US3590996A - Floatation of sulfide ores - Google Patents
Floatation of sulfide ores Download PDFInfo
- Publication number
- US3590996A US3590996A US796159A US3590996DA US3590996A US 3590996 A US3590996 A US 3590996A US 796159 A US796159 A US 796159A US 3590996D A US3590996D A US 3590996DA US 3590996 A US3590996 A US 3590996A
- Authority
- US
- United States
- Prior art keywords
- compound
- flotation
- group
- sulfide
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- -1 cyano, acetonyl Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000001475 halogen functional group Chemical group 0.000 claims description 4
- 238000005188 flotation Methods 0.000 abstract description 25
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 6
- 125000002947 alkylene group Chemical group 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 125000004474 heteroalkylene group Chemical group 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 229910052569 sulfide mineral Inorganic materials 0.000 abstract description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000417 fungicide Substances 0.000 abstract description 3
- 239000004009 herbicide Substances 0.000 abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 abstract description 2
- 229910052745 lead Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012991 xanthate Substances 0.000 description 7
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 241000605112 Scapanulus oweni Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001266 acyl halides Chemical class 0.000 description 2
- 125000005354 acylalkyl group Chemical group 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- LJOODBDWMQKMFB-UHFFFAOYSA-N cyclohexylacetic acid Chemical compound OC(=O)CC1CCCCC1 LJOODBDWMQKMFB-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- RXYSSJPZTOKZIC-UHFFFAOYSA-N o-propan-2-yl n-(2-hydroxyethyl)carbamothioate Chemical compound CC(C)OC(=S)NCCO RXYSSJPZTOKZIC-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010665 pine oil Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- IAMALOVTVCLUKP-IHWYPQMZSA-N (z)-2-chlorobut-2-enoyl chloride Chemical compound C\C=C(/Cl)C(Cl)=O IAMALOVTVCLUKP-IHWYPQMZSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- OXHOPZLBSSTTBU-UHFFFAOYSA-N 1,3-bis(bromomethyl)benzene Chemical compound BrCC1=CC=CC(CBr)=C1 OXHOPZLBSSTTBU-UHFFFAOYSA-N 0.000 description 1
- DBGSRZSKGVSXRK-UHFFFAOYSA-N 1-[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]-3,6-dihydro-2H-pyridine-4-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CCC(=CC1)C(=O)O DBGSRZSKGVSXRK-UHFFFAOYSA-N 0.000 description 1
- QHDHNVFIKWGRJR-UHFFFAOYSA-N 1-cyclohexenol Chemical compound OC1=CCCCC1 QHDHNVFIKWGRJR-UHFFFAOYSA-N 0.000 description 1
- ZVKQNIUBLJYSGN-UHFFFAOYSA-N 2,3,5-trimethylhexan-3-ol Chemical compound CC(C)CC(C)(O)C(C)C ZVKQNIUBLJYSGN-UHFFFAOYSA-N 0.000 description 1
- FQONOTCENZKKQT-UHFFFAOYSA-N 2-aminoethyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OCCN FQONOTCENZKKQT-UHFFFAOYSA-N 0.000 description 1
- MDFFZNIQPLKQSG-UHFFFAOYSA-N 2-bromoprop-2-en-1-ol Chemical compound OCC(Br)=C MDFFZNIQPLKQSG-UHFFFAOYSA-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
- GUGQQGROXHPINL-UHFFFAOYSA-N 2-oxobutanoyl chloride Chemical compound CCC(=O)C(Cl)=O GUGQQGROXHPINL-UHFFFAOYSA-N 0.000 description 1
- QCJPGIFKFKZXAQ-UHFFFAOYSA-N 4-(3-fluoroazetidin-1-yl)piperidine Chemical compound C1C(F)CN1C1CCNCC1 QCJPGIFKFKZXAQ-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- VJDDQSBNUHLBTD-GGWOSOGESA-N [(e)-but-2-enoyl] (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(=O)\C=C\C VJDDQSBNUHLBTD-GGWOSOGESA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- MXMOTZIXVICDSD-UHFFFAOYSA-N anisoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1 MXMOTZIXVICDSD-UHFFFAOYSA-N 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- OIGPMFVSGDDYHS-UHFFFAOYSA-N copper sulfanylidenemolybdenum Chemical compound [S].[Cu].[Mo] OIGPMFVSGDDYHS-UHFFFAOYSA-N 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
- 125000004093 cyano group Chemical group *C#N 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
- 239000002283 diesel fuel Substances 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 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
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- SRXOJMOGPYFZKC-UHFFFAOYSA-N methyl 4-chloro-4-oxobutanoate Chemical compound COC(=O)CCC(Cl)=O SRXOJMOGPYFZKC-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QBKJZGQCMYQSLM-UHFFFAOYSA-N o-ethyl n-(2-hydroxyethyl)carbamothioate Chemical compound CCOC(=S)NCCO QBKJZGQCMYQSLM-UHFFFAOYSA-N 0.000 description 1
- DUJGSBQTJWXYSJ-UHFFFAOYSA-N o-ethyl n-hydroxycarbamothioate Chemical compound CCOC(=S)NO DUJGSBQTJWXYSJ-UHFFFAOYSA-N 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VJDDQSBNUHLBTD-UHFFFAOYSA-N trans-crotonic acid-anhydride Natural products CC=CC(=O)OC(=O)C=CC VJDDQSBNUHLBTD-UHFFFAOYSA-N 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- WCJYTPVNMWIZCG-UHFFFAOYSA-N xylylcarb Chemical compound CNC(=O)OC1=CC=C(C)C(C)=C1 WCJYTPVNMWIZCG-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 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
Definitions
- FLOATATION 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, 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.
- 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 different 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.
- additives 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 a novel class of compounds. These compounds can be employed as collection agents in a flotation process. With some of these compounds better recoveries are realized and with others, improved selectivity is achieved. Certain of these compounds produce improvement in both aspects.
- the present invention concerns novel compounds corresponding to the formula wherein R represents H, a hydrocarbyl group, or a heterohydrocarbyl group, wherein said groups can be substituted with up to two functional groups and contain from 1 to 10 carbon atoms; R, represents an alkylene or heteroalkylene group having a heteroatom substituted in the carbon chain, and R represents a hydrocarbyl or heterohydrocarbyl group, except for aryl, wherein either of said groups can be substituted except in the alpha position with up to two functional groups.
- the novel compounds can be prepared by the reaction of an amino alcohol with a xanthate ester and contacting the product produced with an acyl halide.
- novel compounds can be employed to improved the flotation process of separating sulfide minerals from ores by employing an effective quantity of at least one of the novel compounds set forth herein in the flotation process.
- novel compounds are also useful as fungicides and herbicides.
- novel compounds of the present invention correspond to the formula wherein R represents H, a hydrocarbyl group selected from the group consisting of alkyl or alkenyl containing up to 10 carbon atoms, alkaryl, aryl, aralkyl, cycloalkyl, cycloalkenyl, aralkenyl or acylalkyl groups, wherein the acyclic carbon chain portions preferably contain up to 3 carbon atoms and the cyclic group contains from 5 to 10 carbon atoms and a heterohydrocarbyl radical selected from the group consisting of alkoxy, alkenyloxy, alkoxy carbonyl, alkoxycarbonylalkyl, aryloxy, arylalkoxy, alkylthio and arylthio groups, wherein said heterohydrocarbyl groups can contain up to two identical or different functional groups preferably selected from the group consisting of halo, alkoxy, cyano, and di-loweralkyla
- novel compounds as defined herein can be prepared, for example, by reacting an aminoalcohol with a xanthate ester to prepare a hydroxy-thionourethane and then acylating the HO-R -moiety with an acyl halide, anhydride, or ketene.
- the reactions can be represented as follows:
- novel compounds as defined herein have a special utility as flotation collectors and can be employed in standard flotation processes to concentrate copper sulfide and other like minerals from sulfide ores in preference to iron sulfides
- a pulp is first prepared by wet grinding a sulfide containing 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 a flotation collector compound as defined herein is Example 1
- a novel compound corresponding to the formula was prepared in the following manner.
- Example 2 A new compound within the scope of the invention defined herein and corresponding to the formula was prepared in the following manner: A solution of 16.3 grams of isopropyl 2-hydroxyethylthionocarbamate in 25 ml. of 50 percent diketene/acetone was let stand for a week. The oil obtained on addition of 100 ml. of water was taken up in ether. This extract was dried over MgSO The solid was later removed by filtration and the ether removed by distillation, the last traces with a vacuum. The structure as set forth above was confirmed by infrared and NMR analyses. The yield was 89 percent. The calculated and actual elemental analysis for the product corresponding to the formula set forth above is Percent Example 3 Another novel compound within the scope of the present invention is prepared in the following manner. The reaction is set forth as:
- the compound is prepared as follows.
- Example 4 A new compound corresponding to the formula was prepared in the following manner.
- Example 5 A new compound within the scope of the present invention was prepared corresponding to the formula
- a starting material compound corresponding to the formula was prepared as follows: To 18.1 grams of 2-(2-hydroxyethyl)- thioethylamine was added 22.5 grams of methyl isopropylx anthate. The mixture was heated in a hot water bath to drive off most of the evolved CH SH gas. The mixture was then heated to 65 C. under a reduced pressure of 20 mm. to remove the last traces of CH Sl-l. The yield was nearly quantitative. The structure of this starting material was 4by infrared and NMR analysis. To 17.9 grams of the so-prepared starting material in 35 ml. of ether and 8.9 ml.
- Example 7 Various species of flotation collector compounds within the scope of the present invention were employed in the recovery remaining ether and the methyl acetate were removed under 5 of pp and molybdenum fr m a S lfide ore obtained from d d pressure f 4 b h i to 70 C 19 7 grams or South America employing the following procedure: The ore about a 93 percent yield of the product was obtained, Th sample was ground for 5 minutes at 66 percent solids with no structure of the novel compound corresponding to that set reagents The p p Cohdmohed 8 minutes with forth above was continued by infrared and NMR analysis.
- Eleof a Speclfic flotahoh collector compound and menu analysis gave 452 percent 3 percent and 0.13 lbs./ton of a standard frother. During the conditioning percent. Calculated analysis for a compound corresponding to Penod the P was adlusted 5 3 value of 3909i The P p m above structure is (3,453 percent percent and was then floated for seven minutes and the tailings assayed for 3 percent copper and molybdenum.
- a standard flotation collector consisting of a thionocarbamate compound corresponding to the Example 6 15 formula
- Other species of compounds within the scope of the present H s CH invention were prepared according to one of the procedures g 3 set forth in Examples l4. The starting materials consisted of 1 2 a compound corresponding to the formula OH;
- OHCHFIL OCH(CHJ)E s o 0. 03 0. 23s 86. s
- Example 8 Various novel collectors within the scope of the present invention were tested on a copper sulfide ore from the Southeastern United States. The ore sample was ground for 4% minutes at 59 percent solids with 2.0 lbs/ton of lime. The pulp was conditioned for 2 minutes with an amount of a specific collector and 0.16 lbs/ton of a standard frother at a pH of 10.5. The pulp was then floated for 8% minutes and the tailings assayed for copper. The results obtained are set forth in the following Table III. The same control flotation collector was employed as in Example 7.
- a sample of ore was ground at 60 percent solids to 35 percent minus 200 mesh Tyler. To the pulp was added 0.9 lbs/ton lime, 0.08 lbs/ton diesel oil, 0.01 lbs/ton of a collector compound to be tested and 0.06 lbs/ton frother. The ore was floated for 8 minutes. Both the concentrate and tailings were filtered, dried and assayed for Mo and Cu. The same control collector compound was employed as in Examples 7 and 8.
- the xanthate starting materials employed herein in the preparation of the novel compounds can be prepared in a manner well known in the art.
- an alcohol corresponding to R,OH, wherein R is the same as defined hereinbefore can be reacted as the corresponding alkali metal alkoxide, with CS, to prepare a product corresponding to the formula wherein M is the alkali metal ion.
- the product can then be contacted with, for example, methyl chloride, to prepare the corresponding xanthate ester i R C-SCH;
- Alcohols which may be employed include, for example, cyclohexanol, cyclohexenol, allyl alcohol, cinnamyl alcohol. 2-bromo-allyl alcohol; 2,3,5-trimethyl-3-hexanol; 2,3,4- trimethyl-Z-hexanol and the like.
- Acylating agents which can be used in preparing the novel compounds of the present invention can be prepared by converting carboxylic acids to the corresponding acyl chloride by contacting said acids with thionyl chloride by processes well known in the art.
- Carboxylic acids which may be employed in clude, for example, cinnamic acid, a-bromocaproic acid, pelargonic acid, methacrylic acid, 3-cyanophenylacetic acid, cyclohexylacetic acid, cyanoacetic acid, Z-phenoxybutanoic acid, methoxyacetic acid and the like.
- a compound corresponding to the formula can be prepared by reacting ethylenimine and pivalic acid to prepare a compound corresponding to the formula (CH3)3CC CHQCH3XHQ and reacting this compound with methyl isopropyl xanthate to Another compound corresponding to the formula is prepared by reacting 17.0 grams of aniosoyl chloride with 16.3 grams of ethyl 2-hydroxyethylthionocarbamate to produce the indicated compound having a molecular weight of 283.
- a. subjecting the sulfide containing ore in the form of a pulp to flotation collector comprising a compound corresponding the formula wherein R represents H, a hydrocarbyl radical selected from the group consisting of alkyl or alkenyl containing up to 10 carbon atoms, aryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, aralkenyl or acylalkyl groups wherein the acyclic carbon chain portion contains up to 3 carbon atoms and the cyclic groups contains from 5 to 10 carbon atoms, a heterohydrocarbyl selected from the group consisting of alkoxy, alkenyloxy, alkoxy carbonyl, alkoxycarbonylalkyl, aryloxy, alkylthio, arylthio, or oxyalkyl group; R represents a member selected 0 from the group consisting of an alkylene or heteroalkylene wherein X is a member selected from the group consisting
- R and R contain up to two functional groups other than in the alpha position of R selected from the group consisting of halo, alkoxy, cyano, acetonyl, or di-loweralkylamino group.
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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 corresponding to the formula WHEREIN R and R2 are hydrocarbyl groups and R1 represents an alkylene or heteroalkylene group. Certain of the indicted compounds provide for enhanced recovery and/or selectivity of sulfide minerals of Cu, Zn, Mo, Co, Ni, Pb and As over iron sulfide. The compounds are also useful as fungicides and herbicides.
Description
United States Patent [72] Inventor Guy 11. Harris Concord, Calif. 21 Appl. No. 796,159 [22] Filed Feb. 3, 1969 [45] Patented July 6,1971 [73] Assignee The Dow Chemical Company Mldland, Mich.
[541 F LOATATION OF SULFIDE ORES 10 Claims, No Drawings [52] U.S.Cl 209/166, 200/455 [51] 1nt.Cl B03d1/02, C07c 153/07 [50] Field ofSearch 209/106, 167; 252/61; 260/455 56] References Cited UNlTED STATES PATENTS 1,640,218 8/1927 Sayre 209/166 1,674,166 6/1928 Douglass 209/166 2,691,635 10/1954 Harris 209/166X 2,835,625 5/1958 Lo 260/455X 3,012,053 12/1961 Lesslie 260/455 3,224,863 12/1965 DAmico 260/455X 3,290,351 12/1966 McKay 260/455 FOREIGN PATENTS 750,568 6/1956 Great Britain 260/455 1,179,312 12/1958 France 260/455 Primary Examiner-Tim R. Miles Assistant Examingr -Robert l-lalper Azrorn vs-Griswold and Burdick and Bruce M. Kanuch 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 ofa flotation collector corresponding to the formula wherein R and R are hydrocarbyl groups and R represents an alkylene or heteroalkylene group. Certain of the indicted compounds provide for enhanced recovery and/or selectivity of sulfide minerals of Cu, Zn, Mo, Co, Ni, Pb and As over iron sulfide. The compounds are also useful as fungicides and herbicides.
FLOATATION 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, 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 particles of different 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 additives 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 afl'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 a novel class of compounds. These compounds can be employed as collection agents in a flotation process. With some of these compounds better recoveries are realized and with others, improved selectivity is achieved. Certain of these compounds produce improvement in both aspects.
SUMMARY The present invention concerns novel compounds corresponding to the formula wherein R represents H, a hydrocarbyl group, or a heterohydrocarbyl group, wherein said groups can be substituted with up to two functional groups and contain from 1 to 10 carbon atoms; R, represents an alkylene or heteroalkylene group having a heteroatom substituted in the carbon chain, and R represents a hydrocarbyl or heterohydrocarbyl group, except for aryl, wherein either of said groups can be substituted except in the alpha position with up to two functional groups. The novel compounds can be prepared by the reaction of an amino alcohol with a xanthate ester and contacting the product produced with an acyl halide. The novel compounds can be employed to improved the flotation process of separating sulfide minerals from ores by employing an effective quantity of at least one of the novel compounds set forth herein in the flotation process. The novel compounds are also useful as fungicides and herbicides.
PREFERRED EMBODIMENTS The novel compounds of the present invention correspond to the formula wherein R represents H, a hydrocarbyl group selected from the group consisting of alkyl or alkenyl containing up to 10 carbon atoms, alkaryl, aryl, aralkyl, cycloalkyl, cycloalkenyl, aralkenyl or acylalkyl groups, wherein the acyclic carbon chain portions preferably contain up to 3 carbon atoms and the cyclic group contains from 5 to 10 carbon atoms and a heterohydrocarbyl radical selected from the group consisting of alkoxy, alkenyloxy, alkoxy carbonyl, alkoxycarbonylalkyl, aryloxy, arylalkoxy, alkylthio and arylthio groups, wherein said heterohydrocarbyl groups can contain up to two identical or different functional groups preferably selected from the group consisting of halo, alkoxy, cyano, and di-loweralkylamino groups; R, represents an alkylene or heteroalkylene group containing up to 8 carbon atoms and wherein the hetero atom is substituted in the carbon chain and is preferably selected from the group consisting of wherein X is a hydrocarbyl or heterohydrocarbyl group and not H; preferably X is a lower alkyl group containing up to 5 carbon atoms; and R represents a hydrocarbyl group selected from the group consisting of an alkyl or alkenyl group, preferably containing up to 8 carbon atoms, an aralkyl group, preferably containing from 1 to 3 carbon atoms, in the alkyl portion, and an alicyclic or cycloakenyl group, preferably containing from 3 to 8 carbon atoms, wherein said hydrocarbyl groups can be substituted, except in the alpha position, with up to two identical or diflerent functional groups preferably selected from the group consisting of alkoxy, halo, cyano, acetonyl and dilower alkylamino groups. R, R, and R are further characterized in that the total number'of carbon atoms in said groups preferably ranges from about 4 to about 25.
The novel compounds as defined herein can be prepared, for example, by reacting an aminoalcohol with a xanthate ester to prepare a hydroxy-thionourethane and then acylating the HO-R -moiety with an acyl halide, anhydride, or ketene. The reactions can be represented as follows:
The novel compounds as defined herein have a special utility as flotation collectors and can be employed in standard flotation processes to concentrate copper sulfide and other like minerals from sulfide ores in preference to iron sulfides In a flotation process a pulp is first prepared by wet grinding a sulfide containing 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 a flotation collector compound as defined herein is Example 1 A novel compound corresponding to the formula was prepared in the following manner.
To 30 grams (0.2 moles) of methyl isopropylxanthate was added 12.2 grams (0.2 moles) of 2-aminoethanol. The mixture became hot and there was a vigorous evolution of methyl mercaptan. After an hour of heating on the steam bath, the residual methyl mercaptan was removed by applying a vacuum. The structure of the product, confirmed by infrared and NMR analyses, corresponded to the formula The product was a viscous liquid. A sample of this product was distilled under vacuum and had a boiling point of 120- 122 C. at 0.7 mm. Hg.
A solution of 16.3 grams of the product prepared above, 10.2 grams of acetic anhydride, and 8.1 ml. of pyridine in 100 ml. of absolute diethyl ether was let stand for a day. More ether was added and then the mixture was washed twice with water, dilute l-lCl, and finally with saturated aqueous NaH- C0 After drying over MgSO, and removing the solid by filtration, the solvent was stripped off by heating to 75 C. under a reduced pressure of 20 mm. The yield was 16.9 grams (76.5 percent yield) of the novel compound designated above. The structure of the new compound was identified by infrared analysis. A sample of the compound was distilled under a reduced pressure and was found to have a boiling point of lO9ll2C.00.l mm.llg.
Example 2 A new compound within the scope of the invention defined herein and corresponding to the formula was prepared in the following manner: A solution of 16.3 grams of isopropyl 2-hydroxyethylthionocarbamate in 25 ml. of 50 percent diketene/acetone was let stand for a week. The oil obtained on addition of 100 ml. of water was taken up in ether. This extract was dried over MgSO The solid was later removed by filtration and the ether removed by distillation, the last traces with a vacuum. The structure as set forth above was confirmed by infrared and NMR analyses. The yield was 89 percent. The calculated and actual elemental analysis for the product corresponding to the formula set forth above is Percent Example 3 Another novel compound within the scope of the present invention is prepared in the following manner. The reaction is set forth as:
The compound is prepared as follows.
To 15 grams (0.1 g. mole) of methyl isopropyl xanthate is added 14.5 g. (0.1 g. mole) of 2-aminoethyl pivalate and the mixture warmed. When methyl mercaptan evolution ceases, the last traces are removed under vacuum. The residual oil is induced to crystallize and the resulting solid-the new compoundis found to melt at 4849 C.
Example 4 A new compound corresponding to the formula was prepared in the following manner.
A solution of 16.3 grams of isopropyl 2-hydroxyethylthionocarbamate (0.1 mole), 7.9 gms. of pyridine (0.1 mole) in ml. of ether, was cooled and stirred. 13.6 grams (0.1 mole) of ethyl oxalyl chloride was added with cooling and stirring and when this was complete, the solution was stirred for one hour. The ether solution was dried with Na SO filtered and stripped of ether by heating under a vacuum. The product yield was 81 percent. The product was analyzed by both infrared and NMR analysis. The actual and calculated elemental analysis for the compound having the formula set forth above are:
Percent C H N Calculated... 45. 61 6.51 5.32 Actual- 44.0 6.50 5.80
Example 5 A new compound within the scope of the present invention was prepared corresponding to the formula A starting material compound corresponding to the formula was prepared as follows: To 18.1 grams of 2-(2-hydroxyethyl)- thioethylamine was added 22.5 grams of methyl isopropylx anthate. The mixture was heated in a hot water bath to drive off most of the evolved CH SH gas. The mixture was then heated to 65 C. under a reduced pressure of 20 mm. to remove the last traces of CH Sl-l. The yield was nearly quantitative. The structure of this starting material was 4by infrared and NMR analysis. To 17.9 grams of the so-prepared starting material in 35 ml. of ether and 8.9 ml. of pyridine was added 9.0 grams of acetic anhydride. After 20 hours, additional ether and a small quantity of methanol was added to convert the unreacted acetic anhydride present to methyl acetate. The reaction mixture was then treated with a dilute hydrochloric acid solution to remove the pyridine and then washed with aqueous Nal-lCO to remove the acids. The product mixture was then dried over MgSO filtered and the Example 7 Various species of flotation collector compounds within the scope of the present invention were employed in the recovery remaining ether and the methyl acetate were removed under 5 of pp and molybdenum fr m a S lfide ore obtained from d d pressure f 4 b h i to 70 C 19 7 grams or South America employing the following procedure: The ore about a 93 percent yield of the product was obtained, Th sample was ground for 5 minutes at 66 percent solids with no structure of the novel compound corresponding to that set reagents The p p Cohdmohed 8 minutes with forth above was continued by infrared and NMR analysis. Eleof a Speclfic flotahoh collector compound and menu analysis gave 452 percent 3 percent and 0.13 lbs./ton of a standard frother. During the conditioning percent. Calculated analysis for a compound corresponding to Penod the P was adlusted 5 3 value of 3909i The P p m above structure is (3,453 percent percent and was then floated for seven minutes and the tailings assayed for 3 percent copper and molybdenum. A standard flotation collector consisting of a thionocarbamate compound corresponding to the Example 6 15 formula Other species of compounds within the scope of the present H s CH invention were prepared according to one of the procedures g 3 set forth in Examples l4. The starting materials consisted of 1 2 a compound corresponding to the formula OH;
I ll HOR1NH-C-ORZ and an acylating agent which provided the 4: moiety of the novel compounds. R R the acylating agent, the empirical formula of the prepared compound, and the actual and calculated analysis for each compound are set forth in the following Table I. The method of preparation is listed in the method of preparation column and the number corresponds to one of the Examples 1-4. All the compounds were found to possess collector activity when employed in the flotation separation of sulfide containing ores. 3 5
TABLE I Analysis, percent Method of prep- Calculated Actual aratiori Compound empirical R R3 Acylating agent C H N C H N i l CgHnNOaS l CHzCHz- --iPr (CH3C)2O 46.81 7.37 6.82 46.4 7.3 6. 8
CH; |OI l CuHnNOaS 1 CH-CHziPr (d C-):O b 59. 76 6.80 4.98 59.5 6.9 5.4
C-ZH5 (I) l C9HI1NO3S 1 CH2CH- CzHs (CH3C)2O 49.29 7.82 6. 39 49.4 8.2 4.9
CH3 H C HnNOaS 1 C H-CH: iPr (CH3C)2O 49. 29 7.82 6.39 48. 6 8.0 6. 5
if clzHggNo s 1 -C:HOC2H4 iPr (CH;):CHC)2O 55.14 8. 87 5. 36 51.4 9.8 5.3
H C9Ht7NO4S 4 CzH lPr C2H5O-C-Cl 45.94 7- 28 5.95 45.7 7 3 6.4
CH3 (I) C HirNOaS 1 HCHz- -iPr (CH3C-)2O 49.29 7.82 6.39 48.6 8.0 6.5
CH: (H) C1QH1QNO4S 4 CHCHriPr C'ZHflOC-Cl 48.17 7.68 5. 62 47.3 7.9 6.9
ll CiaHirNOaS 4 CQH4- iPi' rbC-Cl 58.40 6.41 5.24 58.6 6.4 7.1
II CuHziNOaS 1 -C5H1 C2H5 (CH3-C-)2O 53.41 8.56 5.66 53. 2 8.6 6. 2
i C1aHnNO4S 4 CzH iPr O-C-Cl 55.10 6.05 4.94 56.7 8.9 5. 3
was employed as a control. The specific collector compounds employed and results are set forth in the following Table ll.
TABLE II Percent Percent Run Number Collector compound Ed 33:1 clfi l l a ii recovered recovere ControL ControL. 0. 12 O. 281 84. 2 64. 4
cu coczurxcocmcnm 2 O CH; HS 0.09 0.234 87.0
OHCHFIL OCH(CHJ)E s o 0. 03 0. 23s 86. s
C2H5O1C|OC2H4NCOCH(CH3)2 l. l
Example 8 Example 9 Various novel collectors within the scope of the present invention were tested on a copper sulfide ore from the Southwestern United States. The ore sample was ground for 4% minutes at 59 percent solids with 2.0 lbs/ton of lime. The pulp was conditioned for 2 minutes with an amount of a specific collector and 0.16 lbs/ton of a standard frother at a pH of 10.5. The pulp was then floated for 8% minutes and the tailings assayed for copper. The results obtained are set forth in the following Table III. The same control flotation collector was employed as in Example 7.
In this example a copper-molybdenum sulfide containing ore from Western United States was treated in a manner similar to that described in Examples 7 and 8.
A sample of ore was ground at 60 percent solids to 35 percent minus 200 mesh Tyler. To the pulp was added 0.9 lbs/ton lime, 0.08 lbs/ton diesel oil, 0.01 lbs/ton of a collector compound to be tested and 0.06 lbs/ton frother. The ore was floated for 8 minutes. Both the concentrate and tailings were filtered, dried and assayed for Mo and Cu. The same control collector compound was employed as in Examples 7 and 8.
TABLE III Lbs. Percent Percent Saber Collector compound add gz i iaiii co r e ls'gl'jffifiilii::::::::::::::::::::::::::::::::31:33:: 3:93 3:??? 32:? 1 O 0 H HS 0. 008 0.324 60.1
C H5PJOCzH I IC Hol I OCH(CH )z (CHghCHii?OC H4OC H NQOCH(CH I'IS CH ]OCzH410 OCH(CH 4 0 CH S 0. 025 0. 092 87. 2
CH3% OC IHCHQNE OCH(CH )3 CzH O( )OC H51 1( OCH(CH )g i JOC2H4I M JOCH(CH CH3COCuH1gNCOC2H5 8... 0 CH3 HS 0.13 0 110 85.5
CHi JOJJHCHQI I OCEKCHQQ CgH O 3 OC3H6.-\L(H:O CH(CH3)'2 3OCzH4NOCH(CH;)g
11 CH 0 CuH NQ O C3H5 0. 13 0. 118 84. 5
ll 0 HS The results obtained are shown in the accompanying Table IV.
prepare the indicated novel compound.
The xanthate starting materials employed herein in the preparation of the novel compounds, for example, as in Example 1, can be prepared in a manner well known in the art. For example, an alcohol corresponding to R,OH, wherein R is the same as defined hereinbefore, can be reacted as the corresponding alkali metal alkoxide, with CS, to prepare a product corresponding to the formula wherein M is the alkali metal ion. The product can then be contacted with, for example, methyl chloride, to prepare the corresponding xanthate ester i R C-SCH;
Alcohols which may be employed include, for example, cyclohexanol, cyclohexenol, allyl alcohol, cinnamyl alcohol. 2-bromo-allyl alcohol; 2,3,5-trimethyl-3-hexanol; 2,3,4- trimethyl-Z-hexanol and the like.
Acylating agents which can be used in preparing the novel compounds of the present invention can be prepared by converting carboxylic acids to the corresponding acyl chloride by contacting said acids with thionyl chloride by processes well known in the art. Carboxylic acids which may be employed in clude, for example, cinnamic acid, a-bromocaproic acid, pelargonic acid, methacrylic acid, 3-cyanophenylacetic acid, cyclohexylacetic acid, cyanoacetic acid, Z-phenoxybutanoic acid, methoxyacetic acid and the like.
Other acylating agents which can be employed to prepare the novel compounds include thiochloroformates such as and alkenylchloroformates such as O 0H2=c11-cH,o c'o1 and the like.
Other novel compounds may be prepared in a manner similar to that described in the foregoing examples. For example, a compound corresponding to the formula can be prepared by reacting ethylenimine and pivalic acid to prepare a compound corresponding to the formula (CH3)3CC CHQCH3XHQ and reacting this compound with methyl isopropyl xanthate to Another compound corresponding to the formula is prepared by reacting 17.0 grams of aniosoyl chloride with 16.3 grams of ethyl 2-hydroxyethylthionocarbamate to produce the indicated compound having a molecular weight of 283. Similarly, by employing 10.4 grams of crotonyl chloride, 15.4 grams of crotonic anhydride, 13.8 grams of 2- chlorocrotonyl chloride, or 15.0 grams of 3-carbomethoxypropionyl chloride instead of anisoyl chloride, compounds corresponding to the following formula are prepared:
and
O H S respectively.
Other compounds within the scope of the present invention may be prepared by a method as defined herein by choosing various starting materials.
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.
What 1 claim is:
1. In a process of concentrating sulfide ores by flotation in the presence of a flotation collector, the improvement which comprises:
a. subjecting the sulfide containing ore in the form of a pulp to flotation collector comprising a compound corresponding the formula wherein R represents H, a hydrocarbyl radical selected from the group consisting of alkyl or alkenyl containing up to 10 carbon atoms, aryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, aralkenyl or acylalkyl groups wherein the acyclic carbon chain portion contains up to 3 carbon atoms and the cyclic groups contains from 5 to 10 carbon atoms, a heterohydrocarbyl selected from the group consisting of alkoxy, alkenyloxy, alkoxy carbonyl, alkoxycarbonylalkyl, aryloxy, alkylthio, arylthio, or oxyalkyl group; R represents a member selected 0 from the group consisting of an alkylene or heteroalkylene wherein X is a member selected from the group consisting ofa hydrocarbyl or heterohydrocarbyl radical wherein the hetero atom is substituted in the carbon chain; and R represents a hydrocarbyl selected from the group consisting of an alkyl or alkenyl group, containing up to 8 carbon atoms, an aralkyl, containing from I to 3 carbon atoms in the alkyl portion, and analicyclic or cycloakenyl group, containing from 3 to 8 carbon atoms, wherein R, R and R, are further characterized in that the total number of carbon atoms in said groups range from about 4 to about 25.
2. The process as defined in claim 1 wherein R and R contain up to two functional groups other than in the alpha position of R selected from the group consisting of halo, alkoxy, cyano, acetonyl, or di-loweralkylamino group.
3. The process as defined in claim 1 wherein X is a lower alkyl group containing up to 5 carbon atoms.
4. The process as defined in claim 1 wherein from about 0.01 to about 0.25 pound of compound per ton of sulfide ore pulp is employed.
5. The process defined in claim I wherein said compound consists of 0 CH3 H S ll 1 a CH; OCHCH N- OCH(CH )2 6. The process defined in claim 1 wherein said compound consists of r H s CH3C-OCH2CHZNCOCH(CH3):
7. The process as defined in claim 1 wherein said compound consists of 0 CH H S 8. The process as defined in claim 1 wherein said compound consists of OH: H S
9. The process as defined in claim 1 wherein said compound consists of O H S
Claims (9)
- 2. The process as defined in claim 1 wherein R and R2 contain up to two functional groups other than in the alpha position of R2, selected from the group consisting of halo, alkoxy, cyano, acetonyl, or di-loweralkylamino group.
- 3. The process as defined in claim 1 wherein X is a lower alkyl group containing up to 5 carbon atoms.
- 4. The process as defined in claim 1 wherein from about 0.01 to about 0.25 pound of compound per ton of sulfide ore pulp is employed.
- 5. The process defined in claim 1 wherein said compound consists of
- 6. The process defined in claim 1 wherein said compound consists of
- 7. The process as defined in claim 1 wherein said compound consists of
- 8. The process as defined in claim 1 wherein said compound consists of
- 9. The process as defined in claim 1 wherein said compound consists of
- 10. The process as defined in claim 1 wherein said compound consists of
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3853751A (en) * | 1972-02-08 | 1974-12-10 | Dow Chemical Co | Flotation of sulfide ores using dithiocarbamates |
US4122004A (en) * | 1976-12-27 | 1978-10-24 | The Dow Chemical Company | Froth flotation process |
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 |
US4702822A (en) * | 1985-07-12 | 1987-10-27 | The Dow Chemical Company | Novel collector composition for froth flotation |
AU594845B2 (en) * | 1984-08-17 | 1990-03-15 | American Cyanamid Company | Neutral circuit sulfide collectors |
Citations (9)
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US1640218A (en) * | 1925-07-23 | 1927-08-23 | Metals Recovery Co | Concentration of ores |
US1674166A (en) * | 1926-06-25 | 1928-06-19 | Du Pont | Process of concentrating ores and minerals by flotation |
US2691635A (en) * | 1953-05-20 | 1954-10-12 | Dow Chemical Co | Process for the manufacture of dialkyl thionocarbamates |
GB750568A (en) * | 1953-06-22 | 1956-06-20 | Ciba Ltd | New thiocarbamic acid esters and process for their manufacture |
US2835625A (en) * | 1956-01-19 | 1958-05-20 | Rohm & Haas | Isopropoxycarbonyl dimethyldithio-carbamate |
FR1179312A (en) * | 1956-04-24 | 1959-05-22 | Monsanto Canada Ltd | nu, nu'-di- (carboxyalkylthiocarbamyl) polymethylenediamines |
US3012053A (en) * | 1958-08-06 | 1961-12-05 | Monsanto Chemicals | Alkylenebis (thionocarbamates) |
US3224863A (en) * | 1962-06-13 | 1965-12-21 | Monsanto Co | Vegetation control with unsaturated hydrocarbon esters of n,n-disubstituted thionocarbamic acids |
US3290351A (en) * | 1959-01-16 | 1966-12-06 | Monsanto Canada Ltd | Aryl esters of 3, 4-dichloro-phenyl thionocarbamates |
-
1969
- 1969-02-03 US US796159A patent/US3590996A/en not_active Expired - Lifetime
-
1970
- 1970-01-06 GB GB689/70A patent/GB1293742A/en not_active Expired
- 1970-01-06 ZA ZA700085A patent/ZA7000085B/en unknown
- 1970-01-28 ZM ZM11/70A patent/ZM1170A1/en unknown
- 1970-01-30 DE DE19702004105 patent/DE2004105A1/en active Pending
- 1970-01-30 FR FR7003436A patent/FR2046117A5/fr not_active Expired
- 1970-02-02 ES ES376141A patent/ES376141A1/en not_active Expired
- 1970-02-02 BE BE745341D patent/BE745341A/en unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1640218A (en) * | 1925-07-23 | 1927-08-23 | Metals Recovery Co | Concentration of ores |
US1674166A (en) * | 1926-06-25 | 1928-06-19 | Du Pont | Process of concentrating ores and minerals by flotation |
US2691635A (en) * | 1953-05-20 | 1954-10-12 | Dow Chemical Co | Process for the manufacture of dialkyl thionocarbamates |
GB750568A (en) * | 1953-06-22 | 1956-06-20 | Ciba Ltd | New thiocarbamic acid esters and process for their manufacture |
US2835625A (en) * | 1956-01-19 | 1958-05-20 | Rohm & Haas | Isopropoxycarbonyl dimethyldithio-carbamate |
FR1179312A (en) * | 1956-04-24 | 1959-05-22 | Monsanto Canada Ltd | nu, nu'-di- (carboxyalkylthiocarbamyl) polymethylenediamines |
US3012053A (en) * | 1958-08-06 | 1961-12-05 | Monsanto Chemicals | Alkylenebis (thionocarbamates) |
US3290351A (en) * | 1959-01-16 | 1966-12-06 | Monsanto Canada Ltd | Aryl esters of 3, 4-dichloro-phenyl thionocarbamates |
US3224863A (en) * | 1962-06-13 | 1965-12-21 | Monsanto Co | Vegetation control with unsaturated hydrocarbon esters of n,n-disubstituted thionocarbamic acids |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3853751A (en) * | 1972-02-08 | 1974-12-10 | Dow Chemical Co | Flotation of sulfide ores using dithiocarbamates |
US4122004A (en) * | 1976-12-27 | 1978-10-24 | The Dow Chemical Company | Froth flotation process |
US4387034A (en) * | 1981-10-23 | 1983-06-07 | Thiotech, Inc. | Mixed alkylthionocarbamates flotation collectors and ore dressing methods in which the collectors are employed |
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 |
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 |
AU594845B2 (en) * | 1984-08-17 | 1990-03-15 | American Cyanamid Company | Neutral circuit sulfide collectors |
US4702822A (en) * | 1985-07-12 | 1987-10-27 | The Dow Chemical Company | Novel collector composition for froth flotation |
Also Published As
Publication number | Publication date |
---|---|
GB1293742A (en) | 1972-10-25 |
ES376141A1 (en) | 1972-03-01 |
DE2004105A1 (en) | 1970-08-06 |
BE745341A (en) | 1970-08-03 |
ZM1170A1 (en) | 1971-03-22 |
ZA7000085B (en) | 1971-02-24 |
FR2046117A5 (en) | 1971-03-05 |
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