CN1305577C - 用于硫化物矿石的收集剂 - Google Patents
用于硫化物矿石的收集剂 Download PDFInfo
- Publication number
- CN1305577C CN1305577C CNB038154137A CN03815413A CN1305577C CN 1305577 C CN1305577 C CN 1305577C CN B038154137 A CNB038154137 A CN B038154137A CN 03815413 A CN03815413 A CN 03815413A CN 1305577 C CN1305577 C CN 1305577C
- Authority
- CN
- China
- Prior art keywords
- carbon atom
- contain
- alkyl
- flotation
- reagent
- 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 - Fee Related
Links
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 29
- 238000005188 flotation Methods 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical group [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910000340 lead(II) sulfide Inorganic materials 0.000 claims 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 claims 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims 1
- 229910052984 zinc sulfide Inorganic materials 0.000 claims 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- -1 diisobutyl ester Chemical class 0.000 description 15
- 239000010949 copper Substances 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000006315 carbonylation Effects 0.000 description 6
- 238000005810 carbonylation reaction Methods 0.000 description 6
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- NAGJZTKCGNOGPW-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [O-]P([O-])([S-])=S NAGJZTKCGNOGPW-UHFFFAOYSA-K 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 2
- 229960002218 sodium chlorite Drugs 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BMMMYFMIMMLCOD-UHFFFAOYSA-N [Na].CC(C)COP(S)(=S)OCC(C)C Chemical compound [Na].CC(C)COP(S)(=S)OCC(C)C BMMMYFMIMMLCOD-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SYFIMIPHNTZHIN-UHFFFAOYSA-N bis(2-methylpropoxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical group CC(C)COP(S)(=S)OCC(C)C SYFIMIPHNTZHIN-UHFFFAOYSA-N 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- YJNALOLHXQQOIK-UHFFFAOYSA-N di(butan-2-yloxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCC(C)OP(S)(=S)OC(C)CC YJNALOLHXQQOIK-UHFFFAOYSA-N 0.000 description 1
- SZXCCXFNQHQRGF-UHFFFAOYSA-N di(propan-2-yloxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CC(C)OP(S)(=S)OC(C)C SZXCCXFNQHQRGF-UHFFFAOYSA-N 0.000 description 1
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- RPOLJNCRBSMWRU-UHFFFAOYSA-N dipentoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCOP(S)(=S)OCCCCC RPOLJNCRBSMWRU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 150000003947 ethylamines Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011297 pine tar Substances 0.000 description 1
- 229940068124 pine tar Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
-
- 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
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/014—Organic compounds containing phosphorus
-
- 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本发明涉及一种用于硫化物矿石浮选的试剂，该试剂包含至少一种通式(I)的化合物，其中R1、R2和R3彼此独立地是含有1-18个碳原子的烷基、含有2-18个碳原子的烯基、含有6-10个碳原子的芳基或含有7-10个碳原子的烷芳基，以及该试剂的制备方法。
Description
技术领域
本发明涉及烷基酰氨基硫代磷酸二烷基酯在浮选硫化物矿石中的用途，和涉及其制备方法。
背景技术
在通过浮选的硫化物矿石和铜/钼矿石生产中，在商业上使用各种收集剂类型，如二硫代磷酸酯、黄原酸酯、黄原酸甲酸酯和硫羰氨基甲酸酯(Schubert：Aufbereitung fester mineralischer Rohstoffe[固体矿物质原材料的选矿]，卷II，1977，pp.296及以下)及其与起沫剂结合的混合物。浮选工艺从脉石矿物质中分离出铜和钼硫化物。
收集剂引起有价值矿物质表面的润湿，它导致颗粒变成疏水性的。通过向含水浮选矿浆中注入空气，产生空气泡，已经变成疏水性的矿石颗粒对该空气泡具有高亲合力和由空气泡排出到浮选矿浆的表面，同时脉石矿物质保留在矿浆中。商业上的常规起沫剂包括例如醇、丙二醇及其醚和MIBC(甲基异丁基甲醇)。
US-4699711公开了优选地使用短链烷基取代的硫羰氨基甲酸酯的硫化物矿物质的浮选方法。
WO02/38277公开了硫羰氨基甲酸酯和巯基苯并噻唑的混合物作为硫化物矿石特别是与钼和金缔合的铜矿石的浮选收集剂的用途。
Klee，F.C.，Kirch，E.R.，J.Pharm.Sci.，51，1962，423-427公开了在加入钠或钾金属的情况下，通过在无水乙醚中PCl2SN(C2H4)与NaOiBu的反应而制备烷基酰氨基硫代磷酸二烷基酯的方法。
发明内容
本发明的目的是发现用于硫化物型铜和铜/钼矿石的改进收集剂类型，该收集剂具有比现有技术的收集剂更好的浮选结果。
发现对于相同的铜/钼含量，烷基酰氨基硫代磷酸二烷基酯，特别地乙基酰氨基硫代磷酸二异丁基酯导致显著更高的回收率。本发明的目的另外是发现制备烷基酰氨基硫代磷酸二烷基酯的改进方法。它应当特别从更容易得到的原料开始，并且不采用无水溶剂和不采用碱金属也能获得成功。
本发明因此涉及一种用于硫化物矿石浮选的试剂，该试剂包含至少一种如下通式的化合物：
其中
R1、R2和R3彼此独立地是含有1-18个碳原子的烷基、含有2-18个碳原子的烯基、含有6-10个碳原子的芳基或含有7-10个碳原子的烷芳基，和
R4是氢或含有1-18个碳原子的烷基、含有2-18个碳原子的烯基、含有6-10个碳原子的芳基或含有7-10个碳原子的烷芳基。
本发明进一步涉及一种制备如下通式的化合物的方法：
其中
R1、R2和R3彼此独立地是含有1-18个碳原子的烷基、含有2-18个碳原子的烯基、含有6-10个碳原子的芳基或含有7-10个碳原子的烷芳基，和
R4是氢或含有1-18个碳原子的烷基、含有2-18个碳原子的烯基、含有6-10个碳原子的芳基或含有7-10个碳原子的烷芳基，该方法包括
a)在酸性溶液中将通式(R1O)(R2O)PS2Me的二硫代磷酸酯与氧化剂反应，其中Me是阳离子，然后
b)将如此得到的产物与通式HNR3R4的胺反应。
本发明进一步涉及本发明的浮选试剂用于硫化物矿石浮选的用途。硫化物矿石优选是含铜矿石。
本发明进一步涉及通过将本发明的浮选试剂与硫化物矿石接触而浮选硫化物矿石的方法。
采用本发明的浮选试剂，在非铁金属硫化物浮选中，与标准收集剂相比，可以达到选择性和收率的改进结果。
优选地，R1、R2、R3和R4彼此独立地是含有1-10个碳原子的烷基或烯基。例如，R1、R2和R3彼此独立地是C2-C4烷基。特别优选地，R1、R2是丁基，特别是异丁基。R3特别是乙基。R4特别是氢。
Me优选是碱金属、碱土金属、铵离子或氢离子，特别是Na或K。
可以考虑使用能够氧化二硫代磷酸酯的任何物质作为氧化剂，例如亚氯酸盐、例如亚氯酸钠、次氯酸盐或氯酸盐。
可以考虑使用在水溶液中释放氢离子的任何化合物作为酸。优选为无机酸，例如硫酸、硝酸、磷酸或盐酸。如果合适，酸可以是同时用作氧化剂的氧化性酸。
优选的二硫代磷酸酯是二硫代磷酸二异丁酯、二硫代磷酸二乙酯、二硫代磷酸二异丙酯、二硫代磷酸二仲丁酯和二硫代磷酸二戊酯。
浮选可以应用于所有的金属硫化物(Fe除外)，其中特别优选是Cu、Mo、Pb、Zn、和Ni。在Cu和Mo的选矿中观察到特别好的结果。本发明的浮选试剂可用于宽pH范围(2-12)，和以优选0.001-1.0kg/吨粗矿石的浓度加入到含水矿浆中。
与现有技术的黄原酸甲酸酯和硫羰氨基甲酸酯相比，本发明的浮选试剂达到回收率和选择性的显著改进。实施例1、3和5清楚地显示出铜和钼的回收率比采用相应标准试剂高。要强调实施例3，其中比采用相应数量的乙基异丙基硫羰氨基甲酸酯{实施例4(V)}达到显著高4.8和7.1％的77.3％铜回收率和69.5％钼回收率，其中铜或钼含量保持在相同的水平上。
具体实施方式
实施例
A)乙基酰氨基硫代磷酸二异丁酯的制备：
阶段1(氧化)：
R＝C4H9-异丁基
阶段2酰胺化：
2a)
2b)
为制备乙基酰氨基硫代磷酸二异丁酯，1670g(3.17mol)的二异丁基二硫代磷酸钠50％水溶液与725g的22％亚氯酸钠溶液(1.76mol)均质化5分钟。采用恒定搅拌在2-3小时内缓慢加入346g的5O％硫酸，其中反应混合物的温度保持在40-50℃。将混合物搅拌进一步30分钟，然后将反应混合物冷却到30-40℃。
在相分离之后，将有机相(大约778g)滗析，和与250g的70％乙胺溶液反应，在大约2-3小时内缓慢加入该乙胺溶液。通过冷却将温度保持在40-60℃(放热反应)。然后将反应混合物在70-80℃下回流加热大约3小时。
将反应混合物在搅拌下冷却到40-50℃，并加入441g二甘醇。在又30分钟之后，将混合物冷却到20-25℃。使用95g水将反应产物的浓度调整至所需的活性成分含量。
在过滤之后，获得1551g透明微红色油状的产物溶液。
B)作为收集剂的作用
使用如下收集剂/起沫剂联合物：
表1：收集剂/起沫剂联合物
| 实施例No. | 组成 |
| 1 | 收集剂：乙基酰氨基硫代磷酸二异丁酯(27g/t)起沫剂：羰基化残余物(oxo residue)/聚丙二醇甲基醚，Mw＝400g/mol(5∶1，15g/t) |
| 2(对照) | 收集剂：乙基异丙基黄原酸甲酸酯(27g/t)起沫剂：羰基化残余物/聚丙二醇甲基醚，Mw＝400g/mol(5∶1，15g/t) |
| 3 | 收集剂：乙基酰氨基硫代磷酸二异丁酯(6g/t)起沫剂：羰基化残余物/聚丙二醇，Mw＝425g/mol(20g/t) |
| 4(对照) | 收集剂：乙基异丙基硫羰氨基甲酸酯(6g/t)起沫剂：丙二醇甲基醚，Mw＝250g/mol/MIBC(1∶1，28g/t) |
| 5 | 收集剂：乙基酰氨基硫代磷酸二异丁酯(33g/t)起沫剂：羰基化残余物/聚丙二醇，Mw＝425g/mol(40g/t) |
| 6(对照) | 收集剂：乙基异丙基黄原酸甲酸酯(33g/t)起沫剂：羰基化残余物/松油(6∶4，40g/t) |
此处羰基化残余物大致具有如下组成：
组分 浓度范围(wt％)
二-2-乙基己基醚 10-25
2-乙基己酸2-乙基己酯 10-25
C16内酯 4-20
丁酸2-乙基己酯 3-10
2-乙基己烷-1，3-二醇单正丁酸酯 5-15
2-乙基己醇 4-10
C4-C8-缩醛 2-10
2-乙基己烷-1，3-二醇 2-5
醚和酯≥C20 0-20
表2：浮选试验的结果
| 给料 | 浓缩物 | |||||
| 实施例No. | Cu含量(％) | Mo含量(％) | Cu含量(％) | Mo含量(％) | 回收率(％) | 回收率(％) |
| 1 | 1.13 | 0.03 | 11.4 | 0.25 | 92.1 | 80.3 |
| 2(对照) | 11.5 | 0.23 | 91.2 | 76.9 | ||
| 3 | 0.62 | 0.017 | 4.1 | 0.14 | 77.3 | 69.5 |
| 4(对照) | 4.3 | 0.15 | 72.5 | 62.4 | ||
| 5 | 0.83 | - | 10.3 | - | 89.2 | - |
| 6(对照) | 10.2 | - | 86.7 | - | ||
Claims (9)
1.一种试剂用于硫化物矿石浮选的试剂，其试剂包含至少一种如下通式的化合物：
其中
R1，R2和R3彼此独立地是含有1-18个碳原子的烷基、含有2-18个碳原子的烯基、含有6-10个碳原子的芳基、或含有7-10个碳原子的烷芳基，和
R4是氢或含有1-18个碳原子的烷基、含有2-18个碳原子的烯基、含有6-10个碳原子的芳基或含有7-10个碳原子的烷芳基。
2.权利要求1的浮选试剂的用途，其中R1、R2和R3彼此独立地是C2-C4烷基。
3.权利要求1或2的浮选试剂的用途，在2-12的pH范围中的用途。
4.权利要求1或2的浮选试剂的用途，以每吨粗矿石0.001-1.0kg的数量的用途。
5.权利要求1或2的浮选试剂在不含铁硫化物矿石浮选中的用途，其中硫化物矿石是铜硫化物、镍硫化物、锌硫化物、铅硫化物或钼硫化物。
6.一种制备如下通式的化合物的方法：
其中
R1、R2和R3彼此独立地是含有1-18个碳原子的烷基、含有2-18个碳原子的烯基、含有6-10个碳原子的芳基或含有7-10个碳原子的烷芳基，和
R4是氢或含有1-18个碳原子的烷基、含有2-18个碳原子的烯基、含有6-10个碳原子的芳基或含有7-10个碳原子的烷芳基，该方法包括
a)在酸性溶液中将通式(R1O)(R2O)PS2Me的二硫代磷酸盐与氧化剂反应，其中Me是阳离子，然后
b)将得到的产物与通式HNR3R4的胺反应。
7.权利要求6的方法，其中R1、R2和R3彼此独立地是C2-C4烷基。
8.权利要求7的方法，其中R1和R2是丁基，R3是乙基和R4是氢。
9.权利要求8的方法，其中R1和R2是异丁基。
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10235574.6 | 2002-08-03 | ||
| DE10235574A DE10235574C1 (de) | 2002-08-03 | 2002-08-03 | Sammler für sulfidische Erze |
| DE10252451A DE10252451A1 (de) | 2002-11-12 | 2002-11-12 | Verfahren zur Herstellung von Alkylamidothiophosphorsäuredialkylestern |
| DE10252451.3 | 2002-11-12 | ||
| PCT/EP2003/007966 WO2004014562A2 (de) | 2002-08-03 | 2003-07-22 | Sammler für sulfidische erze |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1665598A CN1665598A (zh) | 2005-09-07 |
| CN1305577C true CN1305577C (zh) | 2007-03-21 |
Family
ID=31716598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038154137A Expired - Fee Related CN1305577C (zh) | 2002-08-03 | 2003-07-22 | 用于硫化物矿石的收集剂 |
Country Status (16)
| Country | Link |
|---|---|
| US (2) | US7104404B2 (zh) |
| EP (1) | EP1528957B1 (zh) |
| CN (1) | CN1305577C (zh) |
| AT (1) | ATE311256T1 (zh) |
| AU (1) | AU2003254558B2 (zh) |
| BR (2) | BR0312359B1 (zh) |
| CA (1) | CA2494619C (zh) |
| CL (1) | CL2008000584A1 (zh) |
| DE (1) | DE50301822D1 (zh) |
| ES (1) | ES2250920T3 (zh) |
| MX (1) | MXPA05001344A (zh) |
| PE (2) | PE20081058A1 (zh) |
| PL (1) | PL203935B1 (zh) |
| RU (1) | RU2312712C2 (zh) |
| WO (1) | WO2004014562A2 (zh) |
| ZA (1) | ZA200409677B (zh) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1845097A1 (en) * | 2006-04-10 | 2007-10-17 | Portela & Ca., S.A. | Oxadiazole derivatives as COMT inhibitors |
| US20090266746A1 (en) * | 2008-04-29 | 2009-10-29 | David Henry Behr | Mineral ore flotation aid |
| DE102009010293A1 (de) * | 2009-02-24 | 2010-09-02 | Clariant International Ltd. | Sammler für Verfahren zur Flotation unlöslischer Bestandteile von Kalirohsalzen |
| DE102009010294A1 (de) * | 2009-02-24 | 2010-09-02 | Clariant International Limited | Sammler für Verfahren zur Flotation unlöslischer Bestandteile von Kalirohsalzen |
| CN101549326B (zh) * | 2009-05-15 | 2012-07-04 | 江西理工大学 | 一种难选铜锌硫化矿浮选分离的工艺 |
| US8413816B2 (en) * | 2010-02-16 | 2013-04-09 | Nalco Company | Sulfide flotation aid |
| US8955685B2 (en) | 2010-12-30 | 2015-02-17 | Nalco Company | Glycerides and fatty acid mixtures and methods of using same |
| CN102580859B (zh) * | 2011-01-07 | 2014-02-12 | 四川省地质矿产勘查开发局成都综合岩矿测试中心 | 磷矿正反浮选捕收剂 |
| CN103386366B (zh) * | 2012-05-08 | 2017-08-04 | 上海喜若飞精细化工有限公司 | 一种磷酯化选矿捕收剂的制备方法 |
| CN102806148A (zh) * | 2012-09-07 | 2012-12-05 | 西北矿冶研究院 | 一种高硫铜矿捕收剂 |
| US9446416B2 (en) * | 2012-11-28 | 2016-09-20 | Ecolab Usa Inc. | Composition and method for improvement in froth flotation |
| US9149814B2 (en) | 2013-03-13 | 2015-10-06 | Ecolab Usa Inc. | Composition and method for improvement in froth flotation |
| US9440242B2 (en) * | 2013-10-01 | 2016-09-13 | Ecolab Usa Inc. | Frothers for mineral flotation |
| US9266120B2 (en) * | 2013-10-01 | 2016-02-23 | Ecolab Usa Inc | Collectors for mineral flotation |
| PE20211337A1 (es) | 2014-01-31 | 2021-07-26 | Goldcorp Inc | Proceso para la separacion y recuperacion de sulfuros de metales de una mena o concentrado de sulfuros mixtos |
| CN105418673B (zh) * | 2015-11-25 | 2017-07-07 | 昆明冶金研究院 | 一种氧化锌高效捕收剂的制备方法 |
| WO2019113142A1 (en) | 2017-12-06 | 2019-06-13 | Dow Global Technologies Llc | Flotation separation aid useful for collection of mineral ore fines |
| CN108296028B (zh) * | 2018-01-29 | 2020-07-07 | 中南大学 | 一种硫代羰基酰胺捕收剂及其制备方法与应用 |
| CN114618686B (zh) * | 2022-02-16 | 2024-06-18 | 武汉工程大学 | 一种正丁基硫代磷酸三胺的应用及微细粒辉钼矿的浮选方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3629269A1 (de) * | 1986-08-28 | 1988-03-10 | Hoechst Ag | Verfahren zur herstellung von o-alkyl-amido-thiophosphorsaeure-salzen |
| US4822483A (en) * | 1984-09-13 | 1989-04-18 | The Dow Chemical Company | Collector compositions for the froth flotation of mineral values |
| DE4040475A1 (de) * | 1989-12-23 | 1991-07-04 | Hoechst Ag | Neue dithiophosphorsaeureester und deren verwendung zur faellung und flotation von schwermetallen aus abwaessern |
| CN1063627A (zh) * | 1991-02-02 | 1992-08-19 | 中南工业大学 | 用α-亚硝基膦酸酯作硫化矿捕收剂 |
| CN1294032A (zh) * | 1999-10-29 | 2001-05-09 | 沈阳矿冶研究所 | 贵金属和有色金属硫化矿复合浮选药剂 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1783206A (en) * | 1928-06-21 | 1930-12-02 | George H Wigton | Concentration of ores |
| US1783207A (en) * | 1929-07-03 | 1930-12-02 | George H Wigton | Concentration of ores |
| US2134706A (en) * | 1931-02-24 | 1938-11-01 | Peter C Reilly | Process of flotation and agent therefor |
| US1902839A (en) * | 1931-08-03 | 1933-03-28 | Peter C Reilly | Process of froth flotation and material employed to effect the same |
| US1974885A (en) * | 1932-01-21 | 1934-09-25 | George H Wigton | Froth flotation of oxidized ores |
| US2621789A (en) * | 1950-10-04 | 1952-12-16 | American Cyanamid Co | Froth flotation of sulfide minerals with di-alkyl thiophosphoryl chlorides |
| US4699711A (en) * | 1983-07-25 | 1987-10-13 | Dow Chemical Company | Novel O,O'-, O,S'- or S,S'-dithiodialkylene-bis(mono- or dihydrocarbyl carbamothioates) and S,S'-dithiodialkylene-bis(mono- or dihydrocarbyl carbamodithioates) useful as froth flotation collectors |
| US4699712A (en) * | 1984-06-20 | 1987-10-13 | Thiotech, Inc. | Ore dressing method |
| GB2267851B (en) | 1992-06-09 | 1995-12-13 | American Cyanamid Co | Improved metal recovery by flotation |
| DE10055126C1 (de) * | 2000-11-07 | 2002-05-23 | Clariant Internat Ltd Muttenz | Sammler für die Aufbereitung von Nicht-Eisen-Metallsulfiden und seine Verwendung |
-
2003
- 2003-06-06 PE PE2008000931A patent/PE20081058A1/es not_active Application Discontinuation
- 2003-06-06 PE PE2003000569A patent/PE20040142A1/es not_active Application Discontinuation
- 2003-07-22 AT AT03784037T patent/ATE311256T1/de not_active IP Right Cessation
- 2003-07-22 ES ES03784037T patent/ES2250920T3/es not_active Expired - Lifetime
- 2003-07-22 RU RU2005105947/03A patent/RU2312712C2/ru not_active IP Right Cessation
- 2003-07-22 CA CA2494619A patent/CA2494619C/en not_active Expired - Fee Related
- 2003-07-22 BR BRPI0312359-6A patent/BR0312359B1/pt not_active IP Right Cessation
- 2003-07-22 CN CNB038154137A patent/CN1305577C/zh not_active Expired - Fee Related
- 2003-07-22 DE DE50301822T patent/DE50301822D1/de not_active Expired - Lifetime
- 2003-07-22 BR BRPI0318899-0B1A patent/BR0318899B1/pt not_active IP Right Cessation
- 2003-07-22 EP EP03784037A patent/EP1528957B1/de not_active Expired - Lifetime
- 2003-07-22 PL PL375196A patent/PL203935B1/pl unknown
- 2003-07-22 AU AU2003254558A patent/AU2003254558B2/en not_active Ceased
- 2003-07-22 MX MXPA05001344A patent/MXPA05001344A/es active IP Right Grant
- 2003-07-22 WO PCT/EP2003/007966 patent/WO2004014562A2/de active IP Right Grant
- 2003-07-22 US US10/523,746 patent/US7104404B2/en not_active Expired - Fee Related
-
2004
- 2004-11-30 ZA ZA2004/09677A patent/ZA200409677B/en unknown
-
2006
- 2006-07-21 US US11/490,921 patent/US7553984B2/en not_active Expired - Fee Related
-
2008
- 2008-02-26 CL CL200800584A patent/CL2008000584A1/es unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4822483A (en) * | 1984-09-13 | 1989-04-18 | The Dow Chemical Company | Collector compositions for the froth flotation of mineral values |
| DE3629269A1 (de) * | 1986-08-28 | 1988-03-10 | Hoechst Ag | Verfahren zur herstellung von o-alkyl-amido-thiophosphorsaeure-salzen |
| DE4040475A1 (de) * | 1989-12-23 | 1991-07-04 | Hoechst Ag | Neue dithiophosphorsaeureester und deren verwendung zur faellung und flotation von schwermetallen aus abwaessern |
| CN1063627A (zh) * | 1991-02-02 | 1992-08-19 | 中南工业大学 | 用α-亚硝基膦酸酯作硫化矿捕收剂 |
| CN1294032A (zh) * | 1999-10-29 | 2001-05-09 | 沈阳矿冶研究所 | 贵金属和有色金属硫化矿复合浮选药剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE50301822D1 (de) | 2006-01-05 |
| US7104404B2 (en) | 2006-09-12 |
| AU2003254558A1 (en) | 2004-02-25 |
| CA2494619C (en) | 2011-01-25 |
| US7553984B2 (en) | 2009-06-30 |
| BR0312359B1 (pt) | 2012-09-04 |
| PL375196A1 (en) | 2005-11-28 |
| ZA200409677B (en) | 2005-07-27 |
| BR0312359A (pt) | 2005-04-05 |
| PL203935B1 (pl) | 2009-11-30 |
| AU2003254558B2 (en) | 2008-11-06 |
| PE20040142A1 (es) | 2004-03-22 |
| RU2312712C2 (ru) | 2007-12-20 |
| CN1665598A (zh) | 2005-09-07 |
| ES2250920T3 (es) | 2006-04-16 |
| EP1528957A2 (de) | 2005-05-11 |
| CA2494619A1 (en) | 2004-02-19 |
| PE20081058A1 (es) | 2008-09-04 |
| US20070181467A1 (en) | 2007-08-09 |
| CL2008000584A1 (es) | 2008-06-13 |
| MXPA05001344A (es) | 2005-04-28 |
| EP1528957B1 (de) | 2005-11-30 |
| RU2005105947A (ru) | 2005-08-10 |
| BR0318899B1 (pt) | 2014-09-23 |
| WO2004014562A2 (de) | 2004-02-19 |
| US20050263442A1 (en) | 2005-12-01 |
| WO2004014562A3 (de) | 2004-05-13 |
| ATE311256T1 (de) | 2005-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1305577C (zh) | 用于硫化物矿石的收集剂 | |
| CN1229508C (zh) | 脂族异羟肟酸与油混合的矿物浮选促集剂组合物及其制备方法 | |
| CN106955790B (zh) | 一种n-烷基羟肟酸-o-烃基硫氨酯捕收剂、制备及其应用 | |
| CN101337206B (zh) | 硫化矿浮选捕收剂及二酰基双硫脲应用方法和制备方法 | |
| CN102753485B (zh) | 硫化物浮选辅助方法 | |
| WO2014040686A1 (en) | Composition for dressing phosphate ore | |
| CN102516144B (zh) | 一种硫脲化合物及制备和其在金属矿浮选中的应用 | |
| US7695634B2 (en) | Collector for sulfidic ores | |
| CN1014499B (zh) | 用于选择性浮选铅锌矿的促集剂 | |
| CN1014247B (zh) | 从矿石中回收含金属矿物的方法 | |
| EP1556170B1 (en) | Process for the beneficiation of sulfide minerals | |
| WO2021160860A1 (en) | New frothers for minerals recovery | |
| CA1188014A (en) | Ore flotation method | |
| US20230109502A1 (en) | New frothers for minerals recovery and methods of making and using same | |
| AU2022342271A1 (en) | Composition and method for use of 1-alkyl-5-oxopyrrolidine-3-carboxylic acids as collectors for phosphate and lithium flotation | |
| DE10252451A1 (de) | Verfahren zur Herstellung von Alkylamidothiophosphorsäuredialkylestern |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070321 Termination date: 20170722 |