A sulfide ore collector N-benzenesulfonyl-O-alkylthiocarbamate and its preparation method and application

Abstract

The present invention belongs to the technical field of mineral processing, and mainly relates to a sulfide ore collector N-benzenesulfonyl-O-alkylthiocarbamate, and a preparation method and application thereof. With water as a solvent, thiocyanate benzenesulfonyl chloride is reacted with a catalyst to obtain an intermediate benzenesulfonyl isothiocyanate; the intermediate reacts with an alkyl alcohol to obtain N-benzenesulfonyl-O-alkylthiocarbamate. The method is simple to prepare and has a good reaction effect. The flotation agent has a benzenesulfonic acid group and a thioamino group, which can well improve the effect of the collector on the mineral surface and metal ions. This type of collector has a strong capture ability and selectivity for copper sulfide ores, and exhibits good flotation indicators.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral processing, and mainly relates to a sulfide ore collector N-benzenesulfonyl-O-alkylthiocarbamate and a preparation method and application thereof. Background Art

[0002] Collectors play an important role in the flotation separation process of sulfide ores. Suitable collectors can improve the separation efficiency of sulfide ores. In the flotation separation process of sulfide ores, commonly used collectors include xanthate, black medicine, thiocarbamate, xanthate and thiocarbamate. New collectors mainly include alkoxycarbonylthiocarbamate and alkoxycarbonylthiourea, dialkyl monothiophosphate, dithiocarbamic acid-carbonyl butyl ester, dithiocarbamic acid-carbonyl ethyl ester, O-ethyl-N,N-dimethylthiocarbamate and phenylthiocarbamate. Thiocarbamate compounds have become important metal mineral flotation collectors. This type of compound has good collection ability for gold, silver, copper and lead sulfides, and good selectivity for pyrite. With the increasing poverty, fineness and complexity of metal mineral resources, the difficulty of flotation recovery of metal minerals has increased. The development of new and efficient flotation collectors and the improvement of the hydrophobicity of mineral particles are of great significance to improving the comprehensive recovery rate of metal minerals.

[0003] Existing thiocarbamate collectors show good collection performance for sulfide minerals, but also have problems such as insufficient collection capacity for sulfide minerals, poor selectivity and water solubility. According to the applicant's search, there are currently no reports on N-benzenesulfonyl-O-alkylthiocarbamate compounds and their preparation and flotation applications. Summary of the invention

[0004] The present invention provides a sulfide ore collector N-benzenesulfonyl-O-alkylthiocarbamate, a preparation method and an application thereof. The collector significantly improves the collector selectivity and collection capacity of the mineral, improves the adhesion of flotation foaming, and increases the flotation recovery rate. At the same time, potassium carbonate or zinc chloride is used as a catalyst to synthesize N-benzenesulfonyl-O-alkylthiocarbamate compounds for the first time.

[0005] To achieve the above objectives, the present invention adopts the following technical solutions.

[0006] The sulfide ore collector N-benzenesulfonyl-O-alkylthiocarbamate has a structure shown in Formula 1: In Formula 1, R is a C1-C8 hydrocarbon group.

[0007]

[0008] Furthermore, the R is a hydrocarbon group with a carbon number of 1 to 8, and preferably R is an alkane group with a carbon number of 3 to 6.

[0009] Preferably, R is one of propyl, isopropyl, n-butyl, isobutyl, n-hexyl, isopentyl, and methyl isobutyl.

[0010] The preparation method of N-benzenesulfonyl-O-alkylthiocarbamate specifically comprises the following steps:

[0011] Step 1, add thiocyanate and a certain amount of water into a reaction vessel, control the stirring speed to completely dissolve the materials, add catalyst CT-1, slowly add benzenesulfonyl chloride, control the reaction temperature and time, and after the reaction is completed, separate the organic phase and the aqueous phase, and the oil phase is the intermediate benzenesulfonyl isothiocyanate;

[0012] Step 2: Take a certain amount of alcohol, add catalyst CT-2, dropwise add the intermediate into the reaction vessel, control the reaction temperature and time, and obtain N-benzenesulfonyl-O-alkylthiocarbamate.

[0013] Furthermore, the thiocyanate is one or a combination of sodium thiocyanate, ammonium thiocyanate or potassium thiocyanate.

[0014] Furthermore, the catalyst CT-1 is one or a combination of N,N-dimethylaniline, pyridine or PEG-400.

[0015] Furthermore, the alcohol is one or a combination of n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, and methyl isobutyl carbinol.

[0016] Furthermore, the catalyst CT-2 is one of potassium carbonate and zinc chloride or a mixture of the two.

[0017] Furthermore, the mass ratio of the thiocyanate to water is 1:(1-3.5).

[0018] Furthermore, the molar ratio of the thiocyanate to benzenesulfonyl chloride is 1:(1-1.2).

[0019] Furthermore, the added amount of the catalyst CT-1 is 2% to 10% of the mass of the thiocyanate.

[0020] Furthermore, the molar ratio of the intermediate to the alcohol is: 1:(1-2.5).

[0021] Furthermore, the mass of the catalyst CT-2 added is 1% to 10% of the mass of the intermediate.

[0022] Furthermore, in step 1, the reaction temperature is 10 to 60° C., preferably 10 to 30° C.; and the reaction time is 1 to 5 hours.

[0023] Furthermore, in step 2, the reaction temperature is 30 to 90° C., preferably 30 to 60° C.; and the reaction time is 1 to 8 hours.

[0024] The N-benzenesulfonyl-O-alkylthiocarbamate prepared by the invention is used as a flotation collector for the flotation of non-ferrous metal sulfide ores.

[0025] In the application of the present invention, after the sulfide metal ore is ground, a collector with the structure is added to float the metal minerals through a flotation method.

[0026] The flotation process is as follows: the ore is ground into powder and then put into flotation, a regulator is added to adjust the slurry, the N-benzenesulfonyl-O-alkylthiocarbamate and pine oil are added, and useful minerals are selected by flotation.

[0027] Preferably, the metal ore is copper sulfide ore, lead sulfide ore, copper sulfide associated gold and silver ore, etc.

[0028] In the application of the present invention, the collector is added in the amount of flotation reagent required in the conventional metal ore flotation process.

[0029] In the application described in the present invention, the flotation process of non-ferrous metal sulfide ores is an existing mature process.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows.

[0031] 1. The present invention innovatively proposes a method of introducing benzenesulfonyl groups into thiocarbamate compounds, using N-benzenesulfonyl-O-alkylthiocarbamate as a flotation collector, and efficiently recovering valuable metal minerals from metal ores. The compound has sulfonyl and thioamino groups, which significantly improves the collector selectivity of the mineral, can synergistically chelate metal ions at the molecular level, enhance the adsorption strength of the collector on the surface of the metal mineral, and significantly improve the collection capacity; at the same time, the introduction of the benzene ring strengthens the hydrophobicity of the particles and improves the adhesion of the flotation foam. The collector of the present invention simultaneously improves the adsorption strength and hydrophobic effect of the metal mineral, and improves the flotation recovery rate of the metal mineral.

[0032] 2. The N-benzenesulfonyl-O-alkylthiocarbamate synthesized from the intermediate and the alcohol compound of the present invention uses potassium carbonate or zinc chloride as a catalyst for the first time, which is simple and efficient, and the product purity is greater than 80%, and can be used as a flotation collector without purification. DETAILED DESCRIPTION

[0033] The present invention is further illustrated by the following examples, but the present invention is not limited in any way. Any changes or substitutions made based on the teachings of the present invention belong to the protection scope of the present invention.

[0034] The sulfide ore collector N-benzenesulfonyl-O-alkylthiocarbamate has a structure shown in Formula 1: In Formula 1, R is a C1-C8 hydrocarbon group.

[0035]

[0036] Furthermore, R is a C3-C6 alkane group; preferably, R is one of propyl, isopropyl, n-butyl, isobutyl, n-hexyl, isopentyl, and methyl isobutyl.

[0037] The preparation method of N-benzenesulfonyl-O-alkylthiocarbamate specifically comprises the following steps:

[0038] Step 1, adding thiocyanate and a certain amount of water in a reaction container, the mass ratio of thiocyanate to water is 1: (1-3.5), controlling the stirring speed to completely dissolve the materials, adding catalyst CT-1, the addition amount of catalyst CT-1 is 2% to 10% of the mass of thiocyanate, slowly adding benzenesulfonyl chloride, the molar ratio of thiocyanate to benzenesulfonyl chloride is 1: (1-1.2), controlling the reaction temperature and time, after the reaction is completed, separating the organic phase and the aqueous phase, and the oil phase is the intermediate benzenesulfonyl isothiocyanate;

[0039] Step 2: Take a certain amount of alcohol, add catalyst CT-2, and dropwise add the intermediate into the reaction vessel. The molar ratio of the intermediate to the alcohol is 1:(1-2.5), and the mass of the catalyst CT-2 added is 1%-10% of the mass of the intermediate. Control the reaction temperature and time to obtain N-benzenesulfonyl-O-alkylthiocarbamate.

[0040] Furthermore, the thiocyanate is one or a combination of sodium thiocyanate, ammonium thiocyanate or potassium thiocyanate.

[0041] Furthermore, the catalyst CT-1 is one or a combination of N,N-dimethylaniline, pyridine or PEG-400.

[0042] Furthermore, the alcohol is one or a combination of n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, and methyl isobutyl carbinol.

[0043] Furthermore, the catalyst CT-2 is one of potassium carbonate and zinc chloride or a mixture of the two.

[0044] Furthermore, in step 1, the reaction temperature is 10 to 60° C., preferably 10 to 30° C.; and the reaction time is 1 to 5 hours.

[0045] Furthermore, in step 2, the reaction temperature is 30 to 90° C., preferably 30 to 60° C.; and the reaction time is 1 to 8 hours.

[0046] The N-benzenesulfonyl-O-alkylthiocarbamate prepared by the invention is used as a flotation collector for the flotation of non-ferrous metal sulfide ores.

[0047] In the application of the present invention, after the sulfide metal ore is ground, a collector with the structure is added to float the metal minerals through a flotation method.

[0048] The flotation process is as follows: the ore is ground into powder and then put into flotation, a regulator is added to adjust the slurry, the N-benzenesulfonyl-O-alkylthiocarbamate and pine oil are added, and useful minerals are selected by flotation.

[0049] Preferably, the metal ore is copper sulfide ore, lead sulfide ore, copper sulfide associated gold and silver ore, etc.

[0050] In the application of the present invention, the collector is added in the amount of flotation reagent required in the conventional metal ore flotation process.

[0051] In the application described in the present invention, the flotation process of non-ferrous metal sulfide ores is an existing mature process.

[0052] Example 1.

[0053] Add 81g of sodium thiocyanate and 170ml of water to the reactor, stir thoroughly to ensure that the sodium thiocyanate is completely dissolved. Add 4.8g of N,N-dimethylaniline as a catalyst, slowly add 185g of benzenesulfonyl chloride, control the reaction temperature not to exceed 30°C, react for 3 hours, and let it stand to separate the layers to obtain 182g of the intermediate benzenesulfonyl isothiocyanate.

[0054] Take 74g of isobutanol, add 3.6% potassium carbonate and zinc chloride mixture (mass ratio 2:1), add the intermediate dropwise to the isobutanol solution, control the feeding rate, the reaction temperature is 50°C, react for 6 hours, and obtain N-benzenesulfonyl-O-isobutylthiocarbamate with a purity of 82%.

[0055] Example 2.

[0056] Add 76g of ammonium thiocyanate to the reactor, add 160ml of water, stir well to ensure that the ammonium thiocyanate is completely dissolved. Add 5.5g of N,N-dimethylaniline as a catalyst, slowly add 185g of benzenesulfonyl chloride, control the reaction temperature not to exceed 30°C, react for 3 hours, and let it stand for stratification to obtain 178g of intermediate benzenesulfonyl isothiocyanate.

[0057] Take 113g of methyl isobutyl carbinol, add 3.2g of potassium carbonate, add the intermediate dropwise to the methyl isobutyl carbinol solution, control the feeding rate, the reaction temperature is 50°C, react for 6 hours, and obtain N-benzenesulfonyl-O-methyl isobutyl thiocarbamate with a purity of 81%.

[0058] Example 3.

[0059] Add 81g of sodium thiocyanate and 170ml of water to the reactor, stir thoroughly to ensure that the sodium thiocyanate is completely dissolved. Add 5.5g of pyridine as a catalyst, slowly add 185g of benzenesulfonyl chloride, control the reaction temperature not to exceed 30°C, react for 3 hours, and let it stand to separate the layers to obtain 180g of the intermediate benzenesulfonyl isothiocyanate.

[0060] Take 80g of isobutanol, add 2.2g of zinc chloride, add the intermediate dropwise to the isobutanol solution, control the feeding rate, the reaction temperature is 55°C, react for 6 hours, and obtain N-benzenesulfonyl-O-isobutylthiocarbamate with a purity of 85%.

[0061] Example 4.

[0062] Add 81 g of sodium thiocyanate to the reactor, add 190 ml of water, stir well to ensure that the sodium thiocyanate is completely dissolved, add 4.0 g of N, N-dimethylaniline as a catalyst, slowly add 195 g of benzenesulfonyl chloride, control the reaction temperature not to exceed 30°C, react for 3 hours, and let it stand to separate the layers to obtain 190 g of the intermediate benzenesulfonyl isothiocyanate.

[0063] Take another 85g of isobutanol, add 4.2g of a mixture of potassium carbonate and zinc chloride (mass ratio 2:1), add the intermediate dropwise to the isobutanol solution, control the feeding rate, the reaction temperature is 60°C, react for 5 hours, and obtain N-benzenesulfonyl-O-isobutylthiocarbamate with a purity of 83%.

[0064] Example 5.

[0065] Add 76g of ammonium thiocyanate to the reactor, add 160ml of water, stir well to ensure that the ammonium thiocyanate is completely dissolved. Add 4.5g of N,N-dimethylaniline as a catalyst, slowly add 195g of benzenesulfonyl chloride, control the reaction temperature not to exceed 30°C, react for 3 hours, and let it stand to separate the layers to obtain 185g of the intermediate benzenesulfonyl isothiocyanate.

[0066] Take another 68g of isopropanol, add 2.8g of potassium carbonate, add the intermediate dropwise to the isopropanol solution, control the feeding rate, the reaction temperature is 60°C, react for 5.5 hours, and obtain N-benzenesulfonyl-O-isopropylthiocarbamate with a purity of 80%.

[0067] Application Example 1: A copper-zinc sulfide mine in Fushun.

[0068] The mine is a polymetallic sulfide ore, with copper, zinc, and sulfur as the main elements, and gold and silver as the associated valuable elements. Copper, zinc, sulfur, gold, and silver elements in the ore exist as independent minerals. The copper mineral is mainly chalcopyrite, followed by a small amount of tetrahedrite, chalcocite, and covellite; the zinc mineral is mainly sphalerite; the sulfur mineral is mainly pyrite and pyrrhotite; the gold and silver minerals are mainly silver-gold ore, gold-silver ore, and native silver. The copper grade of the original ore is 1.28%, the zinc grade is 1.98%, and the sulfur grade is 17.61%. Test conditions: grinding fineness -0.075mm accounts for 65%, lime 2000g / t, zinc sulfate 800g / t, sodium sulfite 500g / t, pine oil 20g / t, collector dosage 100g / t, test results are shown in Table 1.

[0069] Table 1 Roughing test results.

[0070]

[0071] It can be seen from the examples that N-benzenesulfonyl-O-alkylthiocarbamate has good collecting power and selectivity for copper-zinc sulfide ore.

[0072] Application Example 2: A copper-arsenic mine in Inner Mongolia.

[0073] The ore mainly contains copper, sulfur, arsenic, iron and other components, and is accompanied by silver. The independent mineral of copper is mainly chalcopyrite, with a content of 1.59%, the independent mineral of sulfur is pyrite and a small amount of marcasite, with a total content of 3.70%; the independent mineral of arsenic is arsenopyrite, with a content of 0.67%; the content is relatively low. The main non-metallic minerals are quartz, feldspar, sericite, carbonate minerals, chlorite and biotite.

[0074] Roughing grinding fineness -0.075mm accounts for 65%, calcium oxide 2000g / t, pine oil 20g / t, collector dosage 80g / t, test results are shown in Table 2.

[0075] Table 2 Roughing test results.

[0076]

[0077] It can be seen from the examples that N-benzenesulfonyl-O-alkylthiocarbamate has good capture ability and selectivity for copper sulfide arsenic ore.

Claims

1. A sulfide ore collector N-benzenesulfonyl-O-alkylthiocarbamate, characterized in that: It has the following structure: 。 2. A method for preparing a sulfide ore collector N-benzenesulfonyl-O-alkylthiocarbamate, characterized in that: The specific steps include: Step 1, add thiocyanate and a certain amount of water into a reaction vessel, control the stirring speed to completely dissolve the materials, add catalyst CT-1, slowly add benzenesulfonyl chloride, control the reaction temperature and time, and after the reaction is completed, separate the organic phase and the aqueous phase, and the oil phase is the intermediate benzenesulfonyl isothiocyanate; Step 2: Take a certain amount of methyl isobutyl carbinol, add catalyst CT-2, dropwise add the intermediate into the reaction container, control the reaction temperature and time, and obtain N-benzenesulfonyl-O-alkylthiocarbamate.

3. The method for preparing N-benzenesulfonyl-O-alkylthiocarbamate according to claim 2, characterized in that: The thiocyanate is one or a combination of sodium thiocyanate, ammonium thiocyanate or potassium thiocyanate.

4. The method for preparing N-benzenesulfonyl-O-alkylthiocarbamate according to claim 2, characterized in that: The catalyst CT-1 is one or a combination of N,N-dimethylaniline, pyridine or PEG-400.

5. The method for preparing N-benzenesulfonyl-O-alkylthiocarbamate according to claim 2, characterized in that: The catalyst CT-2 is one of potassium carbonate and zinc chloride or a mixture of the two.

6. The method for preparing N-benzenesulfonyl-O-alkylthiocarbamate according to claim 2, characterized in that: The mass ratio of the thiocyanate to water is 1:(1-3.5); the molar ratio of the thiocyanate to benzenesulfonyl chloride is 1:(1-1.2); the added amount of the CT-1 is 2%-10% of the mass of the thiocyanate; the molar ratio of the intermediate to the alcohol is: 1:(1-2.5); the added mass of the CT-2 is 1%-10% of the mass of the intermediate.

7. The method for preparing N-benzenesulfonyl-O-alkylthiocarbamate according to claim 2, characterized in that: In the step 1, the reaction temperature is 10-60° C. and the reaction time is 1-5 h; in the step 2, the reaction temperature is 30-90° C. and the reaction time is 1-8 h.

Images