WO2018053948A1 - 一种含唑硫酮结构的浮选捕收剂的应用 - Google Patents

一种含唑硫酮结构的浮选捕收剂的应用 Download PDF

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WO2018053948A1
WO2018053948A1 PCT/CN2016/109394 CN2016109394W WO2018053948A1 WO 2018053948 A1 WO2018053948 A1 WO 2018053948A1 CN 2016109394 W CN2016109394 W CN 2016109394W WO 2018053948 A1 WO2018053948 A1 WO 2018053948A1
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group
formula
flotation collector
flotation
collector according
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French (fr)
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刘广义
黄耀国
麻龙群
牛晓雪
刘俊
钟宏
胡哲
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中南大学
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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
    • B03D1/00—Flotation
    • B03D1/02—Froth-flotation processes
    • 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
    • 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
    • B03D2203/025—Precious metal ores

Definitions

  • the invention belongs to the field of metal beneficiation, and particularly relates to the application of a flotation collector containing an oxazolidine structure.
  • Azonethione compounds 1,3,4-thiadiazole-2-thione, 1,3,4-oxadiazole-2-thione, 1,2,4-triazole-3-thione or 1,2,4,5-tetrazole-3-thione contains a strong coordination ability of N, S atoms, can be used as a ligand to chelate copper, silver and other metal ions, used as a metal corrosion inhibitor.
  • oxathione compounds are generally biologically active and are widely used as herbicides, anthelmintics, plant growth regulators, fungicides, anti-inflammatory agents, and the like.
  • oxathione compounds can be prepared according to the synthetic methods reported in the literature.
  • This route is a three-step synthesis of 1,3,4-thiadiazole-2-thione compounds.
  • a hydrazide compound is prepared, and an organic amide dithiocarbamate is prepared by reacting a hydrazide compound with carbon disulfide and a base.
  • the obtained organic amide dithiocarbamate is in the presence of concentrated sulfuric acid.
  • Low temperature cyclization to obtain 1,3,4-thiadiazole-2-thione compounds Li Zhancai, Li Shuzhen, Fang Shaoming, Hou Shoujun, Nie Xiaobing, Lin Wei. 5-Methyl-1,3,4-thiadiazole Synthesis of -2-thione [J].
  • the preparation method of 1,3,4-oxadiazole-2-thione is mainly prepared by refluxing a hydrazide as a raw material with KOH and CS 2 in a suitable solvent (e.g., Reaction Formula 2).
  • Li et al. use a substituted aryl hydrazide, CS 2 , KOH as a raw material, and ethanol as a solvent, and reflux reaction for 8 hours to obtain 5-phenyl-1,3,4-oxadiazol-2-thione (Y). .Li,J.Liu,H.Zhang,et al. Stereoselective synthesis and fungicidal activities of(E)- ⁇ -(methoxyimino)-benzeneacetate derivatives containing 1,3,4-oxadiazole ring[J].Bioorganic&medicinal chemistry letters,2006 , 16(8): 2278-2282.).
  • 1,2,4-triazole-3-thione compounds is mainly carried out by heating and refluxing the acylthiosemicarbazide in an alkaline medium. Hoggarth refluxed the aroyl thiosemicarbazide in a solution of sodium alkoxide in ethanol and then acidified to synthesize a 5-substituted aryl-1,2,4-triazole-3-thione compound (Hoggarth E..Compounds related to thiosemicarbazide. Part II. 1-Benzoylthiosemicarbazides [J]. Journal of the Chemical Society, 1949: 1163-1167).
  • El-Sayed is prepared by heating and refluxing the acylthiosemicarbazide in the presence of ethanol solution and potassium hydroxide to obtain 5-heptadecyl-1,2,4-triazole-3-thione (El-Sayed R..Substituted thiadiazole , oxadiazole, triazole and triazinone as antimicrobial and surface activity compounds [J]. J. Surfact Deterg, 2013, 16(1): 39–47). Kumsi et al. prepare an aroyl thiosemicarbazide intermediate by reacting an aryl hydrazide with potassium thiocyanate under acidic conditions.
  • the intermediate sodium hydroxide solution is reflux cyclized and then acidified to obtain a 5-substituted aryl-1.
  • 2,4-triazole-3-thione compounds (Kumsi M., Poojary. B, Lobo PL, et al. Synthesis of some fused triazole derivatives containing 4-isobutylphenylethyl and 4-methylthiophenyl moieties [J].Zeitschrift für Naturforschung B, 2010, 65(11): 1353-1358). Russo et al.
  • the 1,2,4,5-tetrazole-3-thione compounds are synthesized mainly by a thiourea route or a dithiosemicarbazide route. Gopalakrishnan et al. mixed aromatic aldehyde, thiourea and ammonium acetate in a ratio of 1:1:2 (molar ratio), and obtained 6-substituted phenyl-1,2,4 under NaHSO 4 ⁇ SiO 2 catalysis and microwave irradiation.
  • Tashtoush et al. react dithiosemicarbazide with a fatty aldehyde or cyclic ketone under acidic conditions to give 6-substituted-1,2,4,5-tetrazole-3-thione (Tashtoush HI, 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) . Tabassum et al.
  • Shang et al. prepared a complex of 5-(3-pyridyl)-1,3,4-oxadiazol-2-thione with Cu(I) and found N, 1,3,4-oxa on the pyridine ring. N and thiocarbonyl S in the oxadiazole ring are bonded to Cu atoms (J. Shang, XY Wu, F. Wang, et al. A new 3D Cu(I) coordination polymer with 4-connected umv topological network [J]. Inorganic Chemistry Communications, 2012, 22: 190-192.). Singh et al.
  • Gudasi et al. synthesized Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of 1,3,4-oxadiazole-2-thione K. Gudasi , M.Patil, R.Vadavi, et al..Transition metal complexes with a new tridentate ligand,5-[6-(5-mercapto-1,3,4-oxadiazol-2-yl)pyridin-2-yl] -1,3,4-oxadiazole-2-thiol [J]. J. Serb. Chem. Soc., 2007, 72(4): 357-366).
  • Singh B. and Singh R. studied transition metal ions such as Co(II), Ni(II) and Cu(II) with 5-(4-pyridine)-1,2,4-triazole-3-thione. Coordination mode of body (Singh B., Singh R..Transition metal Complexes of 3-(4-pyridyl)-triazoline-5-thione [J]. Journal of Inorganic and Nuclear Chemistry, 1972, 34(11): 3449-3454). Scozzafava et al.
  • the object of the present invention is to provide a flotation collector containing an oxathione structure in the flotation of metal minerals, aiming to improve the enrichment and recovery of valuable metals in ores containing copper, silver and gold minerals. effectiveness.
  • X is NH and Y is or
  • R is a C 1 -C 17 hydrocarbon group or an alkoxy ether group having the structure of formula 2;
  • R 1 is a C 1 -C 17 hydrocarbon group
  • R 2 is H or a C 1 -C 3 alkane group
  • n is an integer of 2 to 5;
  • R 4 is a hydrocarbon group of C 1 to C 17
  • R 3 is an ethylene group or a propylene group
  • m is 1 to 3.
  • the present inventors have found that a compound having a main core structure of Formula 1 is used as a flotation collector to contribute to the enrichment and recovery of valuable metals of copper minerals, silver minerals, and gold mineral ores.
  • X is NH, O or S; and the compound of the formula 1 is a five-membered ring azole thione collector. Further preferably, the C atom in Y is bonded to X, and under the preferred conditions, the flotation collector of the compound of the formula 1 has the structure of formula 3:
  • the structural compound of the formula 3 is specifically one of the compounds of the formulae formula 4, formula 5, and formula 6.
  • the floc collector having the azolethione having the structural formulas of Formula 4, Formula 5, and Formula 6 is applied to at least one ore containing a copper mineral, a silver mineral, or a gold mineral, and the valuable metal is recovered by flotation.
  • the structural formula of Formula 4 is a flotation collector having a 1,2,4-triazole-3-thione structure.
  • the structural formula of Formula 5 is a flotation collector having a 1,3,4-oxadiazol-2-thione structure.
  • the structural formula of Formula 6 is a flotation collector having 1,3,4-thiadiazole-2-thione.
  • the R group provides good hydrophobicity of the flotation collector.
  • the R is a hydrocarbon group of C 1 to C 17 , that is, the R is a hydrocarbon group having 1 to 17 carbon atoms.
  • R can be (1) a saturated alkane such as a linear or branched alkane; (2) an olefinic or olefinic alkyl group containing a single or multiple double bonds; (3) a saturated or unsaturated cycloalkane, a cycloalkane
  • the group is preferably a five- or six-membered ring; (4) an alkylaryl group or an arylalkyl group having an aromatic structure, such as an alkyl-substituted phenyl group, an alkyl-substituted fused ring aryl group, or a phenyl group or a fused ring.
  • Arylalkyl is a saturated alkane such as a linear or branched alkane.
  • R is a C 1 -C 17 alkane group, or a C 2 -C 17 olefin group, or a C 6 -C 12 aromatic hydrocarbon group.
  • the R is preferably a C 1 -C 17 alkane group, for example, a C 1 -C 17 linear alkyl group, or a C 1 -C 17 branched alkyl group.
  • R is a C 1 -C 17 linear alkane group.
  • R is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-decyl, n-dodeyl , Zheng Shiji, Zheng Xieji, Zhengjiji, Zhengliuji or Zhengqiji.
  • R is a C 10 to C 17 monoolefin group.
  • the C 10 -C 17 monoolefin group may be an alkyl olefin group (for example, an unsaturated double bond carbon directly bonded to a carbon on a 1,2,4-triazole ring) or an olefin alkyl group (for example, The unsaturated double bond carbon is linked by a saturated carbon and a 1,2,4-triazole ring).
  • R is 1-nonenyl or 3-enylthio.
  • R is propyl, pentyl, hexyl, heptyl, decyl, n-undecyl, n-tridecyl, n-pentadecyl, n-heptadecyl or 8-heptadecenyl.
  • the R may also be selected from the group of the structure of Formula 2.
  • the R 4 group is selected in the same range as R.
  • R 4 is a C 1 -C 17 alkane group, or a C 2 -C 17 olefin group, or a C 6 -C 12 aromatic hydrocarbon group.
  • the R 4 is a C 1 - C 17 linear alkane group or a C 10 - C 17 monoolefin group.
  • R 3 is an ethylene group.
  • R 3 is an ethylene group; and R 4 is a C 1 - C 17 linear alkane group or a C 10 - C 17 monoolefin group.
  • R 4 is propyl, pentyl, hexyl, heptyl, decyl, n-undecyl, n-tridecyl, n-pentadecyl, n-heptadecyl or 8- Heptadecyl.
  • the flotation collector is a 1,2,4,5-tetrazole-3-thione compound having the structure of formula 7;
  • the R 2 and R 1 groups of the compounds of formula 7 are used to provide good hydrophobicity of the collector.
  • R 1 is a hydrocarbon group of C 1 to C 17 , that is, the above R 1 is a hydrocarbon group having 1 to 17 carbon atoms.
  • R 1 may be (1) a saturated alkane such as a linear or branched alkane; (2) an olefinic or olefinic alkyl group containing a single or multiple double bonds; (3) a saturated or unsaturated cycloalkane, a ring
  • the alkane group is preferably a five- or six-membered ring; (4) an alkylaryl group or an arylalkyl group having an aromatic structure, such as an alkyl-substituted phenyl group, an alkyl-substituted fused ring aryl group, or a phenylalkyl group; , fused ring arylalkyl.
  • R 1 is a C 1 -C 17 alkane group, or a C 2 -C 17 olefin group, or a C 6 -C 12 aromatic hydrocarbon group.
  • the R 1 is preferably a C 1 -C 17 alkane group, for example, a C 1 - C 17 linear alkyl group, or a C 1 - C 17 branched alkyl group.
  • R 1 is a C 1 - C 17 linear alkane group.
  • R 1 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-decyl, n-xyl Base, positive thirteen base, positive fourteen base, positive fifteen base, positive sixteen base or positive seventeen base.
  • R 1 is a C 10 to C 17 monoolefin group.
  • the C 10 -C 17 monoolefin group may be an alkyl olefin group (the unsaturated double bond carbon is directly bonded to the carbon on the 1,2,4,5-tetrazole-3-thione core) or An olefin alkyl group (unsaturated double bond carbon is bonded through a saturated carbon and a 1,2,4,5-tetrazole-3-thione core).
  • R 1 is 1-nonenyl or 3-enylthio.
  • R 1 is a propyl group, a pentyl group, a hexyl group, a heptyl group or a decyl group.
  • Preferred groups are all linear groups.
  • R 2 is H, methyl, ethyl, propyl or isopropyl.
  • R 2 is H or a methyl group.
  • the flotation collector of the structural compound of formula 1 is a 1,2,4,5-tetrazole-3-thione compound having the structure of formula 8;
  • the saturated cycloalkane and the 6-position of the 1,2,4,5-tetrazole-3-thione core have a carbon atom to form a spiro ring structure; the spiro ring structure is used to provide The collector is well hydrophobic.
  • the saturated cycloalkane is preferably a five-membered, six-membered, seven-membered, eight-membered saturated cycloalkane, that is, an integer in which n is selected from 2-5.
  • n 3
  • a preferred application method is as follows: the flotation collector of the structure of the formula 1 (or at least one of the preferred compounds of the formula 4, formula 5, formula 6, formula 7, and formula 8) is used as Flotation collector and copper
  • the mineral pulp of minerals, silver minerals and gold minerals meets the purpose of efficiently recovering precious metals such as copper, silver and gold.
  • Step (1) the ore containing at least one of copper mineral, silver mineral and gold mineral is pulverized and pulped to obtain a slurry;
  • Step (2) adding a flotation agent to the slurry of the step (1) for flotation, collecting a flotation concentrate; and the flotation agent comprises the flotation collector.
  • the prior art is employed for the pulverization of the ore.
  • the ore is first crushed by a jaw crusher, a fine crusher, and then ground by a ball mill.
  • the flotation reagent may further comprise a flotation material such as a foaming agent and/or a regulator.
  • the ore slurry is adjusted to pH to obtain a slurry.
  • the flotation collector is added in an amount of 10 to 500 g/t based on the weight of the ore. More preferably, it is 40-100 g/t.
  • the 1,3,4-thiadiazole-2-thione compound of the present invention (the structural compound of the formula 6) can be cooled ( ⁇ 5 ° C) by the corresponding organic amide dithiocarbamate in the presence of concentrated sulfuric acid. Prepared by a cyclization reaction;
  • 1,3,4-oxadiazole-2-thione compound (structural compound of formula 5) can be heated and refluxed by a corresponding N-(N'-carboxamide) dithiocarbamate in a solvent medium and then acidified Preparing or directly hydrating the hydrazide with KOH and CS 2 in an organic solvent and then acidifying;
  • 1,2,4-triazole-3-thione compound (structure compound of formula 4) can be obtained by heating and refluxing acylthiosemicarbazide in an alkaline medium, followed by acidification;
  • 1,2,4,5-tetrazole-3-thione compounds (compounds of the formula 7 and formula 8) can be heated by the corresponding organic aldehyde or ketone with dithiosemicarbazide in an organic medium in the presence of acetic acid. The reaction is prepared.
  • the collector of the invention can improve the flotation index and improve the flotation recovery of metal minerals.
  • every percentage point increase in flotation recovery is a huge improvement, and it can generate tens of billions of economic value for the global mining industry.
  • the present invention is the first to apply an oxazolidone compound to a valuable metal flotation and collection in minerals, and is particularly suitable for enrichment and recovery of valuable metals in ores containing copper, silver or gold minerals. Compared with the existing common collectors, the recovery rate of valuable metals can be improved.
  • Figure 1 is a 1 H NMR chart of 5-phenyl-1,3,4-thiadiazole-2-thione
  • Figure 2 is a 1 H NMR chart of 5-heptyl-1,3,4-thiadiazole-2-thione
  • Figure 3 is a 1 H NMR chart of 5-phenyl-1,3,4-oxadiazol-2-thione
  • Figure 4 is a 1 H NMR chart of 5-pentyl-1,2,4-triazole-3-thione
  • Figure 5 is a 1 H NMR chart of 5-heptyl-1,2,4-triazole-3-thione
  • Figure 6 is a 1 H NMR chart of 6-hexyl-1,2,4,5-tetrazole-3-thione
  • each flotation agent of the following examples is g/t, and is based on the ore weight (t) unless otherwise specified.
  • the concentration of the fixed foaming agent methyl isobutyl methoxide (MIBC) was 15 mg/L, the flow rate of N 2 gas was 200 mL/min, and the particle size was -0.076 mm under a certain concentration of collector and slurry pH.
  • the chalcopyrite of ⁇ +0.038mm was floated in a single bubble tube for 3 minutes, and the recovery rate of chalcopyrite was shown in Table 1.
  • the test results in Table 1 show that the oxazolyl collector has a higher chalcopyrite recovery than the isoamyl xanthate.
  • the concentration of fixed foaming agent MIBC is 15mg/L
  • the flow rate of N 2 gas is 200mL/min
  • the malachite with particle size of -0.076mm ⁇ +0.038mm is Flotation in a single bubble tube for 3 minutes
  • the flotation recovery rate of malachite is shown in Table 2.
  • the test results in Table 2 show that the oxazolidone collector achieved a higher recovery rate of malachite flotation than the isoamyl xanthate and octyl hydroxamic acid.
  • Test procedure one rough selection and one sweep. Grinding fineness: -0.074mm accounted for 90%;
  • Pharmaceutical conditions coarse selection of sodium sulfide 300 g / ton (pH 7.5 of the pulp), sweeping sodium sulfide 800 g / ton (pH 8.0 of the pulp), the remaining pharmaceutical conditions
  • Table 3 The test results of Table 3 show that the azolethione collector of the present invention achieves a higher copper recovery (sweep concentrate) than Dinghuang.
  • the test results of Table 5 show that the azole thione compound + butyl sulphate combination collector of the present invention obtains more than the commonly used collector dicamba and 3-hexyl-4-amino-1,2,4-triazole- 5-thione + butyl xanthate higher copper, gold, silver flotation recovery (coarse concentrate).
  • the use of the flotation collector of the present invention can effectively increase the enrichment and recovery efficiency of valuable metals in at least one ore of copper-containing minerals, silver minerals, and gold minerals.

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Abstract

一种唑硫酮类浮选捕收剂的应用，该应用是将唑硫酮类化合物：1,3,4-噻二唑-2-硫酮、1,3,4-噁二唑-2-硫酮、1,2,4-三唑-3-硫酮或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，有效地改善了铜、银或金矿物的富集和回收。

Description

一种含唑硫酮结构的浮选捕收剂的应用 技术领域
本发明属于金属选矿领域，具体涉及含唑硫酮结构的浮选捕收剂的应用。
背景技术
唑硫酮类化合物：1,3,4-噻二唑-2-硫酮、1,3,4-噁二唑-2-硫酮、1,2,4-三唑-3-硫酮或1,2,4,5-四唑-3-硫酮含有较强配位能力的N、S原子，可作为配体螯合铜、银等金属离子，用作金属缓蚀剂。此外，唑硫酮类化合物普遍具有生物活性，广泛用作除草剂、驱虫药、植物生长调节剂、杀菌剂，消炎剂等。
唑硫酮类化合物的可根据文献报道的合成方法制备。
1,3,4-噻二唑-2-硫酮类化合物常用的合成路线如反应式1所示。
Figure PCTCN2016109394-appb-000001
该路线经三步合成1,3,4-噻二唑-2-硫酮类化合物。先是制备酰肼类化合物，再由酰肼类化合物与二硫化碳和碱反应制备有机酰胺基二硫代氨基甲酸盐，最后，制得的有机酰胺基二硫代氨基甲酸盐在浓硫酸存在下低温环合得到1,3,4-噻二唑-2-硫酮类化合物(李占才,李淑勉,方少明,侯守君,聂晓兵,林烨.5-甲基-1,3,4-噻二唑-2-硫酮的合成[J].化学研究与应用,1997,9(5):91-93；Saha A,Kumar R,Kumar R,et al.Green synthesis of 5-substituted-1,3,4-thiadiazole-2-thiols as new potent nitrification inhibitors[J].Journal of Heterocyclic Chemistry,2010,47(4):838-845)。
1,3,4-噁二唑-2-硫酮的制备方法主要是以酰肼为原料，在适当的溶剂中与KOH、CS2回流反应而制得(如反应式2)。
Figure PCTCN2016109394-appb-000002
Li等以含有取代基的芳香酰肼、CS2、KOH为原料，以乙醇作为溶剂，回流反应8h，制得5-苯基-1,3,4-噁二唑-2-硫酮(Y.Li,J.Liu,H.Zhang,et al. Stereoselective synthesis and fungicidal activities of(E)-α-(methoxyimino)-benzeneacetate derivatives containing 1,3,4-oxadiazole ring[J].Bioorganic&medicinal chemistry letters,2006,16(8):2278-2282.)。Farghaly和El-Kashef以吡啶为溶剂，将酰肼与CS2直接反应，通过加热回流制得1,3,4-噁二唑-2-硫酮(A.R.Farghaly,H.El-Kashef.Synthesis of some new azoles with antiviral potential[J].Arkivoc,2006,11:76-90.)。另外，Rahman等在ZnCl2的作用下将酰肼二硫代氨基甲酸酯转化为相应的1,3,4-噁二唑-2-硫酮(如反应式3)(M.A.Rahman,M.R.Karim,M.Arifuzzaman,et al.ZnCl2catalyzed efficient synthesis of 1,3,4-oxadiazole and 1,3,4-thiadiazole[J].Tetrahedron Letters,2014,55(21):3267-3273.)。
Figure PCTCN2016109394-appb-000003
1,2,4-三唑-3-硫酮类化合物的合成主要通过碱性介质中加热回流环化酰基氨基硫脲而制备。Hoggarth在醇钠的乙醇溶液中回流芳酰基氨基硫脲，然后酸化合成了5-取代芳基-1,2,4-三唑-3-硫酮类化合物(Hoggarth E..Compounds related to thiosemicarbazide.Part II.1-Benzoylthiosemicarbazides[J].Journal of the Chemical Society,1949:1163-1167)。El-Sayed在乙醇溶液和氢氧化钾存在下，加热回流酰基氨基硫脲制备得到5-十七烷基-1,2,4-三唑-3-硫酮(El-Sayed R..Substituted thiadiazole,oxadiazole,triazole and triazinone as antimicrobial and surface activity compounds[J].J.Surfact Deterg,2013,16(1):39–47)。Kumsi等通过芳基酰肼与硫氰酸钾在酸性条件下反应制备芳酰基氨基硫脲中间体，该中间体氢氧化钠溶液中回流环化后，再酸化制备得到5-取代芳基-1,2,4-三唑-3-硫酮类化合物(Kumsi M.,Poojary.B,Lobo P.L.,et al.Synthesis of some fused triazole derivatives containing 4-isobutylphenylethyl and 4-methylthiophenyl moieties[J].Zeitschrift für Naturforschung B,2010,65(11):1353-1358)。Russo等通过酰肼和硫氰酸铵制备酰基氨基硫脲中间体，然后碱性条件下加热回流氨基硫脲类中间体合成1,2,4-三唑-3-硫酮(Russo F.,Santagat M.,Pappalar G..Benzothiazoles derivatives of 1,2,4-triazole[J].Annali Di Chimica,1972,62(5):351)。
1,2,4,5-四唑-3-硫酮类化合物的主要通过硫脲路线或二氨基硫脲路线合成。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 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 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)。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 antimicrobial activity[J].Journal of Molecular Structure,2012,1020:33-40)。
唑硫酮类化合物与铜、金或银的螯合作用也有文献报道。
Mashhadizadeha等报道了1,3,4-噻二唑-2-硫酮类化合物可与Cu(II)形成螯合物(M.H.Mashhadizadeh,K.Eskandari,A.Foroumadi,A.Shafiee.Copper(II)modified carbon paste electrodes based on self-assembled mercapto compounds-gold-nanoparticle[J].Talanta,2008,76(3):497-502)。Kannan和John合成了5-甲基-1,3,4-噻二唑-2-硫酮金纳米粒子(P.Kannan and S.A.John.Synthesis of mercaptothiadiazole-functionalized gold nanoparticles and their self-assembly on Au substrates[J].Nanotechnology 2008,19(8):085602)。Matsumoto等发现5-甲基-1,3,4-噻二唑-2-硫酮通过化学键自组装于金和铜电极表面(F.Matsumoto,M.Ozaki,Y.Inatomi,S.C.Paulson,N.Oyama.Studies on the adsorption behavior of 2,5-dimercapto-1,3,4-thiadiazole and 2-mercapto-5-methyl-1,3,4-thiadiazole at gold and copper electrode surfaces[J].Langmuir 1999,15(3):857-865)。Blajiev等报道了5-甲基-1,3,4-噻二唑-2-硫酮可与铜形成螯合物，对铜表面起缓蚀作用(O.L.Blajiev,T.Breugelmans,R.Pintelon,H.Terryn,A.Hubin.Potentiodynamic EIS investigation of the  2-methyl-5-mercapto-1,3,4-thiadiazole adsorption on copper[J].Electrochimica Acta,2008,53(25):7451-7459)。
Shang等制得了5-(3-吡啶基)-1,3,4-噁二唑-2-硫酮与Cu(I)的配合物，发现吡啶环上的N、1,3,4-噁二唑环中N以及硫代羰基S与Cu原子结合(J.Shang,X.Y.Wu,F.Wang,et al.A new 3D Cu(I)coordination polymer with 4-connected umv topological network[J].Inorganic Chemistry Communications,2012,22:190-192.)。Singh等合成了5-(4-吡啶基)-1,3,4-噁二唑-2-硫酮及其与Cu(II)、Ni(II)的配合物(N.K.Singh,M.K.Bharty,R.Dulare,et al.Synthesis and X-ray crystallographic studies of Ni(II)and Cu(II)complexes of[5-(4-pyridyl)-1,3,4]oxadiazole-2-thione/thiol formed by transformation of N-(pyridine-4-carbonyl)-hydrazine carbodithioate in the presence of ethylenediamine[J].Polyhedron,2009,28(12):2443-2449.)。Al-obaidi等合成了5-取代苯基-1,3,4-噁二唑-2-硫酮，发现其通过1,3,4-噁二唑上的N和硫酮S与Cu(I)、Cu(II)发生配位作用(如式a)(K.H.Al-Obaidi,B.F.Ali,R.Abu-El-Halawa,et al.Synthesis of 1,3,4-mercapto-oxadiazole mono-and dinuclear copper(I)and copper(II)complexes and their microbiological activity[J].Transition metal chemistry,2004,29(7):804-811.)。
Figure PCTCN2016109394-appb-000004
Gudasi等合成了1,3,4-噁二唑-2-硫酮的Mn(II),Co(II),Ni(II),Cu(II)和Zn(II)络合物(K.Gudasi,M.Patil,R.Vadavi,et al..Transition metal complexes with a new tridentate ligand,5-[6-(5-mercapto-1,3,4-oxadiazol-2-yl)pyridin-2-yl]-1,3,4-oxadiazole-2-thiol[J].J.Serb.Chem.Soc.,2007,72(4):357-366)。Xavier和Nallaiyan认为5-(2,6-二苯基-4-亚肼基-吡啶-1-亚甲基)-1,3,4-噁二唑-2-硫酮能延缓铜的腐蚀(J.R.Xavier,R.Nallaiyan.Corrosion inhibitive properties and electrochemical adsorption behaviour of some piperidine derivatives on brass in natural sea water[J].Journal of Solid State Electrochemistry,2012,16(1):391-402.)。
Singh B.和Singh R.研究了Co(II),Ni(II)and Cu(II)等过渡金属离子与5-(4-吡啶)-1,2,4-三唑-3-硫酮配体的配位方式(Singh B.,Singh R..Transition metal  complexes of 3-(4-pyridyl)-triazoline-5-thione[J].Journal of Inorganic and Nuclear Chemistry,1972,34(11):3449-3454)。Scozzafava等研究4,5-二取代-1,2,4-三唑-3-硫酮与Zn(II),Hg(II)and Cu(I)螯合物的结构(Scozzafava A.,Cavazza C.,Supuran C.T.,et al.Complexes with biologically active ligands.Part 11.Synthesis and carbonic anhydrase inhibitory activity of metal complexes of 4,5-disubstituted-3-mercapto-1,2,4-triazole derivatives[J].Metal-based drugs,1998,5(1):11-18)。Pergolese和Bigotto认为1,2,4-三唑-3-硫酮以其电离的硫醇形式通过硫、氮的孤对电子与银结合而吸附在银表面(Pergolese B.,Bigotto A..Study by SERS spectroscopy of the adsorption of 1H-1,2,4-triazole-3-thione on silver sols[J].Journal of Molecular Structure,2003,651–653:349–352)。O'Neil和Phillips发现1,2,4-三唑-3-硫酮类化合物对铜的腐蚀具有良好抑制作用(O'Neil R.M.,Phillips E..Corrosion inhibition[P],GB2182030A,1987.5.7)。
Figure PCTCN2016109394-appb-000005
等发现在1,2,4,5-四唑-3-硫酮的过渡金属Cu(I)、Ag(I)、Au(I)、Au(II)和Pd(II)配合物中，金属优先与配体中的硫原子配位(
Figure PCTCN2016109394-appb-000006
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 azathione 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唑硫酮类化合物用作浮选捕收剂的报道。
发明内容
本发明的目的是在于提供一种含唑硫酮结构的浮选捕收剂在金属矿物浮选方面的应用，旨在提高含铜、银、金矿物的矿石中有价金属的富集和回收效率。
一种含唑硫酮结构的浮选捕收剂的应用，将具有式1结构的唑硫酮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；
Figure PCTCN2016109394-appb-000007
Figure PCTCN2016109394-appb-000008
其中，X为NH、O或S，Y为
Figure PCTCN2016109394-appb-000009
或者，
X为NH，Y为
Figure PCTCN2016109394-appb-000010
或
Figure PCTCN2016109394-appb-000011
R为C1～C17的烃基，或具有式2结构的烷氧醚基；
Figure PCTCN2016109394-appb-000012
R1为C1～C17的烃基；R2为H、或者为C1～C3的烷烃基；
n为2～5的整数；
式2中，R4为C1～C17的烃基，R3为亚乙基或亚丙基，m为1～3。
本发明人发现，将具有式1主核结构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。
式1结构化合物中，根据Y的基团的不同，可分为五元环的唑硫酮类捕收剂或六元环的四唑硫酮类捕收剂。
本发明的一种优选的实施方案(方案a)：Y为
Figure PCTCN2016109394-appb-000013
当Y为
Figure PCTCN2016109394-appb-000014
的基团时，X为NH、O或S；所述的式1化合物为五元环的唑硫酮类捕收剂。进一步优选，Y中的C原子和X连接，在该优选条件下，式1结构的化合物的浮选捕收剂具有式3结构：
Figure PCTCN2016109394-appb-000015
所述的式3结构化合物具体为式4、式5、式6结构式的化合物中的一种。将具有式4、式5、式6结构式的唑硫酮类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。
Figure PCTCN2016109394-appb-000016
式4结构式为具有1,2,4-三唑-3-硫酮结构的浮选捕收剂。
Figure PCTCN2016109394-appb-000017
式5结构式为具有1,3,4-噁二唑-2-硫酮结构的浮选捕收剂。
Figure PCTCN2016109394-appb-000018
式6结构式为具有1,3,4-噻二唑-2-硫酮的浮选捕收剂。
所述的式3化合物中，R基团提供所述浮选捕收剂良好的疏水性。
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、稠环芳基烷基。
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。
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。
进一步优选，R为C1～C17的直链烷烃基。
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。
作为优选，R为C10～C17单烯烃基。
所述的C10～C17单烯烃基中，可以为烷基烯烃基(例如，不饱和双键碳直接 和1,2,4-三唑环上的碳连接)或者烯烃烷基(例如，不饱和双键碳通过饱和碳和1,2,4-三唑环连接)。例如，R为1-壬烯基或3-烯壬基。
作为优选，R为丙基、戊基、己基、庚基、壬基，正十一烷基、正十三烷基、正十五烷基、正十七烷基或8-十七烯基。
所述的R还可选自式2结构的基团。R4基团的选取范围和R相同。
作为优选，式2中，R4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。
进一步优选，所述的R4为C1～C17的直链烷烃基或C10～C17单烯烃基。
作为优选，式2中，R3为亚乙基。
进一步优选，式2中，R3为亚乙基；R4为C1～C17的直链烷烃基或C10～C17单烯烃基。
作为优选，式2中，R4为丙基、戊基、己基、庚基、壬基，正十一烷基、正十三烷基、正十五烷基、正十七烷基或8-十七烯基。
本发明的另一种优选方案(方案b)，X为NH，Y为
Figure PCTCN2016109394-appb-000019
或
Figure PCTCN2016109394-appb-000020
当X为NH，Y为
Figure PCTCN2016109394-appb-000021
所述的浮选捕收剂为具有式7结构的1,2,4,5-四唑-3-硫酮类化合物；
Figure PCTCN2016109394-appb-000022
所述的式7化合物中的R2和R1基团用于提供所述捕收剂良好的疏水性。
所述的R1为C1～C17的烃基，也即是所述的R1为碳原子数为1～17的碳氢基团。例如：R1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。
作为优选，R1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。
所述的R1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。
进一步优选，式7中，R1为C1～C17的直链烷烃基。
例如，R1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。
作为优选，式7中，R1为C10～C17单烯烃基。
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，R1为1-壬烯基或3-烯壬基。
更为优选，式7中，R1为丙基、戊基、己基、庚基或壬基。所优选的基团均为直链基团。
式7中，R2为H、甲基、乙基、丙基或异丙基。
作为优选，式7中，R2为H或甲基。
当X为NH，Y为
Figure PCTCN2016109394-appb-000023
所述的式1结构化合物的浮选捕收剂为具有式8结构的1,2,4,5-四唑-3-硫酮类化合物；
Figure PCTCN2016109394-appb-000024
式8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；所述的螺环结构用于提供所述捕收剂良好的疏水性。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。
作为优选，式8中，n为3。
本发明中，一种优选的应用方法，将所述的式1结构的浮选捕收剂(或者为优选的式4、式5、式6、式7、式8化合物的至少一种)作为浮选捕收剂和含铜 矿物、银矿物、金矿物的矿浆接触，达到高效回收的铜、银、金等贵金属的目的。
作为本发明的优选方案，包括以下步骤：
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；
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浮选捕收剂。
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。
作为优选，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。
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在中性或碱性，优选pH为7-13；进一步优选8-10；更为优选8.5-9。
作为优选，步骤(1)中，以所述的矿石重量为基准，所述的浮选捕收剂的投加量为10-500g/t。进一步优选为40-100g/t。
本发明的1,3,4-噻二唑-2-硫酮类化合物(式6结构化合物)可通过相应的有机酰胺基二硫代氨基甲酸盐在浓硫酸存在下低温(<5℃)环合反应制得；
1,3,4-噁二唑-2-硫酮类化合物(式5结构化合物)可通过相应的N-(N'-烃酰胺)二硫代氨基甲酸盐在溶剂介质中加热回流然后酸化制得或直接在有机溶剂中将酰肼与KOH、CS2回流反应后酸化制得；
1,2,4-三唑-3-硫酮类化合物(式4结构化合物)可通过碱性介质中加热回流环化酰基氨基硫脲，然后酸化制得；
1,2,4,5-四唑-3-硫酮类化合物(式7和式8结构化合物)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。
本发明的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。
本发明的有益效果：本发明首次将唑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。
附图说明
图1为5-苯基-1,3,4-噻二唑-2-硫酮1H NMR图；
图2为5-庚基-1,3,4-噻二唑-2-硫酮1H NMR图；
图3为5-苯基-1,3,4-噁二唑-2-硫酮1H NMR图；
图4为5-戊基-1,2,4-三唑-3-硫酮1H NMR图；
图5为5-庚基-1,2,4-三唑-3-硫酮1H NMR图；
图6为6-己基-1,2,4,5-四唑-3-硫酮1H NMR图；
具体实施方式
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。
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，只是采用本发明的唑硫酮类化合物替换常规捕收剂。
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。
实施例1纯黄铜矿单泡管浮选试验
在一定浓度的捕收剂和矿浆pH值条件下，固定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的黄铜矿在单泡管中浮选3分钟，黄铜矿的浮选回收率见表1。表1的试验结果表明，唑硫酮类捕收剂取得了比异戊基黄药更高的黄铜矿回收率。
表1纯黄铜矿单泡管浮选试验条件与结果
Figure PCTCN2016109394-appb-000025
实施例2纯孔雀石单泡管浮选试验
在一定浓度的捕收剂和矿浆pH值条件下，固定起泡剂MIBC的浓度为15mg/L，N2气流速为200mL/min，对粒径为-0.076mm～+0.038mm的孔雀石在单泡管中浮选3分钟，孔雀石的浮选回收率见表2。表2的试验结果表明，唑硫酮类捕收剂取得了比异戊基黄药和辛基羟肟酸更高的孔雀石浮选回收率。
表2纯孔雀石单泡管浮选试验条件与结果
Figure PCTCN2016109394-appb-000026
Figure PCTCN2016109394-appb-000027
实施例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3。表3的试验结果表明，本发明的唑硫酮类捕收剂取得了比丁黄药更高的铜回收率(扫选精矿)。
表3唑硫酮类捕收剂浮选云南东川硫化-氧化铜矿条件及其结果
Figure PCTCN2016109394-appb-000028
Figure PCTCN2016109394-appb-000029
实施例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4。表4的试验结果表明，唑硫酮类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)。
表4西藏昌都氧化-硫化铜矿条件及其结果
Figure PCTCN2016109394-appb-000030
Figure PCTCN2016109394-appb-000031
实施例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5。表5的试验结果表明，本发明的唑硫酮类化合物+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)。
表5江西上饶斑岩铜矿条件及其结果
Figure PCTCN2016109394-appb-000032
Figure PCTCN2016109394-appb-000033
*单位g/t
综上，采用本发明所述的浮选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。

Claims (18)

  1. 一种含唑硫酮结构的浮选捕收剂的应用，其特征在于，将具有式1结构的唑硫酮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；
    Figure PCTCN2016109394-appb-100001
    其中，X为NH、O或S，Y为
    Figure PCTCN2016109394-appb-100002
    或者，
    X为NH，Y为
    Figure PCTCN2016109394-appb-100003
    R为C1～C17的烃基，或具有式2结构的烷氧醚基；
    Figure PCTCN2016109394-appb-100004
    R1为C1～C17的烃基；R2为H、或者为C1～C3的烷烃基；
    n为2～5的整数；
    式2中，R4为C1～C17的烃基，R3为亚乙基或亚丙基，m为1～3。
  2. 如权利要求1所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，式1结构的浮选捕收剂具有式3结构：
    Figure PCTCN2016109394-appb-100005
  3. 如权利要求2所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，式1结构的浮选捕收剂具有式4结构：
    Figure PCTCN2016109394-appb-100006
    Figure PCTCN2016109394-appb-100007
  4. 如权利要求2所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，式1结构的浮选捕收剂具有式5结构：
    Figure PCTCN2016109394-appb-100008
  5. 如权利要求2所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，式1结构的浮选捕收剂具有式6结构：
    Figure PCTCN2016109394-appb-100009
  6. 如权利要求1～5任一项所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，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。
  7. 如权利要求6所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，R为C1～C17的直链烷烃基；或者为C10～C17单烯烃基。
  8. 如权利要求7所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，R为丙基、戊基、己基、庚基、壬基，正十一烷基、正十三烷基、正十五烷基、正十七烷基或8-十七烯基。
  9. 如权利要求1～5任一项所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，式2中，R3为亚乙基。
  10. 如权利要求1～5任一项所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，R4为C1～C17的直链烷烃基或C10～C17单烯烃基。
  11. 如权利要求10所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，式2中，R4为丙基、戊基、己基、庚基、壬基，正十一烷基、正十三烷基、正十五烷基、正十七烷基或8-十七烯基。
  12. 如权利要求1所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，所述的浮选捕收剂为具有式7结构的1,2,4,5-四唑-3-硫酮类化合物：
    Figure PCTCN2016109394-appb-100010
    或为具有式8结构的1,2,4,5-四唑-3-硫酮类化合物：
    Figure PCTCN2016109394-appb-100011
  13. 如权利要求12所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，R1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。
  14. 如权利要求13所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，R1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。
  15. 如权利要求12或13所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，R2为H、甲基、乙基、丙基或异丙基。
  16. 如权利要求12所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，R1为丙基、戊基、己基、庚基或壬基；R2为H或甲基。
  17. 如权利要求12所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，式8所示的化合物中n为3。
  18. 如权利要求1-17任一项所述的含唑硫酮结构的浮选捕收剂的应用，其特征在于，包括以下步骤：
    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；
    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浮选捕收剂。
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