Alkenyl thionocarbamate compound as well as preparation method and application thereof

Abstract

The invention relates to an alkenyl thionocarbamate compound as well as a preparation method and application thereof, the structural formula of the thionocarbamate compound is # imgabs0 #, R, R1 and R2 are respectively and independently one of alkyl, aryl, ester group and halogen; r3 is one of alkyl, alkenyl and aryl; the compound can be used as a sulphide mineral collecting agent and shows excellent performance in the mineral separation process of sulphide minerals which are difficult to separate, such as chalcopyrite and pyrite.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis and mineral flotation, and more specifically to an alkenylthiocarbamate compound and a preparation method and application thereof. Background Art

[0002] With the development of mineral processing technology, various new sulfide ore collectors such as sulfur-nitrogen, esters, and mercaptans have been continuously developed and applied, which significantly improves the recovery rate of sulfide minerals. These collectors have good selectivity and collection performance, and can be effectively adsorbed on the surface of sulfide minerals, making them hydrophobic and flotation separation. Compared with xanthate, these collectors have better collection effect or selectivity for some difficult-to-select sulfide minerals such as chalcopyrite and pyrite. In addition, these collectors are used in small amounts, have good selectivity, and are environmentally friendly, so they are widely used in mineral processing practice.

[0003] At present, the collectors for copper-lead minerals mainly include sodium ethyl xanthate, ethyl thiocyanate, thiamine and black medicine. In recent years, some new collectors for copper-lead minerals have also been developed. These new collectors have stronger selectivity and collection performance, which can further improve the recovery rate of difficult-to-select sulfide minerals. In practical applications, mineral processing workers often use two or more collectors in combination, which can play a synergistic role and improve mineral processing indicators. For example, thiamine is combined with xanthate to float chalcopyrite and galena, and ethyl thiocyanate is combined with 3418 to float brittle sulfide antimony lead ore. Although the compounding method has been widely used in mineral processing plants, as the country's environmental protection requirements are becoming more and more stringent, some mineral processing reagents have caused certain pollution to the mining environment. With the advancement of mineral processing technology and the improvement of environmental protection requirements, the development of new, efficient and environmentally friendly sulfide ore collectors and their combinations remains a hot topic in mining research. Summary of the invention

[0004] Based on the above technical problems existing in the prior art, the present invention provides an alkenylthiocarbamate compound, which can be used as a sulfide mineral collector and exhibits excellent performance in the beneficiation process of difficult-to-be-selected sulfide minerals such as chalcopyrite and pyrite.

[0005] In order to achieve the above object, the technical solution of the present invention is as follows:

[0006] An alkenyl thiocarbamate compound, the structure of which is as follows:

[0007]

[0008] Among them, R, R 1 , R 2 Each is independently one of an alkyl group, an aryl group, an ester group, and a halogen group; R 3 It is one of alkyl, alkenyl and aryl.

[0009] The present invention also provides a method for preparing the above-mentioned alkenyl thiocarbamate compound, which comprises the following steps:

[0010] Adding a halogenated olefin compound, a thiocyanate salt, an alcohol compound, a catalyst, an additive and a solvent into a reaction container, mixing and reacting to obtain an alkenylthiocarbamate compound;

[0011] Wherein, the structure of the halogenated olefin compound is: R, R 1 , R 2 Each is independently one of an alkyl group, an aryl group, an ester group, and a halogen group, and X=F, Cl, I, or OTf; the structure of the alcohol compound is: R 3 -OH, R 3 The catalyst is at least one of a metal salt, a Lewis acid, and a Lewis base; and the additive is at least one of an inorganic acid, an inorganic salt, and an inorganic base.

[0012] In some embodiments, the reaction temperature is 0-150°C; preferably, 60-120°C.

[0013] In some embodiments, the mass ratio of the halogenated olefin compound, the thiocyanate salt, and the alcohol compound is 1:1-10:1-10.

[0014] In some embodiments, the alcohol compound is at least one of methanol, ethanol, isopropanol, isobutanol, and allyl alcohol.

[0015] In some embodiments, the solvent is at least one of dichloromethane, ethyl acetate, dimethyl sulfoxide, diethyl ether, acetone, acetonitrile, N,N-dimethylformamide and water.

[0016] In some embodiments, the thiocyanate is at least one of ammonium thiocyanate, sodium thiocyanate, and potassium thiocyanate.

[0017] In some embodiments, the catalyst includes at least one of palladium acetate, cupric chloride, copper trifluoromethanesulfonate, cupric bromide, cuprous iodide, and ferric chloride.

[0018] In some embodiments, the additive includes (NH 4 ) 2 HPO 4 , KH 2 PO 4 , H 2 SO 4 , HNO 3 , NaOH, Na 2 CO 3 and at least one of a molecular sieve.

[0019] In some embodiments, the reaction time is 0-48 h; preferably, 8-30 h.

[0020] The present invention also provides the use of the alkenyl thiocarbamate compound or the alkenyl thiocarbamate compound obtained by the preparation method described in any of the above embodiments in mineral flotation.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention introduces unsaturated alkenyl groups into the thiocarbamate compounds, which can effectively enhance the adsorption capacity of the alkenyl thiocarbamate compounds on the mineral surface. When used as a collector, compared with traditional collectors, its structural characteristics can show stronger selectivity and collection capacity for difficult-to-float sulfide minerals. Practice shows that in the flotation of chalcopyrite and pyrite, the use of the alkenyl thiocarbamate compounds of the present invention can significantly improve the recovery rate of minerals and generally reduce the dosage of reagents. In addition, the alkenyl thiocarbamate compounds of the present invention also have good foaming properties and antioxidant properties, and can improve the stability during the re-selection process.

[0023] The preparation method of the present invention uses thiocyanate, alkenyl halide and alcohol as reaction raw materials, and directly synthesizes alkenyl thiocarbamate compounds in one step under the action of a catalyst and an additive. The preparation method is simple and efficient, and the reagents used are relatively common and economical, and the cost is low.

[0024] The preparation method of the present invention greatly simplifies the synthesis process, reduces the multi-step reaction to a single-step operation, and greatly improves the synthesis efficiency; and the reaction conditions are mild, no special equipment or harsh environment is required, and the practicality and generalizability of the method are enhanced. In addition, the reagents used in the present invention are commonly used reagents with low toxicity, which overcomes the limitations of the prior art such as the need to use highly toxic reagents and harsh reaction conditions, not only reducing the production cost, but also causing little pollution to the environment, and being green and environmentally friendly. DETAILED DESCRIPTION

[0025] Many specific details are set forth in the following description to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art can make similar modifications without violating the connotation of the present invention, so the present invention is not limited to the specific implementation disclosed below.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0027] Example 1

[0028] In the reaction tube, 100 g of methyl bromocyclopentenecarboxylate (CAS: 320608-71-7), 100 g of sodium thiocyanate, 10 mL of ethanol, 100 mg of CuI catalyst, 50 mg of (NH 4 ) 2 HPO 4 and 100 mL of acetone, then heated to 80°C while stirring for reaction. After 12 hours, stirring was stopped and the mixture was cooled to room temperature. The solvent was then removed by rotary evaporation to obtain a crude product. Finally, the crude product was purified by column chromatography to obtain the target product.

[0029] Example 2

[0030] 100 g of ethyl chlorocyclopentene carboxylate (CAS: 66839-38-1), 100 g of potassium thiocyanate, 10 mL of methanol, 100 mg of CuI catalyst, 5 g of (NH 4 ) 2 HPO 4 and 100 mL of acetone, then heated to 80°C while stirring for reaction. After 8 hours, stirring was stopped and the mixture was cooled to room temperature. The solvent was then removed by rotary evaporation to obtain a crude product. Finally, the crude product was purified by column chromatography to obtain the target product.

[0031] Example 3

[0032] Add 100 g of methyl iodocyclopentenecarboxylate (CAS: 149512-06-1), 100 g of ammonium thiocyanate, 10 mL of ethanol, 10 mg of palladium acetate catalyst, 5 g of Na 2 CO 3 and 100 mL of ethyl acetate, then heated to 60°C for reaction while stirring. After 24 hours, stirring was stopped and the mixture was cooled to room temperature. The solvent was then removed by rotary evaporation to obtain a crude product. Finally, the crude product was purified by column chromatography to obtain the target product.

[0033] Example 4

[0034] Add 100 g of methyl bromocyclopentenecarboxylate, 100 g of sodium thiocyanate, 10 mL of isobutyl alcohol, and 100 mg of FeCl 3 Catalyst, 10 g NaOH and 100 mL acetonitrile were added, and then the temperature was raised to 80°C while stirring for reaction. After 16 hours, stirring was stopped and the mixture was cooled to room temperature. The solvent was then removed by rotary evaporation to obtain a crude product. Finally, the crude product was purified by column chromatography to obtain the target product.

[0035] Example 5

[0036] 100 g of methyl chlorocyclopentene carboxylate, 100 g of sodium thiocyanate, 10 mL of allyl alcohol, 50 mg of CuI catalyst, 5 g of (NH 4 ) 2 HPO 4 and 100 mL of N,N-dimethylformamide, then heated to 120°C for reaction while stirring. After 12 hours, stirring was stopped and the mixture was cooled to room temperature. The solvent was then removed by rotary evaporation to obtain a crude product. Finally, the crude product was purified by column chromatography to obtain the target product.

[0037] Example 6

[0038] An application example of the collector prepared in Example 1 of the present invention in the flotation separation of lead, antimony and zinc comprises the following steps:

[0039] 1. Mineral raw materials:

[0040] The mineral raw materials used are low-grade lead-antimony tailings, with lead content of 0.34%, antimony 0.27%, and zinc 1.08%. Phase analysis shows that the lead-antimony minerals are mainly antimony sulfide, with a small amount of galena and stibnite, the zinc minerals are mainly sphalerite, the sulfur minerals are mainly pyrite, and a small amount of arsenopyrite. The gangue minerals are mainly siliceous minerals, with a small amount of carbonate minerals.

[0041] 2. Flotation reagents and operating conditions:

[0042]

[0043] In the flotation operation, the lead-antimony tailings are finely ground until the mineral monomers are fully dissociated, and then lime and sodium carbonate are added to adjust the pH value to 8.5-9, and then sodium hexametaphosphate is used as a mineral dispersant to improve the dispersibility of the mineral, and then zinc sulfate and sodium sulfite are added as zinc mineral inhibitors, and then lead nitrate is added as a lead-antimony mineral activator, and finally the collector prepared in Example 1 and butylamine black medicine are added as collectors for lead-antimony minerals to efficiently collect low-grade lead-antimony tailings. The whole process includes one roughing, three scavenging and two concentrating, and finally a high-quality mixed concentrate is obtained. According to the test, the lead grade of the obtained mixed concentrate is 10.77% and the antimony grade is 9.93%; the recovery rates of lead and antimony are 67.20% and 65.43% respectively.

[0044] Comparative Example 1

[0045] 1. Mineral raw materials:

[0046] The mineral raw material used is low-grade lead-antimony tailings, which are the same batch of ore samples as the minerals in Example 6. The lead content in the ore is 0.34%, antimony is 0.27%, and zinc is 1.08%. Phase analysis shows that the lead-antimony minerals are mainly antimony brittle sulfide, with a small amount of galena and stibnite, the zinc minerals are mainly sphalerite, the sulfur minerals are pyrite, and a small amount of arsenopyrite. The gangue minerals are mainly siliceous minerals, with a small amount of carbonate minerals.

[0047] 2. Flotation reagents and operating conditions:

[0048]

[0049]

[0050] In the flotation operation, the tailings are finely ground until the mineral monomers are fully dissociated, and then lime and sodium carbonate are added to adjust the pH value to 8.5-9, and then sodium hexametaphosphate is used as a mineral dispersant to improve the dispersibility of the mineral, and then zinc sulfate and sodium sulfite are added as zinc mineral inhibitors, and then lead nitrate is added as a lead-antimony mineral activator, and finally butyl xanthate and butylamine black medicine are added as collectors of lead-antimony minerals to efficiently collect low-grade lead-antimony tailings. The whole process includes one roughing, three scavenging and two concentrating, and finally obtains high-quality mixed lead-antimony concentrate; after testing, the lead grade in the mixed lead-antimony concentrate is 9.57% and the antimony grade is 8.94%; the recovery rates of lead and antimony are 62.15% and 59.30% respectively.

[0051] Example 7

[0052] An application example of the collector prepared in Example 4 of the present invention in the flotation separation of copper, lead and zinc comprises the following steps:

[0053] 1. Mineral raw materials:

[0054] The mineral raw materials used are low-grade copper-lead-zinc ore, with lead content of 1.37%, copper content of 0.36%, and zinc content of 2.85%. Phase analysis shows that the lead is mainly galena, the zinc mineral is mainly sphalerite, the copper mineral is mainly chalcopyrite, and the other sulfur minerals are pyrite, with a small amount of arsenopyrite. The gangue minerals are mainly siliceous minerals, with a small amount of carbonate minerals.

[0055] 2. Flotation reagents and operating conditions:

[0056]

[0057]

[0058] In the flotation operation, the ore is finely ground until the mineral monomers are fully dissociated, and then lime and sodium carbonate are added to adjust the pH value to 8.5-9, and then sodium hexametaphosphate is used as a mineral dispersant to improve the dispersibility of the mineral, and then zinc sulfate and sodium sulfite are added as zinc mineral inhibitors, and then lead nitrate is added as a copper-lead mineral activator, and finally the collector prepared in Example 4 and aniline black medicine are added as collectors for copper-lead minerals to efficiently capture low-grade copper-lead minerals. The whole process includes one roughing, three scavenging and two concentrating, and finally a high-quality mixed concentrate is obtained.

[0059] The experimental verification shows that the reagent prepared by the above process of the present invention can efficiently recover low-grade copper-lead ore. In a given ore, the lead content is 1.37% and the copper content is 0.36%. Through one roughing, three sweeping and two fine treatments, a mixed copper-lead concentrate with a lead grade of 42.57% and a copper grade of 11.39% is finally obtained, and the recovery rates of lead and copper reach 89.54% and 91.17% respectively.

[0060] Comparative Example 2

[0061] 1. Mineral raw materials:

[0062] The mineral raw material used is low-grade copper-lead-zinc ore, which is the same batch of ore samples as the ore in Example 7. The lead content in the ore is 1.37%, copper is 0.36%, and zinc is 2.85%. Phase analysis shows that the lead is mainly galena, the zinc mineral is mainly sphalerite, the copper mineral is mainly chalcopyrite, and the other sulfur minerals are pyrite and a small amount of arsenopyrite. The gangue minerals are mainly siliceous minerals, and there are also a small amount of carbonate minerals.

[0063] 2. Flotation reagents and operating conditions:

[0064]

[0065] In the flotation operation, the ore is finely ground until the mineral monomers are fully dissociated, and then lime and sodium carbonate are added to adjust the pH value to 8.5-9, and then sodium hexametaphosphate is used as a mineral dispersant to improve the dispersion of the mineral, and then zinc sulfate and sodium sulfite are added as zinc mineral inhibitors, and then lead nitrate is added as a copper-lead mineral activator, and finally butyl xanthate and aniline black medicine are added as copper-lead mineral collectors to efficiently collect low-grade copper-lead minerals. The whole process includes one roughing, three scavenging and two concentrating, and finally a high-quality mixed concentrate is obtained.

[0066] After experimental verification, in the given ore, the lead content is 1.37% and the copper content is 0.36%. Through one roughing selection, three sweeping selections and two fine selections, a mixed copper-lead concentrate with a lead grade of 40.22% and a copper grade of 8.53% was finally obtained. The recoveries of lead and copper were 87.44% and 89.50% respectively.

[0067] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0068] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. An alkenyl thiocarbamate compound, characterized in that: Its structure is as follows: Among them, R, R 1 , R 2 Each is independently one of an alkyl group, an aryl group, an ester group, and a halogen group; R 3 It is one of alkyl, alkenyl and aryl.

2. The method for preparing alkenyl sulfate amino ester compounds according to claim 1, characterized in that: The following steps are involved: Adding a halogenated olefin compound, a thiocyanate salt, an alcohol compound, a catalyst, an additive and a solvent into a reaction container, mixing and reacting to obtain an alkenylthiocarbamate compound; Wherein, the structure of the halogenated olefin compound is: R, R 1 , R 2 Each is independently one of an alkyl group, an aryl group, an ester group, and a halogen group, and X=F, Cl, I, or OTf; the structure of the alcohol compound is: R 3 -OH, R 3 The catalyst is at least one of a metal salt, a Lewis acid, and a Lewis base; and the additive is at least one of an inorganic acid, an inorganic salt, and an inorganic base.

3. The method for preparing alkenyl thiocarbamate compounds according to claim 2, characterized in that: The reaction temperature is 0-150°C.

4. The method for preparing alkenyl thiocarbamate compounds according to claim 2, characterized in that: The mass ratio of the halogenated olefin compound, the thiocyanate salt and the alcohol compound is 1:1-10:1-10.

5. The method for preparing alkenyl thiocarbamate compounds according to claim 2, characterized in that: The alcohol compound is at least one of methanol, ethanol, isopropanol, isobutanol and allyl alcohol.

6. The method for preparing alkenyl thiocarbamate compounds according to claim 2, characterized in that: The solvent is at least one of dichloromethane, ethyl acetate, dimethyl sulfoxide, ether, acetone, acetonitrile, N,N-dimethylamide and water.

7. The method for preparing alkenyl thiocarbamate compounds according to claim 2, characterized in that: The thiocyanate is at least one of ammonium thiocyanate, sodium thiocyanate and potassium thiocyanate.

8. The method for preparing alkenyl thiocarbamate compounds according to claim 2, characterized in that: The catalyst includes at least one of palladium acetate, cupric chloride, copper trifluoromethanesulfonate, cupric bromide, cuprous iodide and ferric chloride.

9. The method for preparing alkenyl thiocarbamate compounds according to claim 2, characterized in that: The additive includes at least one of (NH4)2HPO4, KH2PO4, H2SO4, HNO3, NaOH, Na2CO3 and molecular sieves.

10. Use of the alkenyl thiocarbamate compound according to claim 1 or the thiocarbamate compound obtained by the preparation method according to claims 2 to 9 in mineral flotation.

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