Efficient collecting agent for multiphase copper ore as well as preparation method and application of efficient collecting agent

Abstract

The invention provides a multi-phase copper ore efficient collecting agent and a preparation method and application thereof. The multi-phase copper ore efficient collecting agent is a hydrate of thiazole mercaptan and benzothiazole mercaptan. The efficient collecting agent for the multi-phase copper ore is a hydrate of thiazolethiol and benzothiazolethiol, has good selectivity on copper sulfide and part of copper oxide minerals represented by chalcopyrite, bornite, chalcocite and malachite, is remarkable in collecting and recycling effect, and is particularly suitable for flotation separation of low-grade complex multi-phase copper ore.

Description

Technical Field

[0001] The invention belongs to the field of metallurgy and chemical industry, and specifically relates to a multiphase copper ore efficient collector and a preparation method and application thereof. Background Art

[0002] my country ranks first in the world in both the development and consumption of mineral resources. It is a country with a large number of mineral resources and a large consumer. Among them, the consumption of copper accounts for about 50% of the world's total consumption, but the reserves of copper resources account for only about 4% of the world. The consumption and external dependence of copper resources have been rising year by year. In 2020, the external dependence has exceeded 80%, becoming a major safety hazard for economic development. The types of copper ores in my country are complex, and the overall performance is that there are more poor ores and fewer rich ores. They are mainly distributed in southwestern regions such as Yunnan, Guizhou and Sichuan and provinces such as Inner Mongolia. The efficient recovery of low-grade complex multiphase copper ores has always been a difficulty and hot spot in the field of mineral processing. Improving the level of mineral processing technology for low-grade complex multiphase copper ores in my country has important economic value and practical significance. Due to the large difference in the natural floatability of copper minerals of different phases, the influence of the interlaced floatability between minerals, and the serious entrainment of mineralized foam, the requirements for copper collectors in the flotation process are relatively high. It is necessary to accurately capture copper minerals of different phases and reduce the entrainment of minerals with good floatability such as pyrite into the flotation foam. Although thiocarbamate and xanthate are stable in production and widely available as copper collectors, their disadvantages are that their collection capacity and selectivity are not strong (especially for surface-oxidized copper sulfide minerals), and their large usage leads to increased return water treatment costs. Therefore, it is very important to research and develop efficient collectors for multiphase copper ores to reduce the cost and risk of flotation. Summary of the invention

[0003] The first purpose of the present invention is to provide a multiphase copper ore efficient collector; the second purpose is to provide a preparation method of the multiphase copper ore efficient collector; the third purpose is to provide the application of the multiphase copper ore efficient collector.

[0004] The first object of the present invention is achieved in that the multiphase copper ore efficient collector is a hydrate of thiazole mercaptan and benzothiazole mercaptan.

[0005] The second object of the present invention is achieved by comprising the following steps: A. Add hydrochloric acid to the No. 1 reaction tank, and then add N,N-dimethylaniline, nitric acid and hydrogen in sequence, stir for 20-30 minutes, and reflux at a constant temperature of 80-90°C for 400-480 minutes to obtain material a: B. Feed material a into the No. 2 reaction tank, add catalyst and react to obtain material b:

[0006] C. Feed material b into the No. 3 reaction tank, add sodium thiosulfate under nitrogen atmosphere to react and obtain material c: (2C6H4(N2)N(CH3)2Cl+2Na2S2O3+2H2O→2C6H4(SH)N(CH3)2+2NaCI+Na2SO4+H2SO4+2N2); D. Feed material c into the No. 4 reaction tank, add 2-chlorothiazole and sodium hydrosulfide aqueous solution to react to obtain material d: (C3H2ClNS+NaSH→C3H3NS2+NaCI); E. Feed material d into the No. 5 reaction tank, add an oxidant to obtain the final product, i.e., the target multiphase copper ore efficient collector (C6H4(SH)N(CH3)2+I2→C7H5NS+CH4; 2C7H5NS+2NaHS+O2→2C7H5NS2+2NaOH).

[0007] The third object of the present invention is achieved by applying the multiphase copper ore efficient collector to the flotation process of low-grade complex multiphase copper ore.

[0008] The hydrophobic group of thiazole mercaptan in the multiphase copper ore efficient collector of the present invention is relatively small, so that the steric hindrance is reduced, the molecules are arranged more closely on the mineral surface, the hydrophobicity of the target mineral is improved, and the adhesion of the mineral particles and bubbles is promoted; the electrostatic potential energy distribution of the benzothiazole mercaptan molecule makes it easier to be directional adsorbed on the mineral surface, the adsorption free energy is relatively high, and the flotation efficiency is high; thiazole mercaptan is a non-ionic collector, less electron transfer occurs during the adsorption process, the non-selective reaction with other ions in the ore pulp is reduced, and thus the selectivity for the target mineral is improved; in an acidic or neutral medium, thiazole mercaptan exists in a molecular form, has high stability, and can be effectively adsorbed on the mineral surface; and under alkaline conditions, it may be converted into an ionic form, and the adsorption behavior is further adjusted.

[0009] The multiphase copper ore efficient collector of the present invention is a hydrate of thiazole mercaptan and benzothiazole mercaptan, which has good selectivity for copper sulfide represented by chalcopyrite, bornite, chalcocite and malachite and some copper oxide minerals, has a significant capture and recovery effect, and is particularly suitable for the flotation separation of low-grade complex multiphase copper ores.

[0010] The advantages of the present invention are: 1. The preparation method is simple, the group selectivity is good, and it can be more effectively adsorbed on the surface of different copper minerals, thereby improving the efficient flotation enrichment and recovery effect of different phases of copper minerals; 2. Good degradability after production and use, it will naturally degrade after being stored in the tailings pond for a certain period of time, and is environmentally friendly; 3. Low cost and easy to put into industrial scale production; 4. The production process does not produce three wastes, does not cause secondary pollution, and is environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 It is a schematic diagram of the process flow of the present invention. DETAILED DESCRIPTION

[0012] The present invention is further described below in conjunction with the embodiments, 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.

[0013] The multiphase copper ore efficient collector of the present invention is a hydrate of thiazolethiol and benzothiazolethiol.

[0014] The mass ratio of the thiazole thiol to the benzothiazole thiol is (2:1) to (3:1).

[0015] The method for preparing the multiphase copper ore efficient collector of the present invention comprises the following steps: A. Add hydrochloric acid to the No. 1 reaction tank, then add N, N-dimethylaniline, nitric acid and hydrogen in sequence, stir for 20-30 minutes, and reflux at a constant temperature of 80-90°C for 400-480 minutes to obtain material a; B. Feed material a into the second reaction tank, add sodium sulfite to react and obtain material b; C. Feed material b into reaction tank No. 3, add sodium thiosulfate under nitrogen atmosphere to react and obtain material c; D. Feed material c into reaction tank No. 4, add 2-chlorothiazole and sodium hydrosulfide aqueous solution to react to obtain material d; E. Feed material d into the No. 5 reaction tank and add iodine to react, thus obtaining the target multiphase copper ore efficient collector.

[0016] The mass ratio of hydrochloric acid, N,N-dimethylaniline, nitric acid and hydrogen described in step A is 2:1:1:8.

[0017] The catalyst described in step B is sodium sulfite or hydrogen peroxide.

[0018] The reaction temperature in step B is 200-260° C. and the reaction time is 40-60 min.

[0019] The reaction temperature in step C is 40-60°C; the reaction time is 20-30 minutes.

[0020] In step D, the amount of 2-chlorothiazole and sodium hydrosulfide aqueous solution added is 1 / (8~12) of the mass of material c.

[0021] The reaction temperature in step D is 60-80°C; the reaction time is 20-30 min.

[0022] The application described in the present invention is the application of the multi-phase copper ore efficient collector in the flotation process of low-grade complex multi-phase copper ore.

[0023] The present invention is further described below with specific implementation cases: Example 1

[0024] A. Add hydrochloric acid to reaction tank No. 1, then add N,N-dimethylaniline, nitric acid and hydrogen in sequence, stir for 20 minutes, and reflux at a constant temperature of 80-85°C for 480 minutes to obtain material a; wherein the mass ratio of hydrochloric acid, N,N-dimethylaniline, nitric acid and hydrogen is 2:1:1:8; B. Feed material a into the No. 2 reaction tank, add sodium nitrite or hydrogen peroxide as a catalyst, and react at a temperature of 250-260°C for 40 minutes to obtain material b; C. Feed material b into the No. 3 reaction tank, add sodium thiosulfate under nitrogen atmosphere, and react at a temperature of 50-60°C for 20 minutes to obtain material c; D. Feed material c into the No. 4 reaction tank, add an aqueous solution of 2-chlorothiazole to react and obtain material d; wherein the amount of 2-chlorothiazole and sodium hydrosulfide aqueous solution added is 1 / 8 of the mass of material c; E. Feed material d into the No. 5 reaction tank, add iodine to adjust the pH to 10 to obtain the final product, i.e., the target multiphase copper ore efficient collector.

[0025] Example 2 A. Add hydrochloric acid to reaction tank No. 1, then add N,N-dimethylaniline, nitric acid and hydrogen in sequence, stir for 30 minutes, and reflux at a constant temperature of 80-85°C for 400 minutes to obtain material a; wherein the mass ratio of carbon disulfide, N,N-dimethylaniline, nitric acid and hydrogen is 3:2:2:8; B. Feed material a into the No. 2 reaction tank, add the catalyst sodium nitrite, and react at a temperature of 200-220°C for 60 minutes to obtain material b; C. Feed material b into the No. 3 reaction tank, add sodium thiosulfate under nitrogen atmosphere, and react at a temperature of 40-50°C for 30 minutes to obtain material c; D. Feed material c into the No. 4 reaction tank, add 2-chlorothiazole and sodium hydrosulfide aqueous solution to react to obtain material d; wherein the amount of 2-chlorothiazole aqueous solution added is 1 / 12 of the mass of material c; E. Feed material d into the No. 5 reaction tank, add ammonia water to adjust the pH to 8 to obtain the final product, i.e., the target multiphase copper ore efficient collector.

[0026] Example 3 A. Add hydrochloric acid to reaction tank No. 1, then add N,N-dimethylaniline, nitric acid and hydrogen in sequence, stir for 25 minutes, and reflux at a constant temperature of 83-86°C for 450 minutes to obtain material a; wherein the mass ratio of carbon disulfide, N,N-dimethylaniline, nitric acid and hydrogen is 2.5:1.5:1.5:8; B. Feed material a into the No. 2 reaction tank, add nitrous acid as a catalyst, and react at a temperature of 230-250°C for 50 minutes to obtain material b; C. Feed material b into the No. 3 reaction tank, add sodium thiosulfate under nitrogen atmosphere, and react at a temperature of 45-55°C for 25 minutes to obtain material c; D. Feed material c into the No. 4 reaction tank, add 2-chlorothiazole and sodium hydrosulfide aqueous solution to react to obtain material d; wherein the amount of 2-chlorothiazole aqueous solution added is 1 / 10 of the mass of material c; E. Feed material d into the No. 5 reaction tank, add iodine to adjust the pH to 9 to obtain the final product, i.e., the target multiphase copper ore efficient collector.

[0027] Example 4 A. Add hydrochloric acid to reaction tank No. 1, then add N,N-dimethylaniline, nitric acid and hydrogen in sequence, stir for 24 minutes, and reflux at a constant temperature of 85-88°C for 420 minutes to obtain material a; wherein the mass ratio of carbon disulfide, N,N-dimethylaniline, nitric acid and hydrogen is 2:2:2:8; B. Feed material a into the No. 2 reaction tank, add catalyst hydrogen peroxide, and react at a temperature of 220-240°C for 53 minutes to obtain material b; C. Feed material b into the No. 3 reaction tank, add sodium thiosulfate under nitrogen atmosphere, and react at a temperature of 42-45°C for 26 minutes to obtain material c; D. Feed material c into the No. 4 reaction tank, add 2-chlorothiazole and sodium hydrosulfide aqueous solution to react to obtain material d; wherein the amount of 2-chlorothiazole aqueous solution added is 1 / 9 of the mass of material c; E. Feed material d into the No. 5 reaction tank, add iodine to adjust the pH to 8.5 to obtain the final product, i.e., the target multiphase copper ore efficient collector.

[0028] Example 5 A. Add hydrochloric acid to reaction tank No. 1, then add N,N-dimethylaniline, nitric acid and hydrogen in sequence, stir for 26 minutes, and reflux at a constant temperature of 86-89°C for 415 minutes to obtain material a; wherein the mass ratio of carbon disulfide, N,N-dimethylaniline, nitric acid and hydrogen is 3:1:1:8; B. Feed material a into the No. 2 reaction tank, add the catalyst sodium nitrite, and react at a temperature of 240-250°C for 43 minutes to obtain material b; C. Feed material b into the No. 3 reaction tank, add sodium thiosulfate under nitrogen atmosphere, and react at a temperature of 53-58°C for 27 minutes to obtain material c; D. Feed material c into the No. 4 reaction tank, add 2-chlorothiazole and sodium hydrosulfide aqueous solution to react to obtain material d; wherein the amount of 2-chlorothiazole aqueous solution added is 1 / 11 of the mass of material c; E. Feed material d into the No. 5 reaction tank, add iodine to adjust the pH to 9.5 to obtain the final product, i.e., the target multiphase copper ore efficient collector.

[0029] Example 6 The multiphase copper ore efficient collector prepared in Example 3 was tested as follows: the ore containing various copper sulfides to be treated was ground to -0.074 mm accounting for 70-75%, then added to the flotation machine for stirring, the copper collector was added and stirred for 1 minute, and then the frother 24K was added and stirred for 1 minute, and clean water was added to adjust the pulp concentration to 40-50%, and then aerated flotation was performed for 3 minutes to obtain a foam product as a copper rough concentrate, and the flotation tank continued to add copper collector and stirred for 1 minute, and aerated flotation was performed for 2 minutes to obtain a foam product as a copper middling ore, and the pulp retained in the flotation tank was the tailings. The test process is shown in Figure 1 , the test results are shown in Table 1.

[0030] Table 1 Small-scale test flotation results of copper ore

[0031] By using the existing reagents (i.e., ethiocarbamate, ethyl xanthate, butyl ammonium black medicine and ethyl thiocyanate), the copper recovery rate of tailings is between 6.01% and 10.48%, and by using the newly synthesized multi-phase copper ore high-efficiency collector, the copper recovery rate of tailings is 5.68%, indicating that the new reagent has good collection capacity; by using the existing reagents (i.e., ethiocarbamate, ethyl xanthate, butyl ammonium black medicine and ethyl thiocyanate), the copper grade of the copper concentrate is between 2.87% and 3.59%, and by using the newly synthesized multi-phase copper ore high-efficiency collector, the copper grade of the copper concentrate is 3.83%, indicating that the new reagent has the best selectivity.

[0032] Example 7 Experiments were conducted with the multiphase copper ore efficient collectors prepared in Example 1, Example 2, Example 4 and Example 5, respectively, using the same method as Example 6. The results all showed that the multiphase copper ore efficient collector of the present invention had good selectivity and significant capture and recovery effect.

Claims

1. A highly efficient collector for multiphase copper ore, characterized in that: The multi-phase copper ore efficient collector is a hydrate of thiazole mercaptan and benzothiazole mercaptan.

2. The multiphase copper ore efficient collector according to claim 1, characterized in that: The mass ratio of the thiazole thiol to the benzothiazole thiol is (2:1) to (3:1).

3. A method for preparing a high-efficiency collector for multiphase copper ore according to claim 1 or 2, characterized in that: The following steps are involved: A. Add hydrochloric acid to the No. 1 reaction tank, then add N, N-dimethylaniline, nitric acid and hydrogen in sequence, stir for 20-30 minutes, and reflux at a constant temperature of 80-90°C for 400-480 minutes to obtain material a; B. Feed material a into the No. 2 reaction tank, add a catalyst to react and obtain material b; C. Feed material b into reaction tank No. 3, add sodium thiosulfate under nitrogen atmosphere to react and obtain material c; D. Feed material c into reaction tank No. 4, add 2-chlorothiazole and an aqueous solution of sodium hydrosulfide to react to obtain material d; E. Feed material d into the No. 5 reaction tank and add an oxidant to obtain the final product, i.e., the target multiphase copper ore efficient collector.

4. The preparation method according to claim 3, characterized in that: The mass ratio of hydrochloric acid, N,N-dimethylaniline, nitric acid and hydrogen described in step A is (2-3): (1-2): (1-2):

8.

5. The preparation method according to claim 3, characterized in that: The catalyst described in step B is sodium nitrite or hydrogen peroxide.

6. The preparation method according to claim 3, characterized in that: The reaction temperature in step B is 200-260° C. and the reaction time is 40-60 min.

7. The preparation method according to claim 3, characterized in that: The reaction temperature in step C is 40-60°C; the reaction time is 20-30 minutes.

8. The preparation method according to claim 3, characterized in that: In step D, the amount of aqueous solution of 2-chlorothiazole added is 1 / (8~12) of the mass of material c.

9. The preparation method according to claim 3, characterized in that: The reaction temperature in step D is 60-80°C; the reaction time is 20-30 min.

10. An application of the multiphase copper ore efficient collector according to claim 1 or 2, characterized in that: The application of the multiphase copper ore efficient collector in the flotation process of low-grade complex multiphase copper ore.

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