CN1214704A - 硫化物矿物的新颖聚合物抑制剂 - Google Patents
硫化物矿物的新颖聚合物抑制剂 Download PDFInfo
- Publication number
- CN1214704A CN1214704A CN97193365A CN97193365A CN1214704A CN 1214704 A CN1214704 A CN 1214704A CN 97193365 A CN97193365 A CN 97193365A CN 97193365 A CN97193365 A CN 97193365A CN 1214704 A CN1214704 A CN 1214704A
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- Prior art keywords
- hydrogen
- unit
- ore
- alkyl
- valency
- 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.)
- Granted
Links
- 229910052569 sulfide mineral Inorganic materials 0.000 title abstract description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 11
- 239000011707 mineral Substances 0.000 claims abstract description 11
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003112 inhibitor Substances 0.000 claims description 23
- 238000005188 flotation Methods 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 10
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical group OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 230000036541 health Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000013055 pulp slurry Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 5
- 229920001897 terpolymer Polymers 0.000 abstract description 18
- 238000009291 froth flotation Methods 0.000 abstract description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 229960001748 allylthiourea Drugs 0.000 abstract 1
- 230000000881 depressing effect Effects 0.000 abstract 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 22
- 239000011701 zinc Substances 0.000 description 21
- 229910052725 zinc Inorganic materials 0.000 description 20
- JCBJVAJGLKENNC-UHFFFAOYSA-M potassium ethyl xanthate Chemical compound [K+].CCOC([S-])=S JCBJVAJGLKENNC-UHFFFAOYSA-M 0.000 description 12
- 235000010755 mineral Nutrition 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000002516 radical scavenger Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- -1 alkyl acrylamide Chemical compound 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 4
- 229910052683 pyrite Inorganic materials 0.000 description 4
- 239000011028 pyrite Substances 0.000 description 4
- VNFYMAPAENTMMO-UHFFFAOYSA-N 5-chloro-2-methylquinoline Chemical compound ClC1=CC=CC2=NC(C)=CC=C21 VNFYMAPAENTMMO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229940008075 allyl sulfide Drugs 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- URMNHHAUVFEMIG-UHFFFAOYSA-N ethyl 6-methyl-2-oxo-4-phenyl-3,4-dihydro-1h-pyrimidine-5-carboxylate Chemical compound CCOC(=O)C1=C(C)NC(=O)NC1C1=CC=CC=C1 URMNHHAUVFEMIG-UHFFFAOYSA-N 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052952 pyrrhotite Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- QHMZMQCSRXWCON-UHFFFAOYSA-N 2-hydroxyethylsulfanylmethanedithioic acid Chemical compound OCCSC(S)=S QHMZMQCSRXWCON-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- VRWKTAYJTKRVCU-UHFFFAOYSA-N iron(6+);hexacyanide Chemical compound [Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] VRWKTAYJTKRVCU-UHFFFAOYSA-N 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052954 pentlandite Inorganic materials 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012622 synthetic inhibitor Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 1
- 239000012989 trithiocarbonate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 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
- B03D1/016—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to 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
- B03D1/008—Organic compounds containing oxygen
-
- 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
- B03D1/012—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
- B03D2201/06—Depressants
-
- 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
-
- 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
- B03D2203/04—Non-sulfide ores
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
本发明披露了在泡沫浮选矿石过程中抑制硫化物矿石以回收有价矿石的新颖的抑制剂以及在泡沫浮选法中使用该抑制剂的方法。新颖的抑制剂是(甲基)丙烯酰胺、烯丙基硫脲和(甲基)丙烯酸羟基烷基酯的三元共聚物。
Description
本发明的背景
在对矿石进行泡沫浮选中的重要因素之一是提供其中脉石矿含量尽可能低的有价矿浓度(value mineral concentrations)。例如当使用硫化物矿时，将浮选的精矿直接输送去熔炼，不需要附加的加工过程，因此其中的脉石杂质就生成在含硫废产物中并产生对环境有害的SO2大气污染。这个问题是如此的普遍，以致于冶炼工宁愿降低进料中的有价矿的浓度，如果脉石硫化物浓度也降低的话。
现在已经发现某些含有某些官能团组合的合成聚合物是一般从其它有价矿和/或脉石矿中分离有价矿石，尤其是从黄铁矿，磁黄铁矿和其它脉石硫化物中分离某些有价矿的非常有效的抑制剂。这些抑制剂能使送入冶炼厂的矿物精矿砂中的脉石矿杂质明显减少，特别是在硫化物矿精矿的情况下，它们对熔炼操作的环境冲击有积极的影响。本文所用的术语“脉石”可以包括所谓的恶性元素(penaltyelements)如砷和锑，尤其是硫化物。
美国专利4,866,150描述了一种据称是脉石硫化物矿抑制剂的新颖的丙烯酰胺和硫脲的共聚物和三元共聚物，而美国专利4,888,106提出了在有价硫化物矿的精选中使用这些聚合物。
美国专利4,744,893提出了一种使用包含丙烯酰胺、含羟基的单体和丙烯酸或盐的三元共聚物的抑制剂来精选有价硫化物矿的方法。该聚合物本身在美国专利4,902,764中披露过。
本发明的概述
本发明涉及一种新颖的包含丙烯酰胺、硫脲和含羟基的(甲基)丙烯酸酯单体的重复单元的三元共聚物，发现该三元共聚物能很好地精选有价矿，相应地，同时能令人惊奇地很好地除去脉石矿和/或将有价矿互相分开。
对包括较好实例的本发明的描述
按本发明，提供新的且有用的三元共聚物，所述三元共聚物包含下式的重复单元： 
其中各R分别为氢或C1-C4烷基，各R1分别为氢或甲基，R2为氢或C1-C4烷基，各R3分别为氢或C1-C4烷基，R4为氢或C1-C4烷基，各X分别为氢或羟基，但条件是至少一个X为羟基，x是约为60％至约98％的摩尔份数，y是约为1％至约20％的摩尔份数，和z是约为1％至约20％的摩尔份数，该聚合物的分子量约为1000至约2×106。
较好的是，该三元共聚物的分子量约为5，000至约500,000，x是约为70-90％的摩尔份数，y是约为5-15％的摩尔份数，和z是约为5-15％的摩尔份数。
在较好的实例中，上式三元共聚物是那些其中包含丙烯酰胺x单元，烯丙基硫脲y单元和甲基丙烯酸羟乙酯或甲基丙烯酸二羟丙酯z单元的三元共聚物。
这些新颖的三元共聚物可由诸如美国专利3,002,960；3,255,142等已有技术中提出的聚合方法来制备，其内容在此参考引用。更具体地说，它们是这样来制备的，即在约40℃至约100℃，较好约为55℃至约70℃的温度下，在绝热或等温的条件下并在合适的催化剂如过氧化物、偶氮化合物或氧化还原体系存在下，将合适的单体进行共聚合。
更具体地说，本发明的聚合物包含那些来自丙烯酰胺本身，烷基丙烯酰胺如甲基丙烯酰胺等和N-取代的丙烯酰胺和甲基丙烯酰胺如N,N’-二甲基丙烯酰胺等的丙烯酰胺作为(x)单元。
如上定义的聚合物的(y)单元来自硫脲衍生物如烯丙基硫脲，N-烯丙基-N’-甲基硫脲，N-烯丙基-N’-苯甲酰基硫脲，N-烯丙基-N-甲基-N’,N’-二甲基硫脲等。
三元共聚物的(z)单元来自含羟基的单体，包括丙烯酸和甲基丙烯酸的羟烷基酯如丙烯酸羟乙酯，甲基丙烯酸羟乙酯，丙烯酸二羟丙酯，甲基丙烯酸二羟丙酯，丙烯酸羟丁酯，丙烯酸羟戊酯，丙烯酸羟己酯，甲基丙烯酸羟丁酯，甲基丙烯酸羟戊酯，甲基丙烯酸羟己酯，丙烯酸二羟乙酯，甲基丙烯酸二羟乙酯，丙烯酸二羟丁酯，甲基丙烯酸二羟丁酯，丙烯酸二羟戊酯，甲基丙烯酸二羟戊酯，丙烯酸二羟环己酯，甲基丙烯酸二羟己酯等。
该聚合物可以包含少量即小于约5％摩尔份数的其它可共聚合的共聚单体如丙烯酸，或由于三元共聚物的补充反应产生的基团如x单元水解生成的含羧基的基团。
本发明新颖的三元共聚物可用于浮选法中的重要矿物的分离；例如通过抑制铜将它从辉钼矿中分离出来；通过抑制黄铁矿和闪锌矿而分离出铅和铜的硫化物；通过抑制磁黄铁矿而使其与镍黄铁矿分离；通过抑制黄铁矿而与硫化铜或闪锌矿分离，等等。
另一方面，本发明提供一种从矿石中精选有价矿同时选择性地除去脉石矿或者将有价矿相互分开的新颖和改进的方法，所述方法包括：
(a)提供包含所述有价矿和脉石矿的磨细的、达到释放大小(liberation-sized)的矿石颗粒的水性液体浆；
(b)用有效量的脉石抑制剂、有价矿浮选促集剂和起泡剂调理所述液体浆，所述抑制剂包含一聚合物，该聚合物包含：
(ⅰ)下式的x单元：
(ⅱ)下式的y单元：(ⅲ)下式的z单元：
其中各R分别为氢或C1-C4烷基，各R1分别为氢或甲基，R2为氢或C1-C4烷基，各R3分别为氢或C1-C4烷基，R4为氢或C1-C4烷基，各X分别为氢或羟基，但条件是至少一个X为羟基，x是约为60％至约98％的摩尔份数，y是约为1％至约20％的摩尔份数，和z是约为1％至约20％的摩尔份数，该聚合物的分子量约为1,000至约2×106，和
(c)对经调理的液体浆进行泡沫浮选，收集脉石或其它有价矿含量已被降低的有价矿。
较好的是，该三元共聚物的分子量约为5,000至约500,000,x是约为70％至约90％的摩尔份数，y是约为5％至约15％的摩尔份数，和z是约为5％至约15％的摩尔份数。
使用本发明的合成抑制剂经泡沫浮选法来精选有价矿的新颖和改进的方法能提供在等级上明显改进的优异的冶金回收。新颖的矿物抑制剂在大范围的pH值和用量(例如从约0.01磅/吨至约5.0磅/吨)下都是有效的。该抑制剂与购得的多种起泡剂和矿物浮选促集剂都是相容的，并且能容易地加到任何目前的操作系统或设备中。而且，当对硫化物矿使用聚合物矿物抑制剂时，可以通过降低保留在待熔炼的有价硫化物精矿中脉石硫化物矿的量来达到显著地减少从熔炼操作中释放出来的SO2。
再者，其它具有强还原或氧化(在某些矿物体系中)性质的化学品也可以与新颖的聚合物一起使用以达到合适的氧化还原条件。换句话说，任何“表面改性”剂都可以用来调制硫化物表面以提高新颖抑制剂聚合物的吸附。这种试剂的例子包括NaCN,Nokes试剂，巯基乙醇，硫代乙醇酸，氰铁酸和氰亚铁酸的钠盐或钾盐，羟乙基三硫代碳酸盐，和其它的三硫代碳酸盐，过氧化氢，臭氧，空气，氧气，二氧化硫，氰化锌，砷Nokes，巯基丙酸，巯基琥珀酸，其它相关的巯基酸，2-硫尿嘧啶，硫甘油等。可与新颖聚合物一起使用的附加化合物披露于Nagaraj等人的出版物，Trans.IMM，第95卷，1986年3月，pp.C17中。这些表面改性剂与本文中的新颖聚合物之比分别约为0.05-5.0∶1，较好约为0.02-2.0∶1，尽管使用的条件和处理过的矿石可能稍微改变这些量。
本发明较好地涉及选择性地分离硫化物，例如从含铅、铜、锌、银、金等的铜矿、复合硫化物矿等，镍和镍钴矿，金矿和金银矿中分离出脉石硫化物，以便于铜-钼、铜-铅、铅-锌、铜-锌的分离等。
下述实施例仅作举例之用，并且除了所附权利要求书中所述外它们不应被理解为是对本发明的限制。除非另有说明，所有的份数和百分数均以重量计。
实施例1
在装有机械搅拌器、冷凝管和温度计的合适的5颈反应器中加入22.4份溶于1∶1异丙醇/水溶液(7.4份)中的33％N-烯丙基硫脲和140份水。用20％硫酸将混合物的pH值调节到6.0至7.0，随后加入0.32份CuSO4·5H2O。
在搅拌下将混合物加热到55℃。在55℃时，用注射泵以0.11cc/min的速度分别同时各注入20cc 19.4％过硫酸铵和16.9％焦亚硫酸钠.氧化还原催化剂加入后10分钟，以1.7gm/min的速度开始加入8.4份(0.064mol)甲基丙烯酸羟乙酯和159份52％丙烯酰胺(1.16mol)的混合物。在55℃时继续聚合直至以十二烷硫醇/碘滴定达到至少95％的单体转化率(2-4小时)。
用20％NaOH将最终共聚物溶液的pH值调节到6.0-7.0。
实施例2
除了甲基丙烯酸羟乙酯被甲基丙烯酸二羟丙酯代替外，其余均按实施例1的过程。获得类似的结果。
实施例3-7
再按实施例1和2的步骤。制得如下表1所示的组合物。
表Ⅰ
| 实施例 | x单元 | y单元 | z单元 |
| 3 | R1=H各R=H | R2=H各R3=CH3 | R1=HR4=H两个X=OH |
| 4 | R1=H各R=CH3 | R2=H各R3=H | R1=CH3R4=H一个X=OH |
| 5 | R1=CH3各R=H | R2=H各R3=H | R1=HR4=C2H5一个X=OH |
| 6 | R1=H各R=C2H5 | R2=H各R3=H | R1=HR4=H一个X=OH |
| 7 | R1=H各R=H | R2=CH3各R3=CH3 | R1=CH3R4=CH3两个X=OH |
实施例8-10
对北非锌矿(North African zinc ore)进行浮选试验。从矿厂取来浆液样品，在实验室浮选机上进行评价。实验室过程包括如下步骤：1)将硫酸铜溶液加入浮选池中活化锌矿，随后调理1分钟，2)加入浮选促集剂-戊基黄原酸钾(PAX)，调理1分钟，3)在浮选池中加入聚合物抑制剂溶于水中的溶液，随后调理1分钟，和4)充气使可浮选的矿物浮选，并收集浮选产物和尾渣。对浮选精矿和尾渣的分析表明，与不加任何抑制剂的参照试验或用AMD/HEM共聚物的试验相比，用实施例1的聚合物特别是在浮选的粗选池阶段中能改进锌的级别。从矿物学上讲由于某些Zn矿被脉石硫化物矿锁定，因而锌回收率的略微损失是不可避免的。
表Ⅱ
| 实施例号 | 浮选促集剂 | 抑制剂 | pH | 锌的回收率 | 锌的级别 | ||||
| 类型 | 用量，份数/吨 | 类型 | 用量，份数/吨 | 粗选池 | 粗选池+选池 | 粗选池 | 粗选池+选池 | ||
| 8C | PAX | 112 | 无 | -- | 10.8 | 66.8 | 99.1 | 42.2 | 19.1 |
| 9C | PAX | 109 | AMD/HEM | 334 | 10.4 | 83.0 | 99.1 | 39.7 | 21.1 |
| 10 | PAX | 115 | AMD/HEM/ATU | 353 | 10.5 | 69.7 | 96.7 | 48.2 | 23.0 |
C=对比例
AMD/HEM=丙烯酰胺/甲基丙烯酸羟乙酯共聚物(90/10)；重均分子量=10K
AMD/HEM/ATU=丙烯酰胺/甲基丙烯酸羟乙酯/烯丙基硫脲三元共聚物(90/5/5)；重均分子量=5K
实施例11-14
对于来自如实施例8-10同样矿厂的另一个浆液样品，将实施例1的聚合物与丙烯酰胺和烯丙基硫脲的共聚物以及丙烯酰胺和甲基丙烯酸二羟丙酯的共聚物进行比较。与对照物或甲基丙烯酸二羟丙酯共聚物或烯丙基硫脲共聚物相比，实施例1的聚合物在粗选池阶段就能获得明显较好的锌级别。实际上，用实施例1聚合物获得的锌粗选池精矿已有足够高的级别(53％)，而不需要再经过清洗的路线，直接可报告为最终的有价矿。这样，初始进料中有64％的锌可以不需要清洗循环。这是一个重要的省工优点。同样值得注意的是用实施例1聚合物时所用的pH值为10.5，而在不存在聚合物抑制剂的情况下为获得高精矿级别一般来说pH值为12.3是必需的。这样，使用实施例1的聚合物就能显著地节约费用。
表Ⅲ
| 实施例号 | 浮选促集剂 | 抑制剂 | pH | 锌的回收率 | 锌的级别 | ||||
| 类型 | 用量，份数/吨 | 类型 | 用量，份数/吨 | 粗选池 | 粗选池+选池 | 粗选池 | 粗选池+选池 | ||
| 11C | PAX | 87 | 无 | -- | 12.3 | 72.0 | 99.0 | 45.7 | 36.7 |
| 12C | PAX | 87 | AMD/ATU | 269 | 10.5 | 63.3 | 94.8 | 50.4 | 43.7 |
| 13C | PAX | 82 | AMD/DHPM | 253 | 10.5 | 70.8 | 97.8 | 44.7 | 32.7 |
| 14 | PAX | 88 | AMD/HEM/ATU | 271 | 10.5 | 64.3 | 91.3 | 53.0 | 43.8 |
C=对比例
AMD/ATU=丙烯酰胺/烯丙基硫脲共聚物(90/10)；重均分子量=5K
AMD/DHPM=丙烯酰胺/甲基丙烯酸二羟丙酯共聚物(90/10)；重均分子量=10K
AMD/HEM/ATU=丙烯酰胺/甲基丙烯酸羟乙酯/烯丙基硫脲三元共聚物(90/5/5)；重均分子量=5K
实施例15-17
对于来自如实施例8-10的同样北非矿的第三个浆液样品，将实施例1的聚合物与对照物和丙烯酰胺/甲基丙烯酸羟乙酯共聚物相比较。特别是在粗选池浮选阶段，获得了锌回收率仅有一个小损失的明显较好的锌级别。同样地，粗选池锌精矿的级别已足够高至可以不需要再经过清洗机的路线就可用作最终的产物，这对运行的矿厂来说是一个重要的优点。由于一些锌矿被硫化铁锁定，因而锌回收率有小的损失是不可避免的。
表Ⅲ
| 实施例号 | 浮选促集剂 | 抑制剂 | pH | 锌的回收率 | 锌的级别 | ||||
| 类型 | 用量，份数/吨 | 类型 | 用量，份数/吨 | 粗选池 | 粗选池+选池 | 粗选池 | 粗选池+选池 | ||
| 15C | PAX | 134 | 无 | -- | 12.3 | 60.7 | 99.1 | 47.2 | 26.6 |
| 16C | PAX | 148 | AMD/ATU | 455 | 10.5 | 68.0 | 95.4 | 47.0 | 33.5 |
| 17 | PAX | 122 | AMD/HEM/ATU | 377 | 10.5 | 62.8 | 94.4 | 53.1 | 29.0 |
C=对比例
AMD/ATU=丙烯酰胺/烯丙基硫脲共聚物(90/10)；重均分子量=5K
AMD/HEM/ATU=丙烯酰胺/甲基丙烯酸羟乙酯/烯丙基硫脲三元共聚物(90/5/5)；重均分子量=5K
实施例18-22
分别用实施例3-7的聚合物替代其中所用的聚合物，按实施例10的步骤。获得类似的结果。
在某些情况下，需要硫化物矿的抑制剂以将它们从硫化物矿石或非硫化物矿石中的非硫化物矿中分离出来。这些分离的一些例子为：从煤中除去脉石硫化物矿如黄铁矿；从有价氧化物型矿如锡石中从除去脉石硫化物；通过抑制硫化物矿并浮选非硫化物矿从脉石非硫化物矿如硅石、硅酸盐、碳酸盐等中回收有价硫化物矿如那些基底金属的硫化物。
实施例23
在精选煤过程中评价实施例1的聚合物作为除去硫化铁例如黄铁矿的抑制剂。对硫化物可以达到选择性的抑制。
实施例24
同样评价实施例1的聚合物作为大部分有价硫化物如那些铜、镍和铁的硫化物的抑制剂，并随后浮选分离脉石非硫化物矿如硅石和硅酸盐。达到了对大多数硫化物的抑制，并且使用脂肪酸或胺浮选促集剂浮选掉脉石非硫化物。
实施例25
同样评价实施例1的聚合物作为浮选分离有价锡矿如锡石过程中锡矿中的脉石硫化物的抑制剂。同样达到了对大多数硫化物的抑制，同时使用磺酸盐或磺基琥珀酸盐浮选促集剂来浮选有价非硫化物矿锡石。
本发明的聚合物也可用于其它的分离，包括抑制多种类型硫化物和非硫化物矿石中的硫化物矿。
Claims (6)
1．一种聚合物组合物，它包含下式重复单元：
其中各R分别为氢或C1-C4烷基，各R1分别为氢或甲基，R2为氢或C1-C4烷基，各R3分别为氢或C1-C4烷基，R4为氢或C1-C4烷基，各X分别为氢或羟基，但条件是至少一个X为羟基，x是约为60％至约98％的摩尔份数，y是约为1％至约20％的摩尔份数，和z是约为1％至约20％的摩尔份数，该聚合物的分子量约为1,000至约2×106。
2．如权利要求1所述的聚合物，其中x单元是丙烯酰胺单元，y单元是烯丙基硫脲单元和z单元是甲基丙烯酸羟乙酯或甲基丙烯酸二羟丙酯单元。
3．如权利要求1所述的聚合物，其中各R为氢，各R1为氢，R2为氢，各R3为氢，R4为甲基以及各X为羟基。
4．一种方法，它包括经下述步骤从矿石中精选有价矿石同时选择性地除去脉石或其它有价矿石：
a)提供包含所述有价矿石和所述脉石矿石的磨细的、达到释放大小的矿石颗粒的水性液体浆；
b)分别用有效量的脉石抑制剂、有价矿石浮选促集剂和起泡剂调理所述液体浆，所述抑制剂包含一聚合物，该聚合物包含下式重复单元： 
其中各R分别为氢或C1-C4烷基，各R1分别为氢或甲基，R2为氢或C1-C4烷基，各R3分别为氢或C1-C4烷基，R4为氢或C1-C4烷基，各X分别为氢或羟基，但条件是至少一个X为羟基，x是约为60％至约98％的摩尔份数，y是约为1％至约20％的摩尔份数，和z是约为1％至约20％的摩尔份数，该聚合物的分子量约为1,000至约2×106，和
c)对经调理的液体浆进行泡沫浮选，收集脉石或其它有价矿含量被降低后的有价矿。
5．如权利要求4所述的方法，其中x单元是丙烯酰胺单元，y单元是烯丙基硫脲单元和z单元是甲基丙烯酸羟乙酯或甲基丙烯酸二羟丙酯单元。
6．如权利要求4所述的方法，其中各R、各R1、R2和各R3为氢，R4为甲基以及各X为羟基。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/625,263 | 1996-03-28 | ||
| US08/625,263 US5756622A (en) | 1996-03-28 | 1996-03-28 | Polymeric sulfide mineral depressants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1214704A true CN1214704A (zh) | 1999-04-21 |
| CN1103343C CN1103343C (zh) | 2003-03-19 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97193365A Expired - Fee Related CN1103343C (zh) | 1996-03-28 | 1997-03-26 | 用于精选有价矿的三元共聚物和使用它的方法 |
Country Status (20)
| Country | Link |
|---|---|
| US (2) | US5756622A (zh) |
| EP (1) | EP0889917B1 (zh) |
| CN (1) | CN1103343C (zh) |
| AR (1) | AR006426A1 (zh) |
| AU (1) | AU705721B2 (zh) |
| BG (1) | BG63311B1 (zh) |
| BR (1) | BR9708350A (zh) |
| CA (1) | CA2250055C (zh) |
| ES (1) | ES2152667T3 (zh) |
| GR (1) | GR3034826T3 (zh) |
| ID (1) | ID19553A (zh) |
| IN (1) | IN191595B (zh) |
| MY (1) | MY118127A (zh) |
| OA (1) | OA10887A (zh) |
| PE (1) | PE6498A1 (zh) |
| PL (1) | PL186880B1 (zh) |
| PT (1) | PT889917E (zh) |
| RU (1) | RU2175331C2 (zh) |
| WO (1) | WO1997035897A1 (zh) |
| ZA (1) | ZA972720B (zh) |
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| CN101244404A (zh) * | 2008-03-21 | 2008-08-20 | 北京矿冶研究总院 | 钼铋矿物的分离方法 |
| CN101337206B (zh) * | 2008-08-13 | 2011-02-02 | 中南大学 | 硫化矿浮选捕收剂及二酰基双硫脲应用方法和制备方法 |
| CN105834008A (zh) * | 2016-06-08 | 2016-08-10 | 江西元再生资源有限公司 | 一种铜尾矿中含砷硫化矿物抑制剂的制备方法 |
| CN106478877A (zh) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | 一种共聚物及其制备方法与应用 |
| CN107427842A (zh) * | 2014-12-23 | 2017-12-01 | 凯米罗总公司 | 用于矿石选矿的选择性絮凝剂 |
| CN107427841A (zh) * | 2014-12-30 | 2017-12-01 | 凯米罗总公司 | 矿石浮选的抑制剂 |
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| CN103788294B (zh) * | 2012-10-30 | 2016-03-30 | 中国石油化工股份有限公司 | 一种丙烯酰胺共聚物及其制备方法和应用 |
| US10654048B2 (en) | 2017-03-09 | 2020-05-19 | Chevron Phillips Chemical Company Lp | Recovery of molybdenum using sodium metabisulfite and a thiocarbonate depressant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4744893A (en) * | 1985-08-28 | 1988-05-17 | American Cyanamid Company | Polymeric sulfide mineral depressants |
| US4902764A (en) * | 1985-08-28 | 1990-02-20 | American Cyanamid Company | Polymeric sulfide mineral depressants |
| US4866150A (en) * | 1988-04-18 | 1989-09-12 | American Cyanamid Company | Polymeric sulfide mineral depressants |
| US4888106A (en) * | 1988-04-18 | 1989-12-19 | American Cyanamid Company | Method of using polymeric sulfide mineral depressants |
-
1996
- 1996-03-28 US US08/625,263 patent/US5756622A/en not_active Expired - Lifetime
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1997
- 1997-02-12 PE PE1997000088A patent/PE6498A1/es not_active IP Right Cessation
- 1997-02-24 MY MYPI97000697A patent/MY118127A/en unknown
- 1997-03-20 IN IN504CA1997 patent/IN191595B/en unknown
- 1997-03-26 AU AU27249/97A patent/AU705721B2/en not_active Ceased
- 1997-03-26 EP EP97921123A patent/EP0889917B1/en not_active Expired - Lifetime
- 1997-03-26 PL PL97328965A patent/PL186880B1/pl not_active IP Right Cessation
- 1997-03-26 RU RU98119541/04A patent/RU2175331C2/ru not_active IP Right Cessation
- 1997-03-26 BR BR9708350A patent/BR9708350A/pt not_active IP Right Cessation
- 1997-03-26 CN CN97193365A patent/CN1103343C/zh not_active Expired - Fee Related
- 1997-03-26 AR ARP970101242A patent/AR006426A1/es unknown
- 1997-03-26 CA CA002250055A patent/CA2250055C/en not_active Expired - Fee Related
- 1997-03-26 ES ES97921123T patent/ES2152667T3/es not_active Expired - Lifetime
- 1997-03-26 PT PT97921123T patent/PT889917E/pt unknown
- 1997-03-26 WO PCT/US1997/005825 patent/WO1997035897A1/en active IP Right Grant
- 1997-03-27 ID IDP971043A patent/ID19553A/id unknown
- 1997-03-27 ZA ZA9702720A patent/ZA972720B/xx unknown
- 1997-12-11 US US08/989,062 patent/US5959054A/en not_active Expired - Lifetime
-
1998
- 1998-09-02 BG BG102747A patent/BG63311B1/bg unknown
- 1998-09-28 OA OA9800181A patent/OA10887A/en unknown
-
2000
- 2000-11-10 GR GR20000402513T patent/GR3034826T3/el not_active IP Right Cessation
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| CN107427841A (zh) * | 2014-12-30 | 2017-12-01 | 凯米罗总公司 | 矿石浮选的抑制剂 |
| CN106478877B (zh) * | 2015-08-31 | 2018-08-17 | 中国石油化工股份有限公司 | 一种共聚物及其制备方法与应用 |
| CN106478877A (zh) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | 一种共聚物及其制备方法与应用 |
| CN105834008A (zh) * | 2016-06-08 | 2016-08-10 | 江西元再生资源有限公司 | 一种铜尾矿中含砷硫化矿物抑制剂的制备方法 |
| CN110035829A (zh) * | 2016-10-07 | 2019-07-19 | 塞特工业公司 | 抑制剂组合物及用于在硫化物矿石的浮选期间抑制脉石硫化物矿物的方法 |
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| CN115921119A (zh) * | 2022-11-29 | 2023-04-07 | 昆明理工大学 | 一种铜钼矿浮选分离抑制剂及应用 |
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Also Published As
| Publication number | Publication date |
|---|---|
| US5756622A (en) | 1998-05-26 |
| US5959054A (en) | 1999-09-28 |
| PL328965A1 (en) | 1999-03-01 |
| EP0889917A1 (en) | 1999-01-13 |
| PE6498A1 (es) | 1998-03-04 |
| BG63311B1 (bg) | 2001-09-28 |
| BR9708350A (pt) | 1999-08-03 |
| GR3034826T3 (en) | 2001-02-28 |
| AU2724997A (en) | 1997-10-17 |
| WO1997035897A1 (en) | 1997-10-02 |
| PL186880B1 (pl) | 2004-03-31 |
| AU705721B2 (en) | 1999-05-27 |
| OA10887A (en) | 2003-02-18 |
| RU2175331C2 (ru) | 2001-10-27 |
| AR006426A1 (es) | 1999-08-25 |
| BG102747A (en) | 1999-05-31 |
| ID19553A (id) | 1998-07-23 |
| IN191595B (zh) | 2003-12-06 |
| ES2152667T3 (es) | 2001-02-01 |
| MY118127A (en) | 2004-09-30 |
| CA2250055C (en) | 2006-01-31 |
| ZA972720B (en) | 1997-10-23 |
| EP0889917B1 (en) | 2000-11-02 |
| CN1103343C (zh) | 2003-03-19 |
| CA2250055A1 (en) | 1997-10-02 |
| PT889917E (pt) | 2001-04-30 |
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