The amine mixtures which we obtain by the hydrogenation of nitrilehydrocarbon mixtures are all mixtures of relatively low molecular weight amines, both saturated and unsaturated, and hydrocarbons. The advantages present in our flotation agents are largely due to the fact that they are composed of mixtures of at least two or more amines and hydrocarbons.
In the past many different flotation agents have been proposed, such as oleic acid, fuel oil, xanthates and the like. It is recognized nowadays that best results are obtained when the ore to be separated by froth flotation is processed in the presence of substances which act as frothers and'substances which act as collectors. These collectors are believed to modify the interfacial tension .of the ore with respect to water. Our flotation agents can be looked upon as an intimate association of frothing agents and collectors. Undoubtedly, the hydrocarbons present act to to modify the surface tension relationships between ore and water, although there is also evidence that the amines we use have some surface tension modifying effect. The amines in our flotation mixtures also behave as frothing agents when used in conjunction with the hydrocarbons present. Mixtures of butylamine and heptylamine will alone act as froth flotation agents.
The action of our amine mixtures appears to be different from the action of the corresponding nitrile mixtures described in the aforesaid Harwood and Pool application 139,611 in that the amine mixtures of the present invention will concentrate by froth flotation a number of minerals and ores not concentrated as eflectively by the nitriles.
The aliphatic nitriles, namely those substances having the formula RCN wherein R is an alkyl group are also commonly described as alkyl cyanides. Propionitrile corresponds,'for example, to ethyl cyanide, butyronitrile is the sameas propyl cyanide, valeronitrile is the same as butylcyanide and yields pentyl amine on reduction. Because of the presence of unsaturated nitriles (cyanides) in our nitrile-hydrocarbon mixture, it will simplify identification of these materials if we refer to them as cyanides and this we do in the specific examples which follow. We shall now give examples of how our invention may be practised.
Example 1 of 84 per cent hydrogen and 16 per cent ammonia. The hydrogenation is continued for two hours in the presence of 2 per cent nickel catalyst. This nitrile-hydrocarbon mixture contains propyl cyanide, propenyl cyanide, butyl cyanide and butenyl cyanide, together with heptane, heptene, octane, octene, nonane and nonene. After hydrogenation the boiling point range is100 C. to 152 C. and the product consists of a solution of about equal parts by weight of butyl, butenyl, pentyl and pentenyl amines in about equal parts by weight of heptane, heptene, octane, octene, nonane and nonene, together with a. small amount of secondary amines. The amount of primary amines is approximately 24.9 per cent by weight and secondary amines 3.3 per cent by weight.
We have found that this amine-hydrocarbon mixture in the concentration of 400 parts per million gives essentially quantitative froth flotation of galena. When used for the flotation of an ore containing 1.5 per cent lead and 6.0 per cent zinc we use the equivalent of 2 pounds of amine-hydrocarbon mixture per ton of ore. The concentration of the amine-hydrocarbon mixture is approximately 400 parts per million. Under these conditions we obtain substantial froth flotation of the lead and after activation of zinc by the use of small amounts of copper sulfate an essentially quantitative recovery of zinc results.
Example 2 A mixture or" unsaturated and saturated nitriles and unsaturated and saturated hydrocarbons, boiling between 140 C. and 180 C., is subjected to hydrogenation under the conditions described in Example 1. The original nitrile-hydrocarbon mixture consists essentially of the following substances: Butyl cyanide, butenyl cyanide, pentyl cyanide, pentenyl cyanide, hexyl cyanide and hexenyl cyanide, together with nonane, decane, nonene and decene. After hydrogenation the amuse boiling point range is 120 C. to 220 C. and the product consists of a mixture of pentyl, pentenyl, hexyl, hexenyl, heptyl and heptenyl amines in about equal quantities, together with the above named saturated and unsaturated hydrocarbons and a small amount of secondary amines. This mixture in the concentration of 425 parts per million produces essentially quantitative froth flotation of galena. A concentration of 400 parts per million of this mixture produces essentially complete froth flotation of collophanite.
Example 3 A fraction of nitrile-hydrocarbons with a boiling point range of 180 C. to 200 C. is subjected to hydrogenating conditions as described under Example 1. The boiling point range of the hydrogenated product is 155 C. to 250 0., and .it consists of heptyl, heptenyl, octyl, and octenyl amines, together with decane, decene, undecane, undecene, dodecane and dodecene and a small amount of secondary amines. A concentration of 450 parts per million of this mixture gives essentially quantitative flotation of ga1ena. We also use it in a concentration of 450 parts per million for the flotation of rutile and chalcopyrite.
' The composition of the amine-hydrocarbon mixture can vary over rather wide limits depending upon the boiling point range of the nitrilehydrocarbon mixture which is subjected to hydrogenation. The product obtained from cracking high molecular weight nitriles may be fractionated so as to give a starting nitrile-hydrocarbon mixture of any boiling point range between the limits of the product; Approximately fifty per cent of the amines and hydrocarbons present will contain one double bond and the remainder will consist of saturated compounds. We believe where the double bond is present that it is in a terminal position. Our flotation agents will consist of two or more saturated or unsaturated amines in a mixture of saturated and um saturated hydrocarbons. It is quite difflcult to separate a saturated nitrile from an unsaturated nitrile of the same number of carbon atoms by distillation and it is also impossible to separate the nitriles from the hydrocarbons of the same boiling point range by distillation alone, so the mixtures which we hydrogenate will consist of at least the saturated and unsaturated nitriles in the presence of the hydrocarbons.
Our results indicate that the flotation agents of this invention can be used to concentrate by froth flotation the following minerals from ores containing the same.
Collophanite Chalcopyrite Pyroiusite Magnetite Malachite Franklinite Galena Apatite Rutile Zincite Chalcocite llmenite Pyrite In using our flotation agents we have proceeded in the accepted ways of this art. The ores are first ground and then mixed with water to form a pulp in the usual way. The flotation agent is then added and for experimental work the mixture subjected to froth flotation in a flotation cell. The mineral concentrate is skimmed off as a froth and collected, its composition and weight then determined.
So far as we are aware we are the first to describe mixtures of saturated and unsaturated aliphatic amines having from three to ten carbon atoms dissolved in straight-chain saturated and unsaturated hydrocarbons, and we broadly claim our invention with respect thereto. This mixture is superior for the flotation of both metallic and non-metallic ores because of the presence of both the saturated and unsaturated straightchain amines. In the presence of the olefins and parafiins the mixture performs the double function of preferentially wetting minerals to be floated'whereby its surface tension is so changed that the mineral will float, together with imparting irothing characteristics to the pulp. Consequently, we do not need any additional frothing agent, but our invention is not to be construed so narrowly as toexclude the addition of further frothing agents. These flotation agents described have a decided advantage over the pure compounds now used because of the cumulative efiect of the various components herein described and also because of their cheapness and. availability.
Having thus described our invention, what we claim is:
1. The process of concentrating ores which comprises subjecting the ore to froth flotation separation in the presence of a mixture of saturated and unsaturated aliphatic amines having from three to ten carbon atoms and saturated and unsaturated aliphatic straight-chain hydrocarbons.
2. In the froth flotation of ores the step comcomprises subjecting an aqueous pulp of the ore' to froth flotation in the presence of a flotation agent comprising a mixture of aliphatic amines containing from three to ten carbon atoms in substantial amounts, together with straightchain aliphatic hydrocarbons.
4. A flotation agent comprising an aliphatic hydrocarbon solution of saturated and unsaturated aliphatic amines having from three to ten carbon atoms.
5. A flotation agent comprising an aliphatic hydrocarbon solution of at least one unsaturated aliphatic amine having from three to ten carbon atoms.
6. A flotation agent comprising a hydrocarbon solution of at least two aliphatic amines chosen from the group consisting of butyl, butenyl, pentyl, pentenyl; hexyl, hexenyl, heptyl and heptenyl amines, one of said chosen amines bein unsaturated.
' ANDERSON W. RALSTON.
WILLIAM O. POOL. JAMES HARWOOD.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4908125A (en) * | 1987-07-07 | 1990-03-13 | Henkel Kommanditgesellschaft Auf Aktien | Froth flotation process for the recovery of minerals and a collector composition for use therein |
US9302274B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Collector compositions and methods of using the same |
US9302272B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Froth flotation processes |
US9302273B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Froth flotation processes |
-
1937
- 1937-11-01 US US172284A patent/US2185968A/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4908125A (en) * | 1987-07-07 | 1990-03-13 | Henkel Kommanditgesellschaft Auf Aktien | Froth flotation process for the recovery of minerals and a collector composition for use therein |
AU603685B2 (en) * | 1987-07-07 | 1990-11-22 | Henkel Kommanditgesellschaft Auf Aktien | A collector for use in and a process for the froth flotation recovery of minerals |
US5122289A (en) * | 1987-07-07 | 1992-06-16 | Henkel Kommanditgesellschaft Auf Aktien | Collector composition for use in a froth flotation process for the recovery of minerals |
US9302274B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Collector compositions and methods of using the same |
US9302272B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Froth flotation processes |
US9302273B2 (en) | 2011-10-18 | 2016-04-05 | Cytec Technology Corp. | Froth flotation processes |
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