WO2019223290A1 - 一种制备硫氨酯并联产2-巯基乙醇或o-烷硫基乙基黄原酸盐的方法 - Google Patents

一种制备硫氨酯并联产2-巯基乙醇或o-烷硫基乙基黄原酸盐的方法 Download PDF

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WO2019223290A1
WO2019223290A1 PCT/CN2018/119879 CN2018119879W WO2019223290A1 WO 2019223290 A1 WO2019223290 A1 WO 2019223290A1 CN 2018119879 W CN2018119879 W CN 2018119879W WO 2019223290 A1 WO2019223290 A1 WO 2019223290A1
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formula
reaction
xanthate
thiourethane
alkyl
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PCT/CN2018/119879
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French (fr)
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钟宏
黄小平
王帅
曹占芳
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中南大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/02—Monothiocarbamic acids; Derivatives thereof
    • C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms
    • 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
    • B03D1/012—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/12—Dithiocarbonic acids; Derivatives thereof
    • C07C329/14—Esters of dithiocarbonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/12—Dithiocarbonic acids; Derivatives thereof
    • C07C329/14—Esters of dithiocarbonic acids
    • C07C329/16—Esters of dithiocarbonic acids having sulfur atoms of dithiocarbonic groups bound to acyclic carbon atoms
    • 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
    • B03D2203/04—Non-sulfide ores

Definitions

  • the invention belongs to the technical field of mineral collection, and in particular relates to a method for preparing thiourethane and producing 2-mercaptoethanol in parallel and a novel O-alkylthioethylxanthate collector.
  • Foam flotation is an important technology for mineral recovery.
  • the addition of flotation agents has changed the physical and chemical properties of the mineral surface, so that hydrophobic mineral particles are concentrated in the foam layer, and hydrophilic mineral particles are deposited in the flotation. Machine bottom to achieve mineral separation.
  • Flotation collector is a key technology for the efficient development and utilization of minerals. Since Keller first used xanthate as a flotation collector for sulfide ore in 1925, xanthate has become the main flotation collector for sulfide ore. It is still the most widely used sulfide ore flotation collector.
  • Thiourethane is a type of sulfur ore flotation collector with better selectivity than xanthate and black drug. It can achieve the flotation separation of minerals in lower pH media. Sulfide ore flotation has been widely used, and it is a very useful sulfide ore flotation collector.
  • thiourethanes There are many synthetic methods of thiourethanes, mainly including one-step catalytic synthesis method, isothiocyanate method, dimethyl sulfate method, xanthate esterification ammonolysis method (thiourethane synthesis process and by-product development Research [D]. Central South University. 2003).
  • the one-step catalytic method (US patent US5041599, German patent DE2408550) has a simple process, few reaction steps, and the product can be obtained in one step. The reaction enters the water phase completely, it is not easy to recycle, and a large amount of industrial wastewater is generated, which pollutes the environment. Therefore, this method is rarely used in industry to produce thiourethane products.
  • Isothiocyanate alcoholysis method (U.S. patents US4482500, US4659853, US6184412; Chinese patent CN1548418A) is based on thiocyanate and reacted with organic halide to obtain intermediate isothiocyanate.
  • the intermediate can be alcoholyzed.
  • the thiourethane product is obtained.
  • the process is complicated, the reaction steps are many, the product yield is low, and a small amount of organic intermediates and phase transfer catalysts are lost with the water phase, which causes some pollution to the environment, so it has not been widely used.
  • the dimethyl sulfate method (CN1169988A) is easy to operate and the reaction efficiency is relatively high, but because dimethyl sulfate is unstable, it will rapidly hydrolyze to sulfuric acid and methanol in water, which makes it difficult to promote it in practical production. Furthermore, methyl mercaptan There are also difficulties in absorption and reuse. Xanthate Esterification Ammonialysis Method (US Patent US2691635, Dai Hongyi, Wang Meijun.
  • 2-Mercaptoethanol has a wide range of applications in fine chemicals because of its molecular structure containing both mercapto and hydroxyl groups. 2-Mercaptoethanol is not only an important intermediate for pesticides, but also a stable component of metal corrosion inhibitors. It is also a metal deactivator for catalysts in catalytic cracking of heavy oil. At the same time, high-purity 2-mercaptoethanol is a raw material for the pharmaceutical industry and the photochemical industry. It is also widely used as an auxiliary in the rubber, textile and paint industries.
  • the synthetic route includes the chloroethanol route, ethylene oxide, and hydrogen sulfide routes, but the method of preparing thiourethanes using alkylxanthates, halogenated ethanol, and fatty amines as well as co-production of 2-mercaptoethanol has not been seen. Report.
  • O-alkylthioethanol is an important pharmaceutical intermediate, and there are not many reports on its preparation method.
  • Johanna prepared 2-benzylthioethanol (Johanna A with benzyl mercaptan and chloroethanol in the presence of sodium hydroxide).
  • Michela B, Anthony L, et al, Inorg. Chim. Acta. 2004, 357: 2687-2693) but this method has a significant disadvantage that benzyl mercaptan has an unpleasant odor.
  • the first object of the present invention is to provide a method for preparing thiourethane, which aims to efficiently produce thiourethane and co-produce 2-mercaptoethanol with high economic value.
  • the second object of the present invention is to further use 2-mercaptoethanol produced by the preparation method of thiourethane to co-produce an O-alkylthioethylxanthate collector with a completely new structure.
  • a third object of the present invention is to provide a collector of O-alkylthioethylxanthate having a completely new structure.
  • the present invention provides a method for preparing thiourethane.
  • the specific steps of the method are as follows:
  • Step 1) The xanthate having the structure of Formula I is subjected to an esterification reaction with 2-haloethanol to obtain an O-alkyl / alkylthioethyl-S-hydroxyethylxanthate having the structure shown in Formula II. (This invention is also referred to as an esterification product);
  • Step 2) performing an ammonolysis reaction of the O-alkyl / alkylthioethyl-S-hydroxyethyl xanthate with the fatty amine represented by Formula III to obtain the thiourethane represented by Formula IV and Mixture of 2-mercaptoethanol;
  • Step 3 After the mixture of thiourethane and 2-mercaptoethanol is subjected to alkaline washing, the oil and water are separated, the oil phase is a thiourethane product, and the water phase is 2-hydroxyethyl mercaptan salt;
  • R 1 is a C 1 to C 16 alkyl group, a C 6 to C 16 aryl group, or an alkylthioethyl group represented by Formula V;
  • R 3 is a C 1 to C 16 alkyl group or a C 6 to C 16 aryl group
  • R 2 is a C 1 to C 8 alkyl group
  • M is Na, K or NH 4 + .
  • R 1 is ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, n-hexyl, isohexyl Group, sec-hexyl, n-octyl, isooctyl, phenyl, benzyl, phenethyl or dodecyl;
  • R 2 is methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl Group, tert-butyl, pentyl, hexyl, phenyl or benzyl.
  • the halogenated element of 2-haloethanol is, for example, Cl, Br, etc .; 2-chloroethanol or 2-bromoethanol is preferred.
  • step 1) after the xanthate and 2-haloethanol are subjected to an esterification reaction, oil and water are separated, and the oil phase is O-alkyl / alkylthioethyl-S having the structure of formula II -Hydroxyethylxanthate, the synthetic route is shown in formula (1):
  • X is Cl or Br.
  • the molar ratio of the xanthate to 2-haloethanol is 1.0: 0.9 to 1.2.
  • the esterification reaction uses water as a solvent.
  • the water source is wide and cheap; on the other hand, the raw materials xanthate and 2-haloethanol can be dissolved in water, making the reaction a homogeneous reaction, and the O-alkyl / alkylthioethyl- S-hydroxyethylxanthate is hardly soluble in water, so high-quality O-alkyl / alkylthioethyl-S-hydroxyethylxanthate can be obtained by simple oil-water separation.
  • the amount of solvent water is 0 to 50 ml of water per 1 mol (preferably 1 to 50 ml of water per 1 mol) of xanthate.
  • the conditions for the esterification reaction are: the reaction temperature is 20 to 100 ° C.
  • the reaction time is 1 to 8 hours.
  • 2-haloethanol is used to replace the prior art halogenated acetic acid and other raw materials, which are easy to hydrolyze under alkaline conditions and have a slightly weaker activity than chloroacetic acid.
  • the inventors have found that the 2- The halogenated ethanol is added to the reaction flask, and then the xanthate is added in batches. After the reaction for a period of time, the solvent water is added, and then the reaction is raised to the set temperature to help ensure a good reaction effect.
  • 2-haloethanol and xanthate are reacted in advance at 20 to 30 ° C for 1 to 2 hours, and then water is added to react at 20 to 100 ° C.
  • water is added to react at 20 to 100 ° C.
  • step 2) the O-alkyl / alkylthioethyl-S-hydroxyethylxanthate of formula II is reacted with the fatty amine to obtain a thiourethane structure of formula IV and A mixture of 2-hydroxyethyl mercaptan salt, the synthetic route is shown in formula (2);
  • the fatty amine is a primary fatty amine; preferably, in Formula III, R 2 is a C 1 to C 8 alkyl group; more preferably, it is methyl, ethyl, n-propyl, isopropyl, butyl, iso Butyl, t-butyl, pentyl, hexyl, phenyl or benzyl.
  • the added amount of the fatty amine is 0.9-1.2 times the molar amount of O-alkyl / alkylthioethyl-S-hydroxyethylxanthate.
  • the conditions for the step 2) ammonolysis reaction are: the reaction temperature is 30 to 100 ° C.
  • the reaction time is 1 to 6 hours.
  • step 2 The mixture obtained in step 2) is subjected to lye washing, wherein 2-mercaptoethanol and base are reacted to obtain 2-hydroxyethyl mercaptan salt (HO-CH 2 -CH 2 -SM); where M is derived from the used alkali cation, preferably M is N a, K, or NH 4 +.
  • the conditions of the alkali washing are: the concentration of the alkali is 0.1 to 5 mol / L, and the number of times of the alkali washing is 1 to 5 times.
  • the present invention also provides a method for preparing 2-mercaptoethanol: 2-mercaptoethanol can be obtained after pickling 2-hydroxyethyl mercaptan Product, the specific route is shown in formula (3).
  • the acid is hydrochloric acid or sulfuric acid; preferably, hydrochloric acid.
  • the pickling conditions are as follows: the acid concentration is 0.01 to 5 mol / L.
  • the process is economical, and the obtained by-product 2-mercaptoethanol can be directly separated and sold, or a new xanthate can be further synthesized to realize recycling.
  • the technical solution of the present invention also provides a method for preparing thiourethane in parallel to produce O-alkylthioethylxanthate, and the 2-hydroxyethylsulfide obtained in step 3) of the method for preparing thiourethane.
  • the alkoxide is subjected to a thioalkylation reaction with an alkyl halide having the formula VI to obtain a 2-alkylthioethanol having the formula VII; then the 2-alkylthioethanol is reacted with carbon disulfide and a base to obtain the formula shown in the formula VIII O-alkylthioethylxanthate.
  • R 1 is a C 1 to C 8 alkyl group, an aryl group, or an alkylthioethyl group represented by Formula V;
  • X is Cl, Br, or I;
  • M is a base cation, preferably Na +, K +, or NH 4 + .
  • the aqueous solution of 2-hydroxyethanethiol salt obtained in step (3) is fully utilized to directly react with the alkyl halide to separate liquid to obtain 2-alkylthioethanol.
  • the synthetic route is shown in formula (4) .
  • 2-Alkylthioethanol, carbon disulfide and a base are reacted to obtain an O-alkylthioethylxanthate having a formula VIII structure with a completely new structure and use.
  • the synthetic route is shown in equation (5).
  • the 2-hydroxyethanethiolate is sodium 2-hydroxyethanethiolate or potassium 2-hydroxyethanethiolate.
  • R 1 is preferably a C 1 to C 8 alkyl or aryl group; more preferably, it is ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, or n-pentyl. , Isopentyl, n-octyl, isooctyl, phenyl, benzyl or phenethyl.
  • X is preferably Cl or Br.
  • the thioalkylation reaction conditions are: the reaction temperature is 5 to 50 ° C, and the reaction time is 0.5 to 3 hours.
  • the alkyl halide is added in an amount of 0.8 to 1.3 times the molar amount of the 2-hydroxyethylthiolate.
  • the conditions for the reaction of the 2-alkylthioethanol, carbon disulfide, and alkali are: the reaction temperature is 10 to 40 ° C, and the reaction time is 1 to 6 hours.
  • the base is NaOH, KOH or NH 3 ⁇ H 2 O.
  • the type of O-alkylthioethylxanthate obtained in formula (I) can be determined by the type of the base to be added. For example, when the base used is sodium hydroxide, O-alkylthioethylxanthate sodium salt is obtained. Similarly, the required potassium or ammonium salt can be obtained.
  • the invention provides a method for preparing thiourethane in parallel to produce 2-mercaptoethanol or O-alkylthioethylxanthate.
  • the reaction circuit is shown in formula (6). The specific steps of the method are as follows:
  • the research of the present invention finds that the use of O-alkyl / alkylthioethyl-S-hydroxyethylxanthate having the formula II structure as a flotation collector is used for the non-ferrous metal sulfide ore in non-ferrous metal ore. Flotation.
  • the invention opens up a brand-new application of a compound having the structural formula of formula II in the field of mineral flotation, and research has found that it exhibits excellent flotation performance in the field of mineral flotation.
  • O-alkyl / alkylthioethyl-S-hydroxyalkyl xanthate compounds have xanthanic acid groups and hydroxyl groups.
  • the present invention also provides a novel O-alkylthioethylxanthate collector having the structure wherein R 1 is an alkylthioethyl structure described in Formula ( I ).
  • the invention provides the application of a novel compound with the structure of formula (I).
  • the compound with the structure of formula (I) is used as a flotation collector to apply to the flotation of metal minerals.
  • the key to the technical solution of the present invention is to replace the conventional chloroalkane or chloroacetic acid with xanthate by using 2-haloethanol (also referred to as halogenated ethanol in the present invention) to convert it into an O-alkyl / alkylthio group.
  • 2-haloethanol also referred to as halogenated ethanol in the present invention
  • Ethyl-S-hydroxyethylxanthate intermediate, and then O-alkyl / alkylthioethyl-S-hydroxyethylxanthate is converted to thiourethane and 2-mercapto by ammonolysis reaction
  • Ethanol salt can be washed with alkali to obtain high-purity thiourethane and 2-hydroxyethyl mercaptan salt.
  • the 2-hydroxyethyl mercaptan salt solution was subjected to acid washing to obtain 2-mercaptoethanol.
  • this method shows obvious advantages: 1) The thiourethane can be well separated from 2-mercaptoethanol through alkaline washing, which avoids multiple acid washing and alkaline washing in the traditional process. No distillation or extraction separation is required, the operation is simple, and the obtained 2-mercaptoethanol is a product with great application prospects; 2) the entire process can obtain high-purity thiourethane products and have efficient collection capabilities Sulfur ore collector O-alkyl / alkylthioethyl-S-hydroxyethyl xanthate, and only sodium chloride in wastewater, green and environmentally friendly.
  • 2-mercaptoethyl mercaptan obtained as a by-product of the thiourethane process is reacted with an alkyl halide to be converted into 2-alkylthioethanol, and the 2-alkylthioethanol is then reacted with carbon disulfide and an alkali to synthesize a new structure.
  • O-alkylthioethylxanthate collector, and the by-product O-alkylthioethylxanthate can be recycled as a raw material.
  • wastewater containing a small amount of xanthate and sodium chloride produced by the esterification reaction of xanthate and 2-haloethanol is directly used in the flotation operation to make full use of the wastewater and reduce the wastewater.
  • the technical scheme of the present invention uses xanthate and 2-haloethanol as the initial raw materials, and simultaneously obtains a high-purity thiourethane product, 2-mercaptoethanol, and a flotation collector O-alkyl / alkylthioethyl- S-hydroxyethylxanthate and O-alkylthioethylxanthate achieve the goal of obtaining a variety of high value-added products in one process.
  • the technical scheme of the present invention is simple in operation, and only requires simple oil-water separation to achieve product separation, which greatly reduces production costs.
  • the method has the characteristics of simple operation, high raw material utilization rate, environmental friendliness, and the like, and the O-alkylthioethylxanthate produced in the synthesis process can be recycled, and it is expected to realize industrial application.
  • FIG. 5 O-isopropyl-N-ethylthiocarbamate hydrogen spectrum
  • FIG. 6 An infrared chart of O-isopropyl-S-hydroxyethylxanthate
  • FIG. 7 An infrared chart of O-isobutyl-S-hydroxyethyl xanthate
  • FIG. 9 An infrared chart of O-isopropyl-N-ethylthiocarbamate
  • FIG. 10 is a benzylthioethanol gaseous map
  • FIG. 11 is a process flow chart of the present invention.
  • Example 1 The oil phase obtained in Example 1 was transferred to a reactor, and then a 7-pressure ethylamine aqueous solution (content: 65-70%) was added to the constant-pressure dropping funnel below 20 ° C. The temperature was raised to 70 ° C, and the reaction was performed for 1 hour and cooled to The reaction solution was washed with 50 parts of 8.3% sodium hydroxide solution at room temperature, and the liquid phase was separated to obtain an oil phase: O-isopropyl-N-ethylthiocarbamate, with a purity of 96.7%, based on O- Yield of isopropyl-S-hydroxyethylxanthate was 85.7%, the aqueous phase was sodium 2-hydroxyethylthiolate, the purity was 28.097%, based on O-isopropyl-S-hydroxyethylxanthate The yield of the acid ester was 98.1%, and then 50 parts of a hydrochloric acid solution with a concentration of 10.95%
  • Example 2 The oil phase obtained in Example 2 was transferred to a reactor, and then a constant pressure dropping funnel was charged with 7 parts of ethylamine aqueous solution (content: 65-70%) below 20 ° C. The temperature was raised to 70 ° C, and the reaction was performed for 1 hour and cooled to The reaction solution was washed with 50 parts of 8.3% sodium hydroxide solution at room temperature, and the liquid phase was separated to obtain an oil phase: O-isobutyl-N-ethylthiocarbamate, with a purity of 95.3%, based on O- The yield of isobutyl-S-hydroxyethylxanthate was 82.7%, the aqueous phase was sodium hydroxyethylthiolate, the purity was 27.97%, based on O-isopropyl-S-hydroxyethylxanthate The yield was 97.9%. Then, 50 parts of a hydrochloric acid solution with a concentration of 10.95% was added to the a
  • Example 7 O-isopropyl-S-hydroxyethylxanthate flotation chalcopyrite
  • the concentration of O-isopropyl-S-hydroxyethylxanthate is 14mg / L
  • the pH of the pulp is 6.5
  • the amount of foaming agent (MIBC) is 15mg / L
  • the speed is 1992r / min
  • the particle size is ⁇
  • the chalcopyrite flotation of 0.076 mm to +0.038 mm is performed for 5 minutes, and the flotation recovery rate of chalcopyrite is 97.94%.
  • Example 8 O-isopropyl-S-hydroxyethylxanthate flotation of pyrite
  • the concentration of O-isopropyl-S-hydroxyethylxanthate is 14mg / L
  • the amount of foaming agent (MIBC) is 15mg / L
  • the speed is 1992r / min
  • the particle size is -0.076mm ⁇ + 0.038 mm pyrite flotation for 5 minutes, when the pulp pH is 2.0, the flotation recovery of pyrite is 45.2%, and when the pulp pH is 6.5, the flotation recovery of pyrite is 15.3%.
  • the concentration of O-benzylthioethylxanthate is 5.3mg / L
  • the amount of foaming agent (MIBC) is 15mg / L
  • the rotation speed is 1992r / min
  • the flotation recovery of chalcopyrite is 97.2%.
  • the ore contains 0.53% copper.
  • the main copper ore is chalcopyrite.
  • the invention uses xanthate and 2-haloethanol as the initial raw materials to obtain a high-purity thiourethane product, and simultaneously produces a flotation collector O-alkyl / alkylthioethyl-S-hydroxyethyl Xanthate and O-alkylthioethylxanthate.
  • a flotation collector O-alkyl / alkylthioethyl-S-hydroxyethyl Xanthate and O-alkylthioethylxanthate.
  • O-alkyl / alkylthioethyl-S-hydroxyethylxanthate can achieve equivalent flotation recovery with less amount of use.
  • Ethyl-S-hydroxyethylxanthate can greatly improve the flotation recovery rate when used in combination.
  • the invention achieves the goal of obtaining a variety of high value-added products in one process.

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Abstract

一种制备硫氨酯的方法，包括：将黄原酸盐和2-卤乙醇进行酯化反应，得到O-烷基-S-羟乙基黄原酸酯；再与脂肪胺进行氨解反应，得到硫氨酯和2-巯基乙醇的混合物；混合物经过碱洗后，油水分离，油相和水相分别为硫氨酯和2-羟基乙硫醇盐，2-羟基乙硫醇盐经酸洗后即可得到2-巯基乙醇。以及一种利用2-羟基乙硫醇盐与烷基卤反应得到2-烷硫基乙醇，再与二硫化碳和碱反应制备O-烷硫基乙基黄原酸盐的方法。

Description

一种制备硫氨酯并联产2-巯基乙醇或O-烷硫基乙基黄原酸盐的方法 技术领域
本发明属于矿物捕收技术领域，具体涉及一种制备硫氨酯并联产2-巯基乙醇以及全新O-烷硫基乙基黄原酸盐捕收剂的方法。
背景技术
随着对矿产资源开采力度的加大，矿石日趋贫、细、杂，有用矿物回收利用越来越困难。泡沫浮选作为矿物回收的一种重要技术，通过浮选药剂的加入改变了矿物表面的物理化学性质，使疏水性的矿粒富集于泡沫层中，亲水性的矿粒沉于浮选机底部，从而实现矿物的分离。浮选捕收剂是矿物高效开发利用的关键技术，自Keller于1925年首次将黄原酸盐用作硫化矿浮选捕收剂以来，黄原酸盐成为硫化矿的最主要浮选捕收剂，并且至今仍然是使用最为广泛的硫化矿浮选捕收剂。硫氨酯(硫代氨基甲酸酯)是一类比黄原酸盐和黑药有更好选择性的硫化矿浮选捕收剂，能在较低pH介质下实现矿物的浮选分离，在硫化矿浮选中得到了广泛的应用，是极具应用价值的硫化矿浮选捕收剂。
硫氨酯的合成方法较多，主要有一步催化合成法、异硫氰酸酯法、硫酸二甲酯法、黄原酸盐酯化氨解法(硫代氨基甲酸酯的合成工艺及副产品开发研究[D].中南大学.2003)。一步催化法(美国专利US5041599，德国专利DE2408550)工艺过程简单、反应步骤少、一步反应即能得到产品，但产率不高，副产品回收利用价值低，硫酸镍、氯化钯等催化剂溶解度大，反应中完全进入水相，不易回收，且有大量工业废水产生，污染环境，故工业上较少采用这种方法生产硫氨酯产品。异硫氰酸醇解法(美国专利US4482500，US4659853，US6184412；中国专利CN1548418A)是以硫氰酸盐为原料，使其与有机卤代物反应得到中间体异硫氰酸酯，中间体醇解即可得到硫氨酯产品，该工艺复杂，反应步骤多，产品产率低，少量有机中间体和相转移催化剂随水相的流失，对环境造成一定的污染，因此也未能得到广泛应用。硫酸二甲酯法(CN1169988A)操作简便，反应效率也比较高，但由于硫酸二甲酯不稳定，在水中会迅速水解成硫酸和甲醇，导致其难以在实践生产中推广，再者甲硫醇的吸收和再利用也存在难题。黄原酸盐酯化氨解法(美国专利US2691635，戴洪义，王美君.乙硫氨酯的制备[J].现代化工，1999，19(1)：27-29)主要是以黄原酸盐和氯乙酸钠为原料进行酯化，然后再与伯胺发生氨解反应。该方法原料来源广泛、工艺流程简单、生产技术易于掌握。但该工艺在生产中，巯基乙酸钠副产品存在于水相中，难于回收和利用，带来一系列环境问题。
2-巯基乙醇由于其分子结构中同时含有巯基和羟基，因此在精细化工中具有广泛的应用。2-巯基乙醇不仅是农药的重要中间体，亦是金属缓蚀剂的稳定组分，也是重油催化裂化中催化剂的金属钝化剂。同时，高纯度的2-巯基乙醇是医药工业和光化学工业的原料，也广泛应用于橡胶、纺织和油漆等行业的助剂。合成的路线有氯乙醇路线，环氧乙烷、硫化氢路线，但是以烷基黄原酸盐、卤乙醇、脂肪胺等为原料制备硫氨酯，同时联产2-巯基乙醇的方法未见报道。
O-烷硫基乙醇是一种重要的医药中间体，有关其制备方法的报道不多，Johanna以苄硫醇和氯乙醇在氢氧化钠存在的条件下制备了2-苄硫基乙醇(Johanna A，Michela B，Anthony L,et al,Inorg.Chim.Acta.2004,357:2687-2693)，但是该方法存在一个明显的缺点是苄硫醇具有难闻的气味。
发明内容
为解决现有技术问题，本发明第一目的在于提供一种制备硫氨酯的方法，旨在高效制得硫氨酯外，还联产具有高经济附加值的2-巯基乙醇。
本发明第二目的在于，进一步利用硫氨酯的制备方法制得的2-巯基乙醇，联产制得具有全新结构的O-烷硫基乙基黄原酸盐捕收剂。
本发明第三目的在于，提供一种具有全新结构的O-烷硫基乙基黄原酸盐的捕收剂。
为了实现上述技术目的，本发明提供一种制备硫氨酯的方法，该方法的具体步骤如下：
步骤1)：具有式Ⅰ结构的黄原酸盐与2-卤乙醇进行酯化反应，得到式Ⅱ所示结构的O-烷基/烷硫基乙基-S-羟乙基黄原酸酯(本发明也称为酯化产物)；
步骤2)：将所述O-烷基/烷硫基乙基-S-羟乙基黄原酸酯与式Ⅲ所示的脂肪胺进行氨解反应，得到式Ⅳ所示的硫氨酯和2-巯基乙醇的混合物；
步骤3)：所述的硫氨酯和2-巯基乙醇的混合物经过碱洗后，油水分离，油相为硫氨酯产品，水相为2-羟基乙硫醇盐；
Figure PCTCN2018119879-appb-000001
R 2-NH 2
式Ⅲ
Figure PCTCN2018119879-appb-000002
式Ⅰ～式Ⅳ中，所述的R 1为C 1～C 16的烷基、C 6～C 16的芳基或式Ⅴ所示的烷硫基乙基；
R 3-S-CH 2-CH 2-
式Ⅴ
式Ⅴ中，R 3为C 1～C 16的烷基或C 6～C 16的芳基；
R 2为C 1～C 8的烷基；M为Na，K或NH 4 +。
作为优选，R 1为乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基、仲戊基、新戊基、正己基、异己基、仲己基、正辛基、异辛基、苯基、苄基、苯乙基或十二烷基；R 2为甲基、乙基、正丙基、异丙基、丁基、异丁基、叔丁基、戊基、己基、苯基或苄基。
2-卤代乙醇的卤代元素例如为Cl、Br等；优选为2-氯乙醇或2-溴乙醇。
优选方案，步骤1)中，将所述的黄原酸盐和2-卤代乙醇进行酯化反应后，油水分离，油相即为式Ⅱ结构的O-烷基/烷硫基乙基-S-羟乙基黄原酸酯，合成路线如式(1)所示：
Figure PCTCN2018119879-appb-000003
式(1)中，X为Cl或Br。
较优选的方案，所述黄原酸盐与2-卤代乙醇的摩尔比为1.0:0.9～1.2。
较优选的方案，所述的酯化反应采用水作溶剂。一方面水的来源广泛且便宜；另一方面原料黄原酸盐和2-卤乙醇都能溶于水，使反应为均相反应，同时反应生成的O-烷基/烷硫基乙基-S-羟乙基黄原酸酯难溶于水，从而经过简单的油水分离就能得到高品质的O-烷基/烷硫基乙基-S-羟乙基黄原酸酯。
进一步优选的方案，溶剂水的用量为0～50ml水/1mol(优选为1～50ml水/1mol)黄原酸盐。
较优选的方案，所述酯化反应的条件为：反应温度为20～100℃。反应时间为1～8h。
本发明中，采用2-卤代乙醇替换现有技术的卤代乙酸等原料，其在碱性条件下容易水解且活性相对氯乙酸稍弱，本发明人研究发现，首先在室温下将2-卤代乙醇加到反应瓶中，然后分批加入黄原酸盐，待反应一段时间后，加入溶剂水，然后升到设定温度下反应，有助于保证良好反应效果。
进一步优选，将2-卤代乙醇、黄原酸盐预先在20～30℃下反应1～2h，随后添加水，在 20～100℃下反应。在该优选的条件下，有助于进一步解决2-卤代乙醇制备过程中存在的易水解和活性稍低的缺陷，可以进一步提升制备效果，提升产物的收率。
作为优选，步骤2)中，所述式Ⅱ的O-烷基/烷硫基乙基-S-羟乙基黄原酸酯与所述的脂肪胺反应，得到式Ⅳ结构的硫氨酯和2-羟基乙硫醇盐的混合物，合成路线如式(2)所示；
Figure PCTCN2018119879-appb-000004
所述的脂肪胺为脂肪伯胺；优选地，式Ⅲ中，R 2为C 1～C 8的烷基；进一步优选为甲基、乙基、正丙基、异丙基、丁基、异丁基、叔丁基、戊基、己基、苯基或苄基。
较优选的方案，所述脂肪胺的加入量为O-烷基/烷硫基乙基-S-羟乙基黄原酸酯摩尔量的0.9～1.2倍。
作为优选，步骤2)氨解反应条件为：反应温度为30～100℃。反应时间为1～6h。
将步骤2)得到的混合物进行碱液洗涤，其中的2-巯基乙醇与碱进行反应得到2-羟基乙硫醇盐(HO-CH 2-CH 2-SM)；其中的M来源于所采用的碱的阳离子，优选的M为N a、K或NH 4 +。
优选的方案，步骤3)中，碱洗的条件为：碱的浓度为0.1～5mol/L，碱洗次数为1～5次。
为了实现硫氨酯副产品2-羟基乙硫醇盐的利用，本发明还提供了一种制备2-巯基乙醇的方法：将2-羟基乙硫醇盐经酸洗后即可得到2-巯基乙醇产品，具体路线如式(3)所示。
Figure PCTCN2018119879-appb-000005
作为优选，所述的酸为盐酸或硫酸；优选为盐酸。
优选的方案，酸洗条件为：酸的浓度为0.01～5mol/L。
该工艺经济性好，得到的副产物2-巯基乙醇可以直接分离销售，也可以进一步合成新型黄原酸盐，实现循环利用。
本发明技术方案，还提供了一种制备硫氨酯并联产O-烷硫基乙基黄原酸盐的方法，将所述制备硫氨酯的方法步骤3)得到的2-羟基乙硫醇盐与式Ⅵ结构的烷基卤进行硫烷基化反应，得到式Ⅶ结构的2-烷硫基乙醇；随后将2-烷硫基乙醇与二硫化碳、碱进行反应，得到式Ⅷ所示的O-烷硫乙基黄原酸盐。
R 1-X
式Ⅵ
R 1-S-CH 2-CH 2-OH
式Ⅶ；
Figure PCTCN2018119879-appb-000006
其中，R 1为C 1～C 8的烷基、芳基或式Ⅴ所示的烷硫基乙基；X为Cl，Br或I；M为碱的阳离子，优选为Na+、K+或NH 4 +。
本发明中，充分利用步骤(3)获得的2-羟基乙硫醇盐的水溶液直接与所述的烷基卤反应，分液得到2-烷硫基乙醇，合成路线如式(4)所示。2-烷硫基乙醇、二硫化碳和碱反应得到具有全新结构和用途的式Ⅷ结构的O-烷硫基乙基黄原酸盐，合成路线如方程式(5)所示。
HO-CH 2-CH 2-SM+R 1-X→R 1-S-CH 2-CH 2-OH+MX    (4)
Figure PCTCN2018119879-appb-000007
作为优选，所述的2-羟基乙硫醇盐为2-羟基乙硫醇钠或2-羟基乙硫醇钾。
作为优选，式Ⅵ中，R 1优选为C 1～C 8的烷基或芳基；进一步优选为乙基、丙基、异丙基、丁基、异丁基、叔丁基、正戊基、异戊基、正辛基、异辛基、苯基、苄基或苯乙基。
式Ⅵ中，X优选为Cl或Br。
优选的方案，所述的硫烷基化反应条件为：反应温度为5～50℃，反应时间为0.5～3h。
优选的方案，所述烷基卤的加入量为2-羟基乙硫醇盐的摩尔量的0.8～1.3倍。
优选的方案，所述的2-烷硫基乙醇、二硫化碳和碱反应的条件为：反应温度为10～40℃，反应时间为1～6h。
优选的方案，原料摩尔配比为2-烷硫基乙醇：CS 2：碱金属氢氧化物＝1.0:1.0～5.0:0.9～1.2。
作为优选，所述的碱为NaOH、KOH或NH 3·H 2O。
式Ⅷ中，获得何种O-烷硫乙基黄原酸盐，可通过添加的碱的种类确定选择。例如，采用的碱为氢氧化钠时，得到O-烷硫乙基黄原酸钠盐。同理，可获得所需要的钾盐或者铵盐。
本发明提供一种制备硫氨酯并联产2-巯基乙醇或O-烷硫基乙基黄原酸盐的方法，反应线路见式(6)，该方法的具体步骤如下：
(1)黄原酸盐与2-卤代乙醇反应生成O-烷基/烷硫基乙基-S-羟乙基黄原酸酯(酯化产物)；
(2)所述的O-烷基/烷硫基乙基-S-羟乙基黄原酸酯与脂肪胺反应，得到硫氨酯和2-巯基乙醇的混合物；
(3)所述的硫氨酯和2-巯基乙醇的混合物经过碱洗后，静置，经油水分离，油相即为高纯度的硫氨酯产品，水相为2-羟基乙硫醇盐，经酸洗后即得2-巯基乙醇产品；
(4)所述的2-羟基乙硫醇盐与烷基卤反应，得到2-烷硫基乙醇产品。
(5)所述的2-烷硫基乙醇与二硫化碳，碱反应，得到O-烷硫基乙基黄原酸盐产品。
Figure PCTCN2018119879-appb-000008
本发明研究发现，采用式Ⅱ结构的O-烷基/烷硫基乙基-S-羟乙基黄原酸酯作用作浮选捕收剂，用于有色金属矿石中的有色金属硫化矿的浮选。
本发明开拓了一种具有式Ⅱ结构式的化合物在矿物浮选领域的全新应用，研究发现，其在矿物浮选领域表现出优异的浮选性能。O-烷基/烷硫基乙基-S-羟烷基黄原酸酯化合物分子具有黄原酸基团和羟基，将其作为浮选捕收剂，除明显改善捕收选择性外，还出人意料地赋予所述的浮选捕收剂良好的起泡性能。
本发明还提供了一种具有式Ⅷ所述的R 1为烷硫基乙基结构的全新的O-烷硫基乙基黄原酸盐捕收剂。
本发明提供了一种式Ⅷ结构所述的全新化合物的应用，将式Ⅷ所述结构的化合物作为浮选捕收剂，应用于金属矿物的浮选。
本发明的技术方案关键在于采用2-卤代乙醇(本发明也称为卤乙醇)替换常规的氯代烷或氯乙酸与黄原酸盐进行酯化反应转化成O-烷基/烷硫基乙基-S-羟乙基黄原酸酯中间产物，再通过氨解反应将O-烷基/烷硫基乙基-S-羟乙基黄原酸酯转化为硫氨酯和2-巯基乙醇盐，经过碱洗就可以得到高纯度的硫氨酯与2-羟基乙硫醇盐。2-羟基乙硫醇盐水溶液经过酸洗得到2-巯基乙醇。该方法相比于现有硫氨酯合成方法展现明显优势：1)通过碱洗就能将硫氨酯与2-巯基乙醇很好的分离，避免了传统工艺中的多次酸洗、碱洗，不需要蒸馏或萃取分离，操作简单，且得到的2-巯基乙醇是一种具有较大应用前景的产品；2)整条工艺能得到高纯度的硫氨酯产品和具有高效捕收能力的硫化矿捕收剂O-烷基/烷硫基乙基-S-羟乙基黄原酸酯，且废水中只有氯化钠，绿色环保。
本发明的技术方案采用硫氨酯工艺副产得到的2-巯基乙硫醇盐与烷基卤反应转化为2-烷硫基乙醇，2-烷硫基乙醇再与二硫化碳和碱反应合成全新结构的O-烷硫基乙基黄原酸盐捕收剂，且副产O-烷硫基乙基黄原酸盐可以作为原料循环使用。
有益效果
本发明的技术方案中，黄原酸盐与2-卤乙醇发生酯化反应产生的含有少量黄原酸盐和氯化钠的废水直接用于浮选作业中，使废水得到充分利用，减少废水的产生。
本发明技术方案以黄原酸盐与2-卤乙醇为最初的原料，同时得到高纯度的硫氨酯产品、2-巯基乙醇和浮选捕收剂O-烷基/烷硫基乙基-S-羟乙基黄原酸酯和O-烷硫基乙基黄原酸盐，实现了一条工艺能得到多种高附加值产品的目标。
本发明技术方案中操作简单，只需简单的油水分离就可实现产品的分离，大大降低了生产成本。该方法具有操作简单，原料利用率高，环境友好等特点，并且，合成工艺中产生的O-烷硫基乙基黄原酸盐可以循环使用，望实现工业化应用。
附图说明
【图1】为O-异丙基-S-羟乙基黄原酸酯核磁氢谱图；
【图2】为O-异丁基-S-羟乙基黄原酸酯核磁氢谱图；
【图3】为苄硫基乙醇核磁氢谱图
【图4】为O-苄硫乙基黄原酸盐核磁氢谱图；
【图5】为O-异丙基-N-乙基硫代氨基甲酸酯氢谱图；
【图6】为O-异丙基-S-羟乙基黄原酸酯红外图；
【图7】为O-异丁基-S-羟乙基黄原酸酯红外图；
【图8】为O-苄硫乙基黄原酸盐红外图；
【图9】为O-异丙基-N-乙基硫代氨基甲酸酯红外图；
【图10】为苄硫基乙醇气质图；
【图11】为本发明的工艺流程图。
具体实施方式
本发明由以下实施例进一步说明，但不受这些实施例的限制。实例中所有份数和百分数除另有规定外均指质量。
实施例1：O-异丙基-S-羟乙基黄原酸酯的制备
将8.13份纯度为99％的2-氯乙醇加入反应器中，分批加入18.9份纯度为83.54％的异丙基黄原酸钠，边加边搅拌，然后加入15份蒸馏水，升温至瓶内温度为60℃，恒温反应5小时后冷却至室温，分液得油相O-异丙基-S-羟乙基黄原酸酯，分析表明O-异丙基-S-羟乙基黄原酸酯的收率为88.3％。产品经柱色谱提纯后进行表征，O-异丙基-S-羟乙基黄原酸酯的 1H NMR如图1所示，红外光谱图如图6所示。
实施例2：O-异丁基-S-羟乙基黄原酸酯的制备
将8.13份纯度为99％的2-氯乙醇加入反应器中，分批加入19.32份纯度为89.0％的异丁 基黄原酸钠，边加边搅拌，然后加入15份蒸馏水，升温至瓶内温度为50℃，恒温反应7小时后冷却至室温，分液得油相O-异丁基-S-羟乙基黄原酸酯，分析表明O-异丁基-S-羟乙基黄原酸酯的收率为78.2％。产品经柱色谱提纯后进行表征，O-异丁基-S-羟乙基黄原酸酯的 1H NMR如图2所示，红外光谱图如图7所示。
实施例3：O-异丙基-N-乙基硫代氨基甲酸酯和2-巯基乙醇的制备
将实施例1得到的油相转移到反应器中，然后恒压滴液漏斗在20℃以下加入7份乙胺水溶液(含量为65～70％)，升温至70℃，反应1小时，冷却至室温，用50份浓度为8.3％的氢氧化钠溶液对反应液洗涤，分液得油相：O-异丙基-N-乙基硫代氨基甲酸酯，纯度为96.7％，基于O-异丙基-S-羟乙基黄原酸酯的收率为85.7％，水相为2-羟基乙硫醇钠，纯度为28.097％，基于O-异丙基-S-羟乙基黄原酸酯的收率为98.1％，再向水相中加入50份浓度为10.95％的盐酸溶液，常温下酸化2h，即得2-巯基乙醇产品，产品收率为92.34％。产品经柱色谱提纯后进行表征，O-异丙基-N-乙基硫代氨基甲酸酯的 1H NMR如图5所示，红外光谱图如图9所示。
实施例4：O-异丁基-N-乙基硫代氨基甲酸酯和2-巯基乙醇的制备
将实施例2得到的油相转移到反应器中，然后恒压滴液漏斗在20℃以下加入7份乙胺水溶液(含量为65～70％)，升温至70℃，反应1小时，冷却至室温，用50份浓度为8.3％的氢氧化钠溶液对反应液洗涤，分液得油相：O-异丁基-N-乙基硫代氨基甲酸酯，纯度为95.3％，基于O-异丁基-S-羟乙基黄原酸酯的收率为82.7％，水相为羟基乙硫醇钠，纯度为27.97％，基于O-异丙基-S-羟乙基黄原酸酯的收率为97.9％。再向水相中加入50份浓度为10.95％的盐酸溶液，常温下酸化2h，即得2-巯基乙醇产品，产品收率为90.34％。
实施例5：苄硫基乙醇的制备
向含有10.0份2-羟基乙硫醇钠的50mL水溶液中加入12.78份苄基氯，10℃反应1h，分液得油相，即为苄硫基乙醇，纯度89.97％，基于2-羟基乙硫醇钠的收率为96.5％。产品经萃取、水洗后提纯进行表征，苄硫基乙醇的 1H NMR如图3所示，气质联用图如图10所示。
实施例6：O-苄硫基乙基黄原酸盐的制备
将18.67份纯度为89.97％苄硫基乙醇转移到三口烧瓶中，加入27.7份纯度为99％的二硫化碳和4.17份纯度为96％的氢氧化钠，控制反应温度为25℃，反应时间为3小时，即得O-苄硫基乙基黄原酸盐，O-苄硫基乙基黄原酸盐纯度为94.3％，基于苄硫基乙醇的收率为99.1％。产品经石油醚/丙酮提纯后，O-苄硫基乙基黄原酸盐的 1H NMR如图4所示，红外光谱图如图8所示。
制得的以上部分目标产物的核磁氢谱见表1
表1核磁共振氢谱解析
Figure PCTCN2018119879-appb-000009
制得的以上部分目标产物的红外解析见表2
表2目标产物红外解析
Figure PCTCN2018119879-appb-000010
Figure PCTCN2018119879-appb-000011
实施例7：O-异丙基-S-羟乙基黄原酸酯浮选黄铜矿
在O-异丙基-S-羟乙基黄原酸酯浓度为14mg/L，矿浆pH为6.5，起泡剂(MIBC)的量为15mg/L，转速为1992r/min，对粒度为-0.076mm～+0.038mm的黄铜矿浮选5分钟，黄铜矿的浮选回收率为97.94％。
实施例8：O-异丙基-S-羟乙基黄原酸酯浮选黄铁矿
在O-异丙基-S-羟乙基黄原酸酯浓度为14mg/L，起泡剂(MIBC)的量为15mg/L，转速为1992r/min，对粒度为-0.076mm～+0.038mm的黄铁矿浮选5分钟，在矿浆pH为2.0时，黄铁矿的浮选回收率为45.2％，在矿浆pH为6.5时，黄铁矿的浮选回收率为15.3％。
实施例9：O-苄硫基乙基黄原酸盐浮选黄铜矿
在O-苄硫基乙基黄原酸盐浓度为5.3mg/L，起泡剂(MIBC)的量为15mg/L，转速为1992r/min，对粒度为-0.076mm～+0.038mm的黄铜矿浮选5分钟，在矿浆pH为8.0时，黄铜矿的浮选回收率为97.2％，
实例例10：斑岩铜钼矿浮选实验
香格里拉某硫化铜矿样，矿石含铜0.53％，主要的铜矿为黄铜矿。
在磨矿细度-200目占64.5％，粗选石灰用量为600g/t，矿浆pH值为8.0左右，经过一粗一扫流程，丁黄药和O-异丙基-S-羟乙基黄原酸酯对铜的浮选结果见表3，浮选结果表明，与丁黄药相比，O-异丙基-S-羟乙基黄原酸酯在用量更少的情况下能达到相当的铜回收率。如果将丁黄药与O-异丙基-S-羟乙基黄原酸酯混合使用，不使用MIBC，铜回收率相比于两种药剂单独使用有较大的提高。
表3铜矿浮选实验条件及结果
Figure PCTCN2018119879-appb-000012
Figure PCTCN2018119879-appb-000013
本发明以黄原酸盐与2-卤乙醇为最初的原料，得到高纯度的硫氨酯产品，同时联产浮选捕收剂O-烷基/烷硫基乙基-S-羟乙基黄原酸酯和O-烷硫基乙基黄原酸盐。通过浮选实施例对比发现，O-烷基/烷硫基乙基-S-羟乙基黄原酸酯具有较高的浮选效果，相比于传统的丁黄药对硫化铜矿的浮选，O-烷基/烷硫基乙基-S-羟乙基黄原酸酯在用量更少的情况能达到相当的浮选回收率，当丁黄药与O-烷基/烷硫基乙基-S-羟乙基黄原酸酯混合使用时能大幅度提高浮选回收率。本发明实现了一条工艺能得到多种高附加值产品的目标。

Claims (10)

  1. 一种制备硫氨酯的方法，其特征在于，包括以下步骤：
    步骤1)：具有式Ⅰ结构的黄原酸盐与2-卤乙醇进行酯化反应，得到式Ⅱ所示结构的O-烷基/烷硫基乙基-S-羟乙基黄原酸酯；
    步骤2)：将所述O-烷基/烷硫基乙基-S-羟乙基黄原酸酯与式Ⅲ所示的脂肪胺进行氨解反应，得到式Ⅳ所示的硫氨酯和2-巯基乙醇的混合物；
    步骤3)：所述的硫氨酯和2-巯基乙醇的混合物经过碱洗后，油水分离，油相为硫氨酯产品，水相为2-羟基乙硫醇盐；
    Figure PCTCN2018119879-appb-100001
    Figure PCTCN2018119879-appb-100002
    R 2-NH 2
    式Ⅲ
    Figure PCTCN2018119879-appb-100003
    式Ⅰ～式Ⅳ中，所述的R 1为C 1～C 16的烷基、C 6～C 16的芳基或式Ⅴ所示的烷硫基乙基；
    R 3-S-CH 2-CH 2-
    式Ⅴ
    式Ⅴ中，R 3为C 1～C 16的烷基或芳基；
    R 2为C 1～C 8的烷基；M为N a，K或NH 4 +。
  2. 如权利要求1所述的方法，其特征在于，所述的2-卤乙醇为2-氯乙醇或2-溴乙醇；
    所述黄原酸盐与2-卤乙醇的摩尔比为1.0:0.9～1.2；
    酯化反应溶剂为水，水的用量为0～50ml水/1mol黄原酸盐；
    所述酯化反应条件为：反应温度为20～100℃，反应时间为1～8h；
    优选地，将2-卤代乙醇、黄原酸盐预先在20～30℃下反应1～2h，随后添加水，在20～100℃下反应。
  3. 根据权利要求1所述的方法，其特征在于：
    所述步骤2)的氨解反应条件为：反应温度为30～100℃，反应时间为1～6h；
    所述脂肪胺的加入量为O-烷基/烷硫基乙基-S-羟乙基黄原酸酯摩尔量的0.9～1.2倍。
  4. 据权利要求1所述的方法，其特征在于：步骤3)中，所述的碱洗条件为：碱的浓度为0.1～5mol/L，碱洗次数为1～5次；
    所述的酸为盐酸或硫酸；酸的浓度为0.01～5mol/L。
  5. 一种制备硫氨酯并联产2-巯基乙醇的方法，其特征在于，将权利要求1～4任一项方法步骤3)得到的2-羟基乙硫醇盐进行酸洗处理，即得2-巯基乙醇产品。
  6. 一种制备硫氨酯并联产O-烷硫基乙基黄原酸盐的方法，其特征在于：将权利要求1～4任一项所述的方法步骤3)得到的2-羟基乙硫醇盐与式Ⅵ结构的烷基卤进行硫烷基化反应，得到式Ⅶ结构的2-烷硫基乙醇；随后将2-烷硫基乙醇与二硫化碳、碱进行反应，得到式Ⅷ所示的O-烷硫乙基黄原酸盐；
    R 1-X
    式Ⅵ
    R 1-S-CH 2-CH 2-OH
    式Ⅶ
    Figure PCTCN2018119879-appb-100004
    其中，R 1为C 1～C 8的烷基、芳基或式Ⅴ所示的烷硫基乙基；X为Cl，Br或I；M为碱的阳离子，优选为Na+、K+或NH 4 +。
  7. 根据权利要求6所述的方法，其特征在于：硫烷基化反应的反应条件为：反应温度为5～50℃，反应时间为0.5～3h,
    所述烷基卤的加入量为2-羟基乙硫醇盐的摩尔量的0.8～1.3倍。
  8. 根据权利要求6所述的方法，其特征在于：
    O-烷硫基乙基黄原酸盐的反应条件为：反应温度为10～40℃，反应时间为1～6h，原料摩尔配比为2-烷硫基乙醇：CS 2：碱金属氢氧化物＝1.0:1.0～5.0:0.9～1.2。
  9. 一种O-烷硫基乙基黄原酸盐捕收剂，其特征在于，具有权利要求6～8任一项方法所示的式Ⅷ结构。
  10. 如权利要求9所述的O-烷硫基乙基黄原酸盐捕收剂的应用，其特征在于，将O-烷硫基乙基黄原酸盐应用于有色金属硫化矿浮选中。
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