A high-efficiency collector for multiphase copper ore, its preparation method and application

Abstract

This invention provides a highly efficient collector for multiphase copper ores, its preparation method, and its application. The highly efficient collector for multiphase copper ores is a hydrate of thiazolium thiol and benzothiazolium thiol. The highly efficient collector for multiphase copper ores described in this invention, a hydrate of thiazolium thiol and benzothiazolium thiol, exhibits good selectivity for copper sulfide minerals such as chalcopyrite, bornite, chalcocite, and malachite, as well as some copper oxide minerals, with significant collection and recovery effects. It is particularly suitable for the flotation separation of low-grade complex multiphase copper ores.

Description

Technical Field

[0001] This invention belongs to the field of metallurgy and chemical engineering, specifically relating to a high-efficiency collector for multiphase copper ore, its preparation method, and its application. Background Technology

[0002] my country ranks first in the world in both mineral resource development and consumption, making it both a major mineral resource country and a major consumer. Copper consumption accounts for approximately 50% of global consumption, but copper reserves represent only about 4% of the global total. The consumption and dependence on foreign copper resources have been rising year after year, exceeding 80% in 2020, posing a significant security threat to economic development. my country's copper ore types are complex, generally characterized by a predominance of low-grade ores and a scarcity of high-grade ores, mainly distributed in southwestern regions such as Yunnan, Guizhou, and Sichuan, and provinces like Inner Mongolia. Efficient recovery of low-grade, complex, multiphase copper ores has always been a challenge and a hot topic in mineral processing. Improving the beneficiation technology for low-grade, complex, multiphase copper ores in my country has significant economic value and practical implications. Due to the large differences in the natural floatability of different phases of copper minerals, and the overlapping influence of floatability between minerals, severe entrainment of mineralized foam occurs. Therefore, the requirements for copper collectors during flotation are high, necessitating precise collection of copper minerals of different phases while minimizing the entrainment of highly floatable minerals such as pyrite in the flotation foam. Although thiocyanates and xanthates are stable and widely available collectors for copper, their drawbacks include poor collecting ability and selectivity (especially for surface-oxidized copper sulfide minerals), and their large usage leads to increased wastewater treatment costs. Therefore, it is crucial to research and develop highly efficient collectors for multiphase copper ores to reduce flotation costs and risks. Summary of the Invention

[0003] The first objective of this invention is to provide a highly efficient collector for multiphase copper ore; the second objective is to provide a method for preparing the aforementioned highly efficient collector for multiphase copper ore; and the third objective is to provide applications of the aforementioned highly efficient collector for multiphase copper ore.

[0004] The first objective of this invention is achieved by the fact that the high-efficiency collector for multiphase copper ore is a hydrate of thiazothiol and benzothiazothiol.

[0005] The second objective of this invention is achieved by including the following steps:

[0006] A. Add hydrochloric acid to reaction vessel No. 1, then add N,N-dimethylaniline, nitric acid and hydrogen gas in sequence, stir for 20-30 minutes, and reflux at 80-90℃ for 400-480 minutes to obtain material a:

[0007]

[0008] B. Feed material a into reaction vessel No. 2, add catalyst and react to obtain material b:

[0009]

[0010] C. Feed material b into reaction vessel No. 3, add sodium thiosulfate under nitrogen atmosphere to react and obtain material c: (2C6H4(N2)N(CH3)2Cl+2Na2S2O3+2H2O→2C6H4(SH)N(CH3)2+2NaCl+Na2SO4+H2SO4+2N2);

[0011] D. Feed material c into reaction vessel No. 4, add 2-chlorothiazol and sodium hydrosulfide aqueous solution to react and obtain material d:

[0012] (C3H2ClNS+NaSH→C3H3NS2+NaCI);

[0013] E. Feed material d into reaction vessel No. 5, add oxidant to obtain the final product, namely the target material multiphase copper ore high-efficiency collector (C6H4(SH)N(CH3)2+I2→C7H5NS+CH4).

[0014] 2C7H5NS+2NaHS+O2→2C7H5NS2+2NaOH).

[0015] The third objective of this invention is achieved by the application of the aforementioned high-efficiency collector for multiphase copper ore in the flotation process of low-grade complex multiphase copper ore.

[0016] The thiazothiols in the multiphase copper ore high-efficiency collector of this invention have smaller hydrophobic groups, reducing steric hindrance and allowing molecules to be more tightly arranged on the mineral surface, improving the hydrophobicity of the target mineral and promoting the adhesion of mineral particles to bubbles. The electrostatic potential distribution of benzothiazothiols makes them easier to be directionally adsorbed onto the mineral surface, with a higher adsorption free energy and higher flotation efficiency. Thiazolethiols are non-ionic collectors, with less electron transfer during adsorption, reducing non-selective reactions with other ions in the pulp, thereby improving the selectivity for the target mineral. In acidic or neutral media, thiazothiols exist in molecular form, have high stability, and can be effectively adsorbed onto the mineral surface; while under alkaline conditions, they may be converted into ionic form, further adjusting the adsorption behavior.

[0017] The multiphase copper ore high-efficiency collector described in this invention is a hydrate of thiazothiol and benzothiazothiol, which has good selectivity for copper sulfide minerals such as chalcopyrite, bornite, chalcocite, and malachite, as well as some copper oxide minerals, with significant collection and recovery effects. It is particularly suitable for flotation separation of low-grade complex multiphase copper ores.

[0018] The advantages of this invention are:

[0019] 1. The preparation method is simple and has good group selectivity, which can more effectively adsorb onto the surface of different copper minerals, thereby improving the efficient flotation enrichment and recovery effect of copper minerals of different phases;

[0020] 2. It has good degradability after production and use, and can naturally degrade after being stored in the tailings dam for a certain period of time, making it environmentally friendly;

[0021] 3. Low cost and easy to scale up for industrial production;

[0022] 4. The production process does not generate any waste or secondary pollution, making it environmentally friendly. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the process flow of the present invention. Detailed Implementation

[0024] The present invention will be further described below with reference to embodiments, but this is not intended to limit the present invention in any way. Any modifications or substitutions made based on the teachings of the present invention shall fall within the protection scope of the present invention.

[0025] The multiphase copper ore high-efficiency collector described in this invention is a hydrate of thiazothiol and benzothiazothiol.

[0026] The mass ratio of the thiazothiol to benzothiazothiol is (2:1) to (3:1).

[0027] The preparation method of the high-efficiency collector for multiphase copper ore according to the present invention includes the following steps:

[0028] A. Add hydrochloric acid to reaction vessel No. 1, then add N,N-dimethylaniline, nitric acid and hydrogen in sequence, stir for 20~30 min, and reflux at 80~90℃ for 400~480 min to obtain material a;

[0029] B. Feed material a into reaction vessel No. 2, add sodium sulfite and react to obtain material b;

[0030] C. Feed material b into reaction vessel No. 3, add sodium thiosulfate under nitrogen atmosphere to react and obtain material c;

[0031] D. Feed material c into reaction vessel No. 4, add 2-chlorothiazol and sodium hydrosulfide aqueous solution to react and obtain material d;

[0032] E. Feed material d into reaction vessel No. 5, add iodine to react, and the target material, multiphase copper ore, is produced as a high-efficiency collector.

[0033] The mass ratio of hydrochloric acid, N,N-dimethylaniline, nitric acid, and hydrogen in step A is 2:1:1:8.

[0034] The catalyst mentioned in step B is sodium sulfite or hydrogen peroxide.

[0035] The reaction temperature in step B is 200~260℃; the reaction time is 40~60min.

[0036] The reaction temperature in step C is 40~60℃; the reaction time is 20~30min.

[0037] In step D, the amount of aqueous solution of 2-chlorothiazolium and sodium hydrosulfide added is 1 / (8~12) of the mass of material c.

[0038] The reaction temperature in step D is 60~80℃; the reaction time is 20~30min.

[0039] The application described in this invention is the use of the high-efficiency collector for multiphase copper ore in the flotation process of low-grade complex multiphase copper ore.

[0040] The invention will be further illustrated below with specific implementation examples:

[0041] Example 1

[0042] A. Add hydrochloric acid to reaction vessel No. 1, then add N,N-dimethylaniline, nitric acid and hydrogen in sequence, stir for 20 min, and reflux at 80~85℃ for 480 min to obtain material a; wherein the mass ratio of hydrochloric acid, N,N-dimethylaniline, nitric acid and hydrogen is 2:1:1:8;

[0043] B. Feed material a into reaction vessel No. 2, add catalyst sodium nitrite or hydrogen peroxide, and react at 250~260℃ for 40 minutes to obtain material b.

[0044] C. Feed material b into reaction vessel No. 3, add sodium thiosulfate under nitrogen atmosphere, and react at 50~60℃ for 20 minutes to obtain material c;

[0045] D. Feed material c into reaction vessel No. 4, add an aqueous solution of 2-chlorothiazolium to react and obtain material d; wherein the amount of 2-chlorothiazolium and sodium hydrosulfide aqueous solution added is 1 / 8 of the mass of material c;

[0046] E. Feed material d into reaction vessel No. 5, add iodine to adjust the pH to 10 to obtain the final product, namely the target substance, multiphase copper ore high-efficiency collector.

[0047] Example 2

[0048] A. Hydrochloric acid was added to reaction vessel No. 1, followed by N,N-dimethylaniline, nitric acid and hydrogen gas in sequence. The mixture was stirred for 30 minutes and then refluxed at a constant temperature of 80~85℃ for 400 minutes to obtain material a. The mass ratio of carbon disulfide, N,N-dimethylaniline, nitric acid and hydrogen gas was 3:2:2:8.

[0049] B. Feed material a into reaction vessel No. 2, add sodium nitrite catalyst, and react at 200~220℃ for 60 minutes to obtain material b.

[0050] C. Feed material b into reaction vessel No. 3, add sodium thiosulfate under nitrogen atmosphere, and react at 40~50℃ for 30 minutes to obtain material c;

[0051] D. Feed material c into reaction vessel No. 4, add 2-chlorothiazolium and sodium hydrosulfide aqueous solution to react and obtain material d; wherein the amount of 2-chlorothiazolium aqueous solution added is 1 / 12 of the mass of material c;

[0052] E. Feed material d into reaction tank No. 5, add ammonia water to adjust the pH to 8 to obtain the final product, namely the target material, multiphase copper ore high-efficiency collector.

[0053] Example 3

[0054] A. Hydrochloric acid was added to reaction vessel No. 1, followed by N,N-dimethylaniline, nitric acid and hydrogen gas in sequence. The mixture was stirred for 25 minutes and then refluxed at a constant temperature of 83~86℃ for 450 minutes to obtain material a. The mass ratio of carbon disulfide, N,N-dimethylaniline, nitric acid and hydrogen gas was 2.5:1.5:1.5:8.

[0055] B. Feed material a into reaction vessel No. 2, add nitrous acid catalyst, and react at 230~250℃ for 50 minutes to obtain material b.

[0056] C. Feed material b into reaction vessel No. 3, add sodium thiosulfate under nitrogen atmosphere, and react at 45~55℃ for 25 minutes to obtain material c;

[0057] D. Feed material c into reaction vessel No. 4, add 2-chlorothiazolium and sodium hydrosulfide aqueous solution to react and obtain material d; wherein the amount of 2-chlorothiazolium aqueous solution added is 1 / 10 of the mass of material c;

[0058] E. Feed material d into reaction vessel No. 5, add iodine to adjust the pH to 9 to obtain the final product, namely the target substance, multiphase copper ore high-efficiency collector.

[0059] Example 4

[0060] A. Hydrochloric acid was added to reaction vessel No. 1, followed by N,N-dimethylaniline, nitric acid and hydrogen gas in sequence. The mixture was stirred for 24 minutes and then refluxed at a constant temperature of 85~88℃ for 420 minutes to obtain material a. The mass ratio of carbon disulfide, N,N-dimethylaniline, nitric acid and hydrogen gas was 2:2:2:8.

[0061] B. Feed material a into reaction vessel No. 2, add hydrogen peroxide as catalyst, and react at 220~240℃ for 53 minutes to obtain material b.

[0062] C. Feed material b into reaction vessel No. 3, add sodium thiosulfate under nitrogen atmosphere, and react at 42~45℃ for 26 minutes to obtain material c;

[0063] D. Feed material c into reaction vessel No. 4, add 2-chlorothiazolium and sodium hydrosulfide aqueous solution to react and obtain material d; wherein the amount of 2-chlorothiazolium aqueous solution added is 1 / 9 of the mass of material c;

[0064] E. Feed material d into reaction vessel No. 5, add iodine to adjust the pH to 8.5 to obtain the final product, namely the target substance, multiphase copper ore high-efficiency collector.

[0065] Example 5

[0066] A. Hydrochloric acid was added to reaction vessel No. 1, followed by N,N-dimethylaniline, nitric acid and hydrogen in sequence. The mixture was stirred for 26 minutes and then refluxed at a constant temperature of 86~89℃ for 415 minutes to obtain material a. The mass ratio of carbon disulfide, N,N-dimethylaniline, nitric acid and hydrogen was 3:1:1:8.

[0067] B. Feed material a into reaction vessel No. 2, add sodium nitrite catalyst, and react at 240~250℃ for 43 minutes to obtain material b.

[0068] C. Feed material b into reaction vessel No. 3, add sodium thiosulfate under nitrogen atmosphere, and react at 53~58℃ for 27 min to obtain material c;

[0069] D. Feed material c into reaction vessel No. 4, add 2-chlorothiazol and sodium hydrosulfide aqueous solution to react and obtain material d; wherein the amount of 2-chlorothiazol aqueous solution added is 1 / 11 of the mass of material c;

[0070] E. Feed material d into reaction vessel No. 5, add iodine to adjust the pH to 9.5 to obtain the final product, namely the target substance, multiphase copper ore high-efficiency collector.

[0071] Example 6

[0072] The high-efficiency collector for multiphase copper ore prepared in Example 3 was tested as follows: The ore containing various copper sulfides was ground to a fineness of -0.074 mm (70-75%), then added to a flotation machine and stirred. A copper collector was added and stirred for 1 minute, followed by the addition of frother 24K and stirring for another minute. Water was added to adjust the pulp concentration to 40-50%, and then aeration and flotation were performed for 3 minutes to obtain a frothy product, which was the copper rough concentrate. The copper collector was then added to the flotation cell and stirred for 1 minute, followed by aeration and flotation for 2 minutes to obtain a frothy product, which was the copper middlings. The pulp remaining in the flotation cell was the tailings. The test procedure is as follows: Figure 1 The experimental results are shown in Table 1.

[0073] Table 1 Results of small-scale copper ore flotation tests

[0074]

[0075] Using existing reagents (i.e., ethyl thiocyanate, ethyl xanthate, butylammonium black powder, and ethyl thiocyanate), the copper recovery rate of tailings ranges from 6.01% to 10.48%. Using the newly synthesized high-efficiency collector for multiphase copper ore, the copper recovery rate of tailings is 5.68%, indicating that the new reagent has better collecting ability. Using existing reagents (i.e., ethyl thiocyanate, ethyl xanthate, butylammonium black powder, and ethyl thiocyanate), the copper grade of copper roughing concentrate ranges from 2.87% to 3.59%. Using the newly synthesized high-efficiency collector for multiphase copper ore, the copper grade of copper roughing concentrate is 3.83%, indicating that the new reagent has the best selectivity.

[0076] Example 7

[0077] Experiments were conducted using the high-efficiency collectors for multiphase copper ore prepared in Examples 1, 2, 4, and 5, respectively, using the same methods as in Example 6. The results all showed that the high-efficiency collectors for multiphase copper ore described in this invention have good selectivity and significant collection and recovery effects.

Claims

1. A method for preparing a high efficiency collector for polymetallic copper ores, characterized by, The aforementioned high-efficiency collector for multiphase copper ore is a hydrate of thiazothiol and benzothiazothiol, and its specific preparation method includes the following steps: A. Add hydrochloric acid to reaction vessel No. 1, then add N,N-dimethylaniline, nitric acid and hydrogen in sequence, stir for 20~30 min, and reflux at 80~90℃ for 400~480 min to obtain material a; B. Feed material a into reaction tank No. 2, add catalyst sodium nitrite or hydrogen peroxide to react and obtain material b. C. Feed material b into reaction vessel No. 3, add sodium thiosulfate under nitrogen atmosphere to react and obtain material c; D. Feed material c into reaction vessel No. 4, add aqueous solution of 2-chlorothiazolium and aqueous solution of sodium hydrosulfide to react and obtain material d; E. Feed material d into reaction vessel No. 5, add oxidant to obtain the final product, namely the target material, multiphase copper ore high-efficiency collector.

2. The production method according to claim 1, characterized by, The mass ratio of the thiazothiol to benzothiazothiol is (2:1) to (3:1).

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

8.

4. The method of claim 1, wherein, The reaction temperature in step B is 200~260℃; the reaction time is 40~60min.

5. The preparation method according to claim 1, characterized in that, The reaction temperature in step C is 40~60℃; the reaction time is 20~30min.

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

7. The preparation method according to claim 1, characterized in that, The reaction temperature in step D is 60~80℃; the reaction time is 20~30min.

8. The preparation method according to any one of claims 1 to 7, characterized in that, The aforementioned high-efficiency collector for multiphase copper ore is applied in the flotation process of low-grade complex multiphase copper ore.

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