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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- 238000005188 flotation Methods 0.000 title claims abstract 19
- CSRUKSZMBWRPRL-UHFFFAOYSA-N tetrazole-5-thione Chemical class S=C1N=NN=N1 CSRUKSZMBWRPRL-UHFFFAOYSA-N 0.000 title claims abstract 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract 5
- 239000011707 mineral Substances 0.000 claims abstract 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000010931 gold Substances 0.000 claims abstract 4
- 229910052737 gold Inorganic materials 0.000 claims abstract 4
- 229910052751 metal Inorganic materials 0.000 claims abstract 2
- 239000002184 metal Substances 0.000 claims abstract 2
- 150000002739 metals Chemical class 0.000 claims abstract 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims 2
- 229910001779 copper mineral Inorganic materials 0.000 claims 2
- 239000008396 flotation agent Substances 0.000 claims 2
- 229910001739 silver mineral Inorganic materials 0.000 claims 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- -1 azole-3-thione compound Chemical class 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 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 1
- 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 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000005673 monoalkenes Chemical class 0.000 claims 1
- 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 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- BOIQZTADZZVXDL-UHFFFAOYSA-N pyrrole-3-thione Chemical compound S=C1C=CN=C1 BOIQZTADZZVXDL-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 2
- 229910052802 copper Inorganic materials 0.000 abstract 2
- 239000010949 copper Substances 0.000 abstract 2
- 238000011084 recovery Methods 0.000 abstract 2
- 229910052709 silver Inorganic materials 0.000 abstract 2
- 239000004332 silver Substances 0.000 abstract 2
Classifications
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- 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种1，2，4，5‑四唑‑3‑硫酮类浮选捕收剂及其应用，该应用是将1，2，4，5‑四唑‑3‑硫酮类化合物作为矿物浮选捕收剂应用于含铜、银或金矿物的矿石中浮选回收有价金属，相对现有技术中的常用浮选捕收剂能有效改善铜、银或金矿物的富集和回收。
The invention discloses a 1,2,4,5-tetrazole-3-thione flotation collector and its application. The application is to use 1,2,4,5-tetrazole-3-thione Compounds are used as mineral flotation collectors in the flotation recovery of valuable metals in ores containing copper, silver or gold minerals, which can effectively improve the copper, silver or gold mineral Enrichment and recovery.
Description
技术领域technical field
本发明属于金属选矿领域，具体涉及一种1，2，4，5-四唑-3-硫酮类浮选捕收剂的应用。The invention belongs to the field of metal beneficiation, and in particular relates to the application of a 1,2,4,5-tetrazole-3-thione flotation collector.
背景技术Background technique
1，2，4，5-四唑-3-硫酮类化合物具有良好的生物活性、光致变色性与金属螯合性能，可作为抗菌剂、除草剂、抗血压药物，也可作为感光材料、光能材料和缓蚀剂，其金属配合物具有光、电、磁功能。1,2,4,5-tetrazole-3-thione compounds have good biological activity, photochromic properties and metal chelating properties, and can be used as antibacterial agents, herbicides, antihypertensive drugs, and photosensitive materials , light energy materials and corrosion inhibitors, and its metal complexes have light, electricity and magnetic functions.
Gopalakrishnan等将芳香醛、硫脲和乙酸铵按1∶1∶2的比例(摩尔比)混合，在NaHSO4·SiO2催化以及微波辐射下可得到6-取代苯基-1，2，4，5-四唑-3-硫酮(Gopalakrishnan M.，Thanusu J.，Kanagarajan V..Easy-to-execute′one-pot′synthesis of 1，2，4，5-tetrazines catalyzed by activated fly ash[J].Journal ofthe Korean Chemical Society，2007，51(6)：520-525；Gopalakrishnan M.，SureshkumarP.，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等将二氨基硫脲与脂肪醛或环酮在酸性条件下反应得到6-取代-1，2，4，5-四唑-3-硫酮(Tashtoush H.I.，Abusahyon F.，Shkoor M.，et al.Dual behavior ofmonothiocarbohydrazones in the cyclization with diethyl acetylenedicarboxylate(DEAD)：synthesis of substituted 1，3-thiazolidin-4-ones[J].Journal of Sulfur Chemistry，2011，32(5)：405-412)。Tabassum等将乙酰苯溶于乙醇溶液中，加入二氨基硫脲和乙酸，在室温下搅拌反应2-3h，制得6-芳基-1，2，4，5-四唑-3-硫酮(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 antimicrobialactivity[J].Journal ofMolecular Structure，2012，1020：33-40)。Gopalakrishnan et al. mixed aromatic aldehyde, thiourea and ammonium acetate in a ratio (molar ratio) of 1:1:2, and obtained 6-substituted phenyl-1,2,4 under NaHSO 4 ·SiO 2 catalysis and microwave irradiation, 5-tetrazole-3-thione (Gopalakrishnan M., Thanusu J., Kanagarajan V..Easy-to-execute′one-pot′synthesis of 1,2,4,5-tetrazines catalyzed by activated fly ash[J ].Journal 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. react dithiosemicarbazide with aliphatic aldehyde or cyclic ketone under acidic conditions to obtain 6-substituted-1,2,4,5-tetrazole-3-thione (Tashtoush HI, Abusahyon F., Shkoor M., et al. Dual behavior of monothiocarbohydrazones in the cycling with diethyl acetylenedicarboxylate (DEAD): synthesis of substituted 1,3-thiazolidin-4-ones [J]. Journal of Sulfur Chemistry, 2011, 32(5): 405-412). Tabassum et al. dissolved acetophenone in ethanol solution, added thiosemicarbazide and acetic acid, stirred and reacted at room temperature for 2-3h, and obtained 6-aryl-1,2,4,5-tetrazole-3-thione (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 antimicrobialactivity[J].Journal of Molecular Structure, 2012, 1020: 33-40).
等发现1，2，4，5-四唑-3-硫酮通过其硫原子与Cu(I)、Ag(I)、Au(I)、Au(II)或Pd(II)配位(H.，Beck W.，Burger K..The molecular structure of sometransition-metal complexes with 1，2，3，4-Tetrazole-5-thiolate Anions[J].European Journal of Inorganic Chemistry，1998，1998(1)：93-99)。Khan等考察了6，6-环戊基-1，2，4，5-四唑-3-硫酮、6，6-环己基-1，2，4，5-四唑-3-硫酮以及6，6-异丁基甲基-1，2，4，5-四唑-3-硫酮在甲酸与乙酸溶液中对碳钢的防腐性能(S.Khan，M.Z.A.Rafiquee，N.Saxena，M.A.Quraishi.Inhibition of carbon steel corrosion by azathionederivatives in organic acid solutions[J].Anti-Corrosion Methods andMaterials，2009，56(3)：145-153)。 found that 1,2,4,5-tetrazole-3-thione coordinates with Cu(I), Ag(I), Au(I), Au(II) or Pd(II) through its sulfur atom ( H., Beck W., Burger K.. The molecular structure of some transition-metal complexes with 1, 2, 3, 4-Tetrazole-5-thiolate Anions [J]. European Journal of Inorganic Chemistry, 1998, 1998 (1) :93-99). Khan et al. investigated 6,6-cyclopentyl-1,2,4,5-tetrazole-3-thione, 6,6-cyclohexyl-1,2,4,5-tetrazole-3-thione And 6,6-isobutylmethyl-1,2,4,5-tetrazole-3-thione in formic acid and acetic acid solution to the corrosion resistance of carbon steel (S.Khan, MZARafiquee, N.Saxena, MAQuraishi.Inhibition of carbon steel corrosion by azathioned derivatives in organic acid solutions [J]. Anti-Corrosion Methods and Materials, 2009, 56(3): 145-153).
目前，现有技术中并没有关于1，2，4，5-四唑-3-硫酮类化合物用作浮选捕收剂的报道。At present, there is no report about 1,2,4,5-tetrazole-3-thione compounds used as flotation collectors in the prior art.
发明内容Contents of the invention
本发明的目的是在于提供一种1，2，4，5-四唑-3-硫酮类捕收剂在金属矿物浮选方面的应用，该1，2，4，5-四唑-3-硫酮类化合物能有效提高含铜、银或金矿物的矿石中有价金属的富集和回收效率。The purpose of the present invention is to provide a kind of 1,2,4, the application of 1,2,4,5-tetrazole-3-thione collector in metal mineral flotation, this 1,2,4,5-tetrazole-3 - Thione compounds can effectively improve the enrichment and recovery efficiency of valuable metals in ores containing copper, silver or gold minerals.
一种1，2，4，5-四唑-3-硫酮类浮选捕收剂的应用，将具有式1或式2结构的1，2，4，5-四唑-3-硫酮类化合物的浮选捕收剂应用于含铜矿物、银矿物、金矿物的至少一种矿石中，浮选回收有价金属；A kind of application of 1,2,4,5-tetrazole-3-thione flotation collector, will have formula 1 or formula 2 structure 1,2,4,5-tetrazole-3-thione The flotation collector of similar compounds is applied to at least one ore containing copper minerals, silver minerals, and gold minerals, and the valuable metals are recovered by flotation;
式1中，R为C1～C17的烃基；R1为H、或者为C1～C3的烷烃基；In Formula 1, R is a C 1 -C 17 hydrocarbon group; R 1 is H, or a C 1 -C 3 alkane group;
式2中，n为2～5的整数。In Formula 2, n is an integer of 2-5.
本发明人发现，将具有式1和式2主核结构(6-取代-1，2，4，5-四唑-3-硫酮)的化合物作为浮选的捕收剂，有助于铜矿物、银矿物、金矿物矿石的有价金属的富集和回收。The inventors have found that the compound with the main core structure of formula 1 and formula 2 (6-substituted-1,2,4,5-tetrazole-3-thione) as a collector for flotation contributes to the Enrichment and recovery of valuable metals from minerals, silver minerals, and gold mineral ores.
所述的式1化合物中的R和R1基团以及式2化合物中的6-螺环结构用于提供所述捕收剂良好的疏水性。The R and R 1 groups in the compound of formula 1 and the 6-spiro ring structure in the compound of formula 2 are used to provide the good hydrophobicity of the collector.
所述的R为C1～C17的烃基，也即是所述的R为碳原子数为1～17的碳氢基团。例如：R可为(1)饱和烷烃，如直链烷烃或支链烷烃；(2)含有单个或多个双键的烯烃基或烯烃烷基；(3)饱和或不饱和环烷烃，环烷烃基优选为五元或六元环；(4)含有芳香结构的烷基芳基或芳基烷基，例如烷基取代的苯基、烷基取代的稠环芳基，或苯基烷基、稠环芳基烷基。The R is a C 1 -C 17 hydrocarbon group, that is, the R is a hydrocarbon group with 1-17 carbon atoms. For example: R can be (1) a saturated alkane, such as a straight-chain alkane or a branched alkane; (2) an alkene group or an alkene alkyl group containing a single or multiple double bonds; (3) a saturated or unsaturated cycloalkane, a cycloalkane The group is preferably a five-membered or six-membered ring; (4) an alkylaryl or arylalkyl group containing an aromatic structure, such as an alkyl-substituted phenyl group, an alkyl-substituted fused ring aryl group, or a phenylalkyl group, Fused ring arylalkyl.
作为优选，R为C1～C17的烷烃基、或者为C2～C17的烯烃基、或者为C6～C12的芳烃基。Preferably, R is a C 1 -C 17 alkane group, or a C 2 -C 17 alkene group, or a C 6 -C 12 arene group.
所述的R优选为C1～C17的烷烃基，例如C1～C17的直链烷基，或者C1～C17的支链烷基。The R is preferably a C 1 -C 17 alkane group, such as a C 1 -C 17 straight chain alkyl group, or a C 1 -C 17 branched chain alkyl group.
进一步优选，式1中，R为C1～C17的直链烷烃基。More preferably, in Formula 1, R is a C 1 -C 17 linear alkane group.
例如，R为甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一基、正十二基、正十三基、正十四基、正十五基、正十六基或正十七基。For example, R is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl , n-thirteen bases, n-tetradecyls, n-pentadecyls, n-hexadecyls or n-heptadecyls.
作为优选，式1中，R为C10～C17单烯烃基。Preferably, in Formula 1, R is a C 10 -C 17 monoalkene group.
所述的C10～C17单烯烃基中，可以为烷基烯烃基(不饱和双键碳直接和1，2，4，5-四唑-3-硫酮母核上的碳连接)或者烯烃烷基(不饱和双键碳通过饱和碳和1，2，4，5-四唑-3-硫酮母核连接)。例如，R为1-壬烯基或3-烯壬基。Among the C 10 -C 17 monoalkene groups, it can be an alkyl olefin group (the unsaturated double bond carbon is directly connected to the carbon on the 1,2,4,5-tetrazole-3-thione core) or Alkene alkyl (unsaturated double-bonded carbon linked by saturated carbon and 1,2,4,5-tetrazole-3-thione core). For example, R is 1-nonenyl or 3-enonyl.
更为优选，式1中，R为丙基、戊基、己基、庚基或壬基。More preferably, in formula 1, R is propyl, pentyl, hexyl, heptyl or nonyl.
式1中，R1为H、甲基、乙基、丙基或异丙基。In formula 1, R 1 is H, methyl, ethyl, propyl or isopropyl.
作为优选，式1中，R1为H或甲基。Preferably, in Formula 1, R 1 is H or methyl.
式2化合物中，饱和环烷烃和所述的1，2，4，5-四唑-3-硫酮母核的6位共用碳原子，组成螺环结构；所述的饱和环烷烃优选为五元、六元、七元、八元的饱和环烷烃，也即是n选自2-5的任意整数。In the compound of formula 2, the saturated cycloalkane and the 6-position shared carbon atoms of the 1,2,4,5-tetrazole-3-thione core form a spiro ring structure; the saturated cycloalkane is preferably five One-membered, six-membered, seven-membered, eight-membered saturated cycloalkane, that is, n is any integer selected from 2-5.
作为优选，式2中，n为3。Preferably, in Formula 2, n is 3.
本发明中，所述的应用方法，将所述的1，2，4，5-四唑-3-硫酮类浮选捕收剂作为浮选捕收剂和含铜矿物、银矿物、金矿物的矿浆接触，达到高效回收铜、银、金等贵金属的目的。In the present invention, in the application method, the 1,2,4,5-tetrazole-3-thione flotation collector is used as a flotation collector and copper-containing minerals, silver minerals, The pulp contact of gold minerals achieves the purpose of efficient recovery of copper, silver, gold and other precious metals.
作为本发明的优选方案，包括以下步骤：As a preferred version of the present invention, comprising the following steps:
步骤(1)：含铜矿物、银矿物、金矿物至少一种的矿石经粉碎、调浆后得矿浆；Step (1): The ore containing at least one of copper minerals, silver minerals, and gold minerals is crushed and pulped to obtain ore pulp;
步骤(2)：向所述的步骤(1)矿浆中投加浮选药剂进行浮选，收集得到浮选精矿；所述的浮选药剂包含所述的1，2，4，5-四唑-3-硫酮类浮选捕收剂。Step (2): adding flotation agents to the slurry in step (1) for flotation, and collecting the flotation concentrate; the flotation agents contain the 1,2,4,5-4 Azole-3-thione flotation collector.
步骤(1)中，对矿石的粉碎采用现有技术。例如，步骤(1)中，所述的矿石先经颚式破碎机、细碎机破碎，随后再经球磨机粉磨。In step (1), prior art is adopted for crushing of ore. For example, in step (1), the ore is first crushed by a jaw crusher and a fine crusher, and then pulverized by a ball mill.
步骤(2)中，所述的浮选药剂还可以包含起泡剂和/或调节剂等浮选物料。In step (2), the flotation agents may also contain flotation materials such as foaming agents and/or regulators.
矿石浆料经调整pH后得到矿浆，本发明中，优选控制矿浆的pH为6-13；进一步优选6-10。The ore slurry is obtained by adjusting the pH. In the present invention, the pH of the ore slurry is preferably controlled to be 6-13; more preferably 6-10.
作为优选，步骤(1)中，以所述的矿石重量为基准，所述的1，2，4，5-四唑-3-硫酮类浮选捕收剂的投加量为10-500g/t。进一步优选为40-100g/t。As preferably, in step (1), based on the ore weight, the dosage of the 1,2,4,5-tetrazole-3-thione flotation collector is 10-500g /t. More preferably, it is 40-100 g/t.
本发明的1，2，4，5-四唑-3-硫酮类化合物可通过相应的有机醛或酮与二氨基硫脲在有机介质中与乙酸存在下加热环合反应制得。The 1,2,4,5-tetrazole-3-thione compound of the present invention can be prepared by heating and ring-closing the corresponding organic aldehyde or ketone with dithiosemicarbazide in the presence of acetic acid in an organic medium.
本发明提供的1，2，4，5-四唑-3-硫酮捕收剂可提升浮选指标，改善金属矿物的浮选回收。对一个已有百余年发展史的矿物加工学科，每提高浮选回收率一个百分点，都是巨大的进步，对全球矿业能产生上百亿的经济价值。The 1,2,4,5-tetrazole-3-thione collector provided by the invention can improve the flotation index and improve the flotation recovery of metal minerals. For a mineral processing discipline with a history of more than 100 years of development, every percentage point increase in flotation recovery rate is a huge improvement, which can generate tens of billions of economic value to the global mining industry.
本发明的有益效果：本发明首次将1，2，4，5-四唑-3-硫酮类化合物应用于矿物中的有价金属浮选捕收，特别适用于含铜、银或金矿物的矿石中有价金属的富集和回收，相对于现有的常用捕收剂能提高有价金属回收率。Beneficial effects of the present invention: the present invention applies 1,2,4,5-tetrazole-3-thione compounds to the flotation collection of valuable metals in minerals for the first time, especially for minerals containing copper, silver or gold The enrichment and recovery of valuable metals in the ore can improve the recovery rate of valuable metals compared with the existing common collectors.
附图说明Description of drawings
图1为实施例1所述的6-己基-1，2，4，5-四唑-3-硫酮1H-NMR图。FIG. 1 is a 1 H-NMR chart of 6-hexyl-1,2,4,5-tetrazole-3-thione described in Example 1.
具体实施方式Detailed ways
以下实施例旨在进一步说明本发明内容，而不是对本发明的保护范围的限定。The following examples are intended to further illustrate the content of the present invention, rather than limit the protection scope of the present invention.
实施例中所有的份数和百分数除另有规定外均指质量。实施例中对矿物的浮选捕收过程都是常规过程，只是采用本发明的1，2，4，5-四唑-3-硫酮类化合物替换常规捕收剂。All parts and percentages in the examples refer to mass unless otherwise specified. The flotation collection process of minerals in the examples is a conventional process, but the 1,2,4,5-tetrazole-3-thione compound of the present invention is used to replace the conventional collector.
以下实施例的各浮选药剂的投加重量单位为g/t，除没有特别限定外，均以矿石重量(t)为基准。The dosage unit of each flotation reagent in the following examples is g/t, and unless otherwise specified, the ore weight (t) is used as a benchmark.
实施例1Example 1
在6-己基-1，2，4，5-四唑-3-硫酮浓度为1×10-5mol/L，矿浆pH为8.5，起泡剂甲基异丁基甲醇(MIBC)的浓度为15mg/L，N2气流速为200mL/min，对粒径为-0.076mm～+0.038mm的黄铜矿浮选3分钟，此时黄铜矿的浮选回收率达到93.2％。When the concentration of 6-hexyl-1,2,4,5-tetrazole-3-thione is 1×10 -5 mol/L, the pH of the pulp is 8.5, and the concentration of foaming agent methyl isobutyl carbinol (MIBC) Chalcopyrite with a particle size of -0.076mm to +0.038mm was floated for 3 minutes, and the N 2 gas flow rate was 200mL/min. At this time, the flotation recovery rate of chalcopyrite reached 93.2%.
实施例2Example 2
在6，6-甲基己基-1，2，4，5-四唑-3-硫酮浓度为2×10-4mol/L，矿浆pH为8.5，起泡剂MIBC的浓度为15mg/L，N2气流速为200mL/min，对粒径为-0.076mm～+0.038mm的孔雀石浮选3分钟，此时孔雀石的浮选回收率为97.6％。When the concentration of 6,6-methylhexyl-1,2,4,5-tetrazole-3-thione is 2×10 -4 mol/L, the pH of the pulp is 8.5, and the concentration of foaming agent MIBC is 15mg/L , N 2 gas flow rate is 200mL/min, and the malachite whose particle size is -0.076mm～+0.038mm is flotation for 3 minutes, and the flotation recovery rate of malachite is 97.6%.
实施例3Example 3
云南东川某硫化-氧化铜矿样，原矿含Cu 0.63％，其氧化率为26.5％。试验流程：一次粗选一次扫选。磨矿细度：-0.074mm占90％；药剂条件：粗选硫化钠300克/吨(矿浆的pH7.5)，扫选硫化钠800克/吨(矿浆的pH8.0)，其余药剂条件及其结果见表1。表1的试验结果表明，6-烃基-1，2，4，5-四唑-3-硫酮捕收剂取得了比丁黄药更高的铜回收率(扫选精矿)。A sulfide-oxidized copper ore sample in Dongchuan, Yunnan, the original ore contains 0.63% Cu, and its oxidation rate is 26.5%. Test process: one rough selection and one sweep. Grinding fineness: -0.074mm accounts for 90%; chemical conditions: roughing sodium sulfide 300 g/ton (pH 7.5 of pulp), sweeping sodium sulfide 800 g/ton (pH 8.0 of pulp), other chemical conditions And its results are shown in Table 1. The test results in Table 1 show that the 6-hydrocarbyl-1,2,4,5-tetrazolium-3-thione collector achieved higher copper recovery (sweep concentrate) than butyl xanthate.
表1 6-烃基-1，2，4，5-四唑-3-硫酮浮选云南东川硫化-氧化铜矿条件及其结果Table 1 Conditions and results of flotation of 6-hydrocarbyl-1,2,4,5-tetrazole-3-thione sulfide-copper oxide ore in Dongchuan, Yunnan
实施例4Example 4
西藏昌都某氧化-硫化铜矿样，原矿含Cu 3.9％，其氧化率为69.4％，主要的氧化铜矿物为孔雀石与蓝铜矿。试验流程：一次粗选一次扫选。磨矿细度：-0.074mm占80％；药剂条件：粗选硫化钠3000克/吨(矿浆的pH8.5)，扫选硫化钠1000克/吨(矿浆的pH9.0)，其余药剂条件及其结果见表2。表2的试验结果表明，6-烃基-1，2，4，5-四唑-3-硫酮捕收剂取得了比异戊基黄药以及异戊基黄药+辛基羟肟酸更高的铜回收率(扫选精矿)。An oxide-sulfide copper ore sample in Qamdo, Tibet, the original ore contains 3.9% Cu, and its oxidation rate is 69.4%. The main copper oxide minerals are malachite and azurite. Test process: one rough selection and one sweep. Grinding fineness: -0.074mm accounts for 80%; chemical conditions: roughing sodium sulfide 3000 g/ton (pH 8.5 of pulp), sweeping sodium sulfide 1000 g/ton (pH 9.0 of pulp), other chemical conditions And its results are shown in Table 2. The test result of table 2 shows, 6-hydrocarbyl-1,2,4,5-tetrazolium-3-thione collector has obtained more than isoamyl xanthate and isoamyl xanthate+octyl hydroxamic acid High copper recovery (sweep concentrate).
表2西藏昌都氧化-硫化铜矿条件及其结果Table 2 Conditions and results of oxidation-sulfide copper deposit in Qamdo, Tibet
实施例5Example 5
江西上饶某斑岩铜矿石矿样，原矿含铜0.39％，含硫1.85％，含金0.21g/t，含银1.18g/t。试验流程：一次粗选；磨矿细度：-0.074mm占68％；药剂条件：石灰用量800克/吨，矿浆pH值为8.5，其余药剂条件及其结果见表3。表3的试验结果表明，本发明的6-庚基-1，2，4，5-四唑-3-硫酮+丁黄药组合捕收剂取得比常用捕收剂丁黄药以及3-己基-4-氨基-1，2，4-三唑-5-硫酮+丁黄药更高的铜、金、银浮选回收率(粗精矿)。A porphyry copper ore sample in Shangrao, Jiangxi Province, the raw ore contains 0.39% copper, 1.85% sulfur, 0.21g/t gold, and 1.18g/t silver. Test process: primary roughing; grinding fineness: -0.074mm, accounting for 68%; chemical conditions: lime dosage 800 g/ton, pulp pH value 8.5, other chemical conditions and their results are shown in Table 3. The test result of table 3 shows, 6-heptyl-1 of the present invention, 2,4,5-tetrazolium-3-thione+dixanthate combined collector obtains than common collector dixanthate and 3- Hexyl-4-amino-1,2,4-triazole-5-thione + butyl xanthate Higher copper, gold, silver flotation recovery (coarse concentrate).
表3江西上饶斑岩铜矿条件及其结果Table 3 Conditions and results of the porphyry copper deposit in Shangrao, Jiangxi
*单位g/t*unit g/t
综上，采用所述的1，2，4，5-四唑-3-硫酮类化合物作为捕收剂能有效提高含铜矿物、银矿物、金矿物的至少一种矿石中有价金属的富集和回收效率。In summary, the use of the 1,2,4,5-tetrazole-3-thione compound as a collector can effectively increase the amount of valuable metals in at least one ore containing copper minerals, silver minerals, and gold minerals. enrichment and recovery efficiency.
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