CN106391323B - A kind of application of 1,2,4,5- tetrazolium -3- thiones flotation collectors - Google Patents
A kind of application of 1,2,4,5- tetrazolium -3- thiones flotation collectors Download PDFInfo
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- CN106391323B CN106391323B CN201610846730.2A CN201610846730A CN106391323B CN 106391323 B CN106391323 B CN 106391323B CN 201610846730 A CN201610846730 A CN 201610846730A CN 106391323 B CN106391323 B CN 106391323B
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- tetrazolium
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- flotation
- thiones
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- 238000005188 flotation Methods 0.000 title claims abstract description 41
- CSRUKSZMBWRPRL-UHFFFAOYSA-N tetrazole-5-thione Chemical class S=C1N=NN=N1 CSRUKSZMBWRPRL-UHFFFAOYSA-N 0.000 title claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 21
- 239000011707 mineral Substances 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010931 gold Substances 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052737 gold Inorganic materials 0.000 claims abstract description 14
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 241001061127 Thione Species 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000007667 floating Methods 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 229910001739 silver mineral Inorganic materials 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 5
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- -1 1,2,3,4-Tetrazole-5-thiolate Anions Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 241000907663 Siproeta stelenes Species 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- CONMNFZLRNYHIQ-UHFFFAOYSA-N 3-methylbutoxymethanedithioic acid Chemical compound CC(C)CCOC(S)=S CONMNFZLRNYHIQ-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 229910001779 copper mineral Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000004907 1,2,4,5-tetrazines Chemical class 0.000 description 1
- NOLHRFLIXVQPSZ-UHFFFAOYSA-N 1,3-thiazolidin-4-one Chemical class O=C1CSCN1 NOLHRFLIXVQPSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 230000004568 DNA-binding Effects 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 101710163270 Nuclease Proteins 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000003070 anti-hyperalgesia Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- STRNXFOUBFLVIN-UHFFFAOYSA-N diethyl but-2-ynedioate Chemical compound CCOC(=O)C#CC(=O)OCC STRNXFOUBFLVIN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002192 fatty aldehydes Chemical class 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses one kind 1,2,4,5 tetrazolium, 3 thiones flotation collector and its application, the application is by 1,2,4,5 tetrazolium, 3 thioketone is applied to flotation recycling valuable metal in the ore of cupric, silver or gold mineral as mineral floating collecting agent, compared with the prior art in common flotation collector can effectively improve the enrichment and recycling of copper, silver or gold mineral.
Description
Technical field
The invention belongs to metal ore dressing field, and in particular to a kind of 1,2,4,5- tetrazolium -3- thiones flotation collectors
Using.
Background technology
1,2,4,5- tetrazolium -3- thioketones have good bioactivity, photochromism and metal-chelating
Can, antiseptic, herbicide, antihyperalgesic thing can be used as, can also be used as photosensitive material, luminous energy material and corrosion inhibiter, its metal is matched somebody with somebody
Compound has the function of light, electricity, magnetic.
Gopalakrishnan etc. is mixed aromatic aldehyde, thiocarbamide and ammonium acetate in 1: 1: 2 ratio (molar ratio),
NaHSO4·SiO26- substituted-phenyls -1,2,4,5- tetrazolium -3- thioketones are can obtain under catalysis and microwave radiation
(Gopalakrishnan M., Thanusu J., Kanagarajan V..Easy-to-execute ' one-pot '
1,2,4,5-tetrazines catalyzed by activated fly ash [J] .Journal of of synthesis of
The Korean Chemical Society, 2007,51 (6)：520-525；Gopalakrishnan M., Sureshkumar
P., Kanagarajan V., Thanusu J..Design, ' one-pot ' synthesis, characterization,
Antibacterial and antifungal activities of novel 6-aryl-1,2,4,5-tetrazinan-3-
Thiones in dry media [J] .Journal of Sulfur Chemistry, 2007,18 (4)：383-392).
Tashtoush etc. by diaminourea thiocarbamide and fatty aldehyde or cyclic ketones react to obtain in acid condition 6- substitute -1,2,4,5- tetrazoliums -
3- thioketones (Tashtoush H.I., Abusahyon F., Shkoor M., et al.Dual behavior of
monothiocarbohydrazones in the cyclization with diethyl acetylene
dicarboxylate(DEAD)：Synthesis of substituted 1,3-thiazolidin-4-ones [J]
.Journal of Sulfur Chemistry, 2011,32 (5)：405-412).It is molten that acetophenone is dissolved in ethanol by Tabassum etc.
In liquid, diaminourea thiocarbamide and acetic acid are added, reaction 2-3h is stirred at room temperature, 6- aryl -1,2,4,5- tetrazolium -3- thioketones are made
(Tabassum S., Parveen M., Ali A., et al.Synthesis of aryl-1,2,4,5-tetrazinane-3-
Thiones, in vitro DNA binding studies, nuclease activity and its antimicrobial
Activity [J] .Journal ofMolecular Structure, 2012,1020：33-40).
Pass through its sulphur atom and Cu (I), Ag (I), Au (I), Au (II) Deng 1,2,4,5- tetrazolium -3- thioketones of discovery
Or Pd (II) coordinations (H., Beck W., Burger K..The molecular structure of some
1,2,3,4-Tetrazole-5-thiolate Anions [J] of transition-metal complexes with
.European Journal of Inorganic Chemistry, 1998,1998 (1)：93-99).Khan etc. has investigated 6,6-
Cyclopenta -1,2,4,5- tetrazolium -3- thioketones, 6,6- cyclohexyl -1,2,4,5- tetrazolium -3- thioketones and 6,6- isobutyl methyl -
1,2,4,5- tetrazolium -3- thioketones in formic acid and acetic acid solution to the antiseptic property of carbon steel (S.Khan, M.Z.A.Rafiquee,
N.Saxena, M.A.Quraishi.Inhibition of carbon steel corrosion by azathione
derivatives in organic acid solutions[J].Anti-Corrosion Methods and
Materials, 2009,56 (3)：145-153).
At present, flotation collector is not used as it on 1,2,4,5- tetrazolium -3- thioketones in the prior art
Report.
The content of the invention
The purpose of the invention is to provide a kind of 1,2,4,5- tetrazolium -3- thiones collecting agents in metalliferous mineral flotation side
The application in face, 1,2,4, the 5- tetrazolium -3- thioketones can effectively improve valuable gold in the ore of cupric, silver or gold mineral
The enrichment of category and organic efficiency.
A kind of application of 1,2,4,5- tetrazolium -3- thiones flotation collectors, by 1,2,4 with 2 structure of formula 1 or formula,
The flotation collector of 5- tetrazolium -3- thioketones is applied to copper-bearing mineral, silver mineral, at least one ore of gold mineral
In, flotation recycling valuable metal；
In formula 1, R C1~C17Alkyl；R1For H or it is C1~C3Alkyl；
In formula 2, n is 2~5 integer.
The inventors discovered that there will be the chemical combination of 2 main nuclear structure of formula 1 and formula (6- substitutes -1,2,4,5- tetrazolium -3- thioketones)
Collecting agent of the thing as flotation, contribute to copper mineral, silver mineral, gold mine ores valuable metal enrichment and recycling.
R and R in 1 compound of formula16- spirane structures in 2 compound of group and formula are used to provide described catch
Receive the good hydrophobicity of agent.
The R is C1~C17Alkyl, that is to say the R is the hydrocarbon group that carbon number is 1~17.Such as：R
Can be (1) saturated alkane, such as linear paraffin or branched paraffin；(2) alkylene or olefin alkylation of single or multiple double bonds are contained；
(3) saturation or unsaturation ring alkane, cycloalkyl group are preferably five yuan or hexatomic ring；(4) alkylaryl containing aromatic structure or
Aryl alkyl, such as alkyl-substituted phenyl, alkyl-substituted fused ring aryl, or phenylalkyl, fused ring aryl alkyl.
Preferably, R is C1~C17Alkyl or be C2~C17Alkylene or be C6~C12Aryl.
The R is preferably C1~C17Alkyl, such as C1~C17Straight chained alkyl, or C1~C17Branched alkane
Base.
Further preferably, in formula 1, R C1~C17Linear paraffin base.
For example, R is methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, just
Decyl, positive hendecyl, positive dodecyl, positive tritriacontyl, positive tetradecyl, positive pentadecyl, positive palmityl or positive heptadecyl.
Preferably, in formula 1, R C10~C17Monoene alkyl.
The C10~C17In monoene alkyl, can be alkyl alkylene (unsaturated double-bond carbon directly and 1,2,4,5- tetra-
On azoles -3- thioketones parent nucleus carbon connection) or olefin alkylation (unsaturated double-bond carbon passes through saturated carbon and 1,2,4,5- tetrazolium -3-
Thioketones parent nucleus connects).For example, R is 1- nonenyls or 3- alkene nonyls.
More preferably, in formula 1, R is propyl group, amyl group, hexyl, heptyl or nonyl.
In formula 1, R1For H, methyl, ethyl, propyl group or isopropyl.
Preferably, in formula 1, R1For H or methyl.
In 2 compound of formula, saturation cycloalkane and described 1,6 shared carbon atoms of 2,4,5- tetrazolium -3- thioketones parent nucleus,
Form spirane structure；The saturation cycloalkane is preferably five yuan, hexa-atomic, seven yuan, eight yuan of saturation cycloalkane, that is to say that n is selected
From the arbitrary integer of 2-5.
Preferably, in formula 2, n 3.
In the present invention, the application process, by described 1,2,4,5- tetrazolium -3- thiones flotation collector as floating
Collecting agent and copper-bearing mineral, the ore pulp contact of silver mineral, gold mineral are selected, reaches the mesh of the noble metals such as high efficiente callback copper, silver, gold
's.
As the preferred solution of the present invention, comprise the following steps：
Step (1)：At least one ore of copper-bearing mineral, silver mineral, gold mineral obtains ore pulp after crushing, sizing mixing；
Step (2)：Floating agent is added into described step (1) ore pulp and carries out flotation, collection obtains flotation concentrate；Institute
The floating agent stated includes described 1,2,4,5- tetrazolium -3- thiones flotation collectors.
In step (1), the crushing to ore uses the prior art.For example, in step (1), the ore is first through jaw
Crusher, crusher machine in small, broken bits, then again through ball mill grinding.
In step (2), the floating agent can also include the flotation materials such as foaming agent and/or conditioning agent.
Ore pulp is obtained after the adjusted pH of ore slurry, in of the invention, the pH for preferably controlling ore pulp is 6-13；Further preferably
6-10。
Preferably, in step (1), on the basis of the ore weight, described 1,2,4,5- tetrazolium -3- thiones
The dosage of flotation collector is 10-500g/t.More preferably 40-100g/t.
1,2,4, the 5- tetrazolium -3- thioketones of the present invention can pass through corresponding organic aldehydes or ketones and diaminourea thiocarbamide
It is made in organic media with heating ring-closure reaction in the presence of acetic acid.
Provided by the invention 1,2,4,5- tetrazolium -3- thioketones collecting agents can lift floatation indicators, improve the floating of metalliferous mineral
Choosing recycling.To the Mineral Processing Subject of an existing over one hundred year development history, flotation recovery rate one percentage point is often improved, is all huge
Big progress, can produce global mining the economic value of over ten billion.
Beneficial effects of the present invention：1,2,4,5- tetrazolium -3- thioketones are applied in mineral by the present invention first
Valuable metal flotation collecting, especially suitable for the enrichment and recycling of valuable metal in the ore of cupric, silver or gold mineral, relatively
Recovery rate of valuable metals can be improved in existing common collecting agent.
Brief description of the drawings
Fig. 1 be embodiment 1 described in 6- hexyls -1,2,4,5- tetrazolium -3- thioketones1H-NMR schemes.
Embodiment
Following embodiments are intended to further illustrate present invention, rather than the restriction to protection scope of the present invention.
In embodiment unless otherwise specified all parts and percentages refer both to quality.Flotation in embodiment to mineral is caught
Receipts process is all conventional process, and simply using the present invention 1,2,4,5- tetrazolium -3- thioketones replace conventional collecting agent.
The unit of weight that adds of each floating agent of following embodiments is g/t, in addition to being not particularly limited, with ore weight
On the basis of amount (t).
Embodiment 1
In 6- hexyls -1,2,4,5- tetrazolium -3- thioketones concentration are 1 × 10-5Mol/L, pH values of pulp 8.5, foaming agent methyl
The concentration of isobutyl carbinol (MIBC) is 15mg/L, N2Gas velocity is 200mL/min, is -0.076mm~+0.038mm to particle diameter
Chalcopyrite flotation 3 minutes, at this time the flotation recovery rate of chalcopyrite reach 93.2%.
Embodiment 2
In 6,6- methylhexyls -1,2,4,5- tetrazolium -3- thioketones concentration are 2 × 10-4Mol/L, pH values of pulp 8.5, blistering
The concentration of agent MIBC is 15mg/L, N2Gas velocity is 200mL/min, and the malachite that particle diameter is -0.076mm~+0.038mm is floated
Select 3 minutes, the flotation recovery rate of malachite is 97.6% at this time.
Embodiment 3
Dongchuan District, Yunnan Province vulcanization-oxidization copper core sample, raw ore contain Cu 0.63%, its oxygenation efficiency is 26.5%.Experiment process：
One roughing once purging selection.Mog：- 0.074mm accounts for 90%；Agentia condition：300 g ton of roughing vulcanized sodium be (ore pulp
PH7.5), scan 800 g ton of vulcanized sodium (pH8.0 of ore pulp), remaining agentia condition and its results are shown in Table 1.The experiment knot of table 1
Fruit shows, 6- alkyl -1,2, and the copper recovery that 4,5- tetrazolium -3- thioketones collecting agents achieve than butyl xanthate higher (scans essence
Ore deposit).
1 6- alkyl -1,2 of table, 4,5- tetrazolium -3- thioketones flotation Dongchuan District, Yunnan Province vulcanization-oxidization copper mine conditions and its result
Embodiment 4
Tibet Changdu oxidation-copper sulfide sample ore, raw ore contain Cu 3.9%, its oxygenation efficiency is 69.4%, main oxidation
Copper mineral is malachite and chessy copper.Experiment process：One roughing once purging selection.Mog：- 0.074mm accounts for 80%；Medicament
Condition：3000 g ton of roughing vulcanized sodium (pH8.5 of ore pulp), scans 1000 g ton of vulcanized sodium (pH9.0 of ore pulp), remaining medicine
Agent condition and its it the results are shown in Table 2.The result of the test of table 2 shows that 6- alkyl -1,2,4,5- tetrazolium -3- thioketones collecting agents achieve
Than isoamyl xanthate and the copper recovery (scavenger concentrate) of isoamyl xanthate+octyl group hydroximic acid higher.
2 Tibet Changdu oxidation of table-copper-sulphide ores condition and its result
Embodiment 5
Jiangxi Shangrao porphyry copper stone ore sample, raw ore cupric 0.39%, sulfur-bearing 1.85%, containing golden 0.21g/t, argentiferous
1.18g/t.Experiment process：One roughing；Mog：- 0.074mm accounts for 68%；Agentia condition：800 g ton of lime consumption,
Slurry pH is 8.5, remaining agentia condition and its results are shown in Table 3.The result of the test of table 3 shows, 6- heptyl -1,2 of the invention,
4,5- tetrazolium -3- thioketones+butyl xanthate combined capturing and collecting agent is obtained than common collecting agent butyl xanthate and 3- hexyl -4- amino -1,2,
Copper, the gold, silver flotation recovery rate (rough concentrate) of 4- triazoles -5- thioketones+butyl xanthate higher.
3 Jiangxi Shangrao porphyry copper condition of table and its result
* unit g/t
To sum up, can be effectively improved containing copper mine as collecting agent using described 1,2,4,5- tetrazolium -3- thioketones
Thing, silver mineral, gold mineral at least one ore in valuable metal enrichment and organic efficiency.
Claims (9)
1. the application of 1,2,4,5- tetrazolium -3- thiones flotation collectors of one kind, it is characterised in that will have 2 structure of formula 1 or formula
1,2,4,5- tetrazolium -3- thioketones flotation collector be applied to copper-bearing mineral, silver mineral, at least the one of gold mineral
In kind ore, flotation recycling valuable metal；
Formula 1
Formula 2
In formula 1, R C1~C17Alkyl；R1For H or it is C1~C3Alkyl；
In formula 2, n is 2 ~ 5 integer.
2. the application of as claimed in claim 11,2,4,5- tetrazolium -3- thiones flotation collectors, it is characterised in that R C1~
C17Alkyl or be C2~C17Alkylene or be C6~C12Aryl.
3. the application of as claimed in claim 11,2,4,5- tetrazolium -3- thiones flotation collectors, it is characterised in that formula 1
In, R C1~C17Linear paraffin base；Or it is C10 ~C17 Monoene alkyl.
4. the application of as claimed in claim 11,2,4,5- tetrazolium -3- thiones flotation collectors, it is characterised in that formula 1
In, R is propyl group, amyl group, hexyl, heptyl or nonyl.
5. the application of as claimed in claim 11,2,4,5- tetrazolium -3- thiones flotation collectors, it is characterised in that formula 1
In, R1For methyl.
6. the application of as claimed in claim 11,2,4,5- tetrazolium -3- thiones flotation collectors, it is characterised in that formula 2
In, n 3.
7. such as the application of 1,2,4,5- tetrazolium -3- thiones flotation collectors of claim 1-6 any one of them, its feature exists
In comprising the following steps：
Step (1)：At least one ore of copper-bearing mineral, silver mineral, gold mineral obtains ore pulp after crushing, sizing mixing；
Step (2)：Floating agent is added into described step (1) ore pulp and carries out flotation, collection obtains flotation concentrate；Described
Floating agent includes the 1,2,4,5- tetrazolium -3- thiones flotation collectors.
8. the application of as claimed in claim 71,2,4,5- tetrazolium -3- thiones flotation collectors, it is characterised in that step
(1) in, the pH of the ore pulp is 6-13.
9. the application of as claimed in claim 71,2,4,5- tetrazolium -3- thiones flotation collectors, it is characterised in that step
(1) in, on the basis of the ore weight, the dosage of described 1,2,4,5- tetrazolium -3- thiones flotation collectors is
10-500g/t。
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| CN1014802B (en) * | 1986-09-03 | 1991-11-20 | 昆明工学院 | Recovery of copper, gold and silver by vulcanizing roasting at law temp.-ore dressing |
| CN1007705B (en) * | 1986-11-27 | 1990-04-25 | 大冶有色金属公司铜录山铜铁矿 | Complexing agent for floating copper ore |
| US5929408A (en) * | 1996-09-26 | 1999-07-27 | Cytec Technology Corp. | Compositions and methods for ore beneficiation |
| EP1944088A1 (en) * | 2007-01-12 | 2008-07-16 | Omya Development Ag | Process of purification of minerals based on calcium carbonate by flotation in the presence of quaternary imidazollum methosulfate |
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