Copper-molybdenum efficient bulk flotation separation collecting agent and preparation method and application thereof

Abstract

The invention provides an efficient copper-molybdenum bulk flotation separation collecting agent as well as a preparation method and application thereof. The efficient copper-molybdenum bulk flotation separation collecting agent is synthesized by taking dithiocarbonate and mixed hydrocarbon oil as raw materials. The novel copper-molybdenum bulk flotation collecting agent is synthesized by taking the dithiocarbonate and the mixed hydrocarbon oil as raw materials, and the copper-molybdenum recovery efficiency is improved in the flotation process. The pretreatment technology before flotation has the advantages of being high in applicability, remarkable in effect and easy to implement on site, technological indexes can be optimized on the basis of an original flotation technology, useful minerals are prevented from being lost in tailings in the flotation circulation process, and optimization of the on-site flotation technology is achieved.

Description

Technical Field

[0001] The invention belongs to the field of metallurgy and chemical industry, and specifically relates to a copper-molybdenum high-efficiency mixed flotation separation collector and a preparation method and application thereof. Background Art

[0002] my country is a country with large resource consumption. Especially in recent years, the demand for mineral resources for economic development has become increasingly urgent. According to statistics, in the current porphyry copper-molybdenum ore, the mineral composition is relatively complex. Generally, it is a "poor, fine, and mixed" mineral with three minerals of copper, molybdenum, and sulfur coexisting. The copper and molybdenum grades in the original ore are low, and they contain each other seriously. The process commonly used in copper-molybdenum flotation is coarse grinding, copper-molybdenum mixed flotation-mixed concentrate regrinding-copper-molybdenum separation, and finally copper concentrate and molybdenum concentrate are obtained. It can be seen that how to obtain copper-molybdenum concentrate with high grade and recovery rate is an important link to improve the efficiency of copper-molybdenum flotation separation.

[0003] Based on the strategic position and consumption demand of copper, molybdenum and other metals in the development of the national economy, developing and utilizing copper, molybdenum and other metal resources and increasing the efficient separation and recovery of copper, molybdenum and other metal resources are one of the effective means to increase the amount of resources. Therefore, it is very important to research and develop new non-toxic and efficient copper-molybdenum collectors to reduce the cost and risk of flotation. Summary of the invention

[0004] The first purpose of the present invention is to provide a copper-molybdenum high-efficiency mixed flotation separation collector; the second purpose is to provide a preparation method of the copper-molybdenum high-efficiency mixed flotation separation collector; the third purpose is to provide the application of the copper-molybdenum high-efficiency mixed flotation separation collector.

[0005] The first object of the present invention is achieved in that the copper-molybdenum high-efficiency mixed flotation separation collector is synthesized using dithiocarbonate and mixed hydrocarbon oil as raw materials.

[0006] The second object of the present invention is achieved by comprising the following steps: A. Add water to reaction tank No. 1, and add sodium hydroxide at a temperature of 30-40°C under stirring to prepare sodium hydroxide solution a; then add methyl isobutyl carbinol solution at a temperature of 30-40°C, and stir for 30-40 minutes to obtain material b; B. Feed material b into the No. 2 reaction tank, control the temperature at 5-10°C, add carbon disulfide, and then control the temperature at 10-20°C and stir the reaction for 20-30 minutes to obtain material c; (A, B process reaction equation: C6H 14 O + NaOH + CS2 → C6H 13 OCS2Na+H2O) C. Feed material c into the No. 3 reaction tank, add mixed hydrocarbon oil, control the temperature at 20-30°C, stir and react for 20-30 minutes to obtain material d; The main function of adding non-polar mixed hydrocarbon solvents is to form a hydrophobic film on the mineral surface through physical adsorption, promote the adhesion of bubbles and mineral particles, and help dithiocarbonate to synergistically enhance the mineral-bubble adhesion efficiency and make it evenly dispersed in the slurry.

[0007] D. Feed material d into reaction tank No. 4, add cross-linking agent 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide / N-hydroxysuccinimide (EDC / NHS), control the temperature to 30-40°C and stir the reaction for 10-20 minutes to obtain material e, which is a functional sodium dithiocarbonate-hydrocarbon oil complex, that is, a high-efficiency mixed flotation separation collector for the target copper and molybdenum.

[0008] The equation for the reaction of EDC / NHS with fatty acids or carboxylic acid groups in mixed hydrocarbon oils to form esters is:

[0009] The addition of EDC / NHS to the reaction forms an ester bond, which has stable chemical properties and high flotation activity. It promotes cross-linking by activating ester groups, enhances the binding force between collector molecules, enhances the adsorption stability on the mineral surface, and enhances the strong capture ability of copper sulfide minerals. In addition, EDC / NHS can covalently link dithiocarbonate with the long chain of hydrocarbon oil to form an amphiphilic structure that is both polar (adsorbing minerals) and non-polar (hydrophobic), thereby enhancing the capture ability of the agent for molybdenum sulfide minerals.

[0010] The third object of the present invention is achieved by applying the copper-molybdenum high-efficiency mixed flotation separation collector in the copper-molybdenum mineral mixed flotation separation process.

[0011] The copper-molybdenum high-efficiency mixed flotation separation collector of the present invention is a high-efficiency mixture synthesized from dithiocarbonate and mixed hydrocarbon oil as raw materials. The added mixed hydrocarbon oil has a dispersing and synergistic effect on the dithiocarbonate obtained by the reaction, and the addition of a cross-linking agent can improve the structural stability and adsorption efficiency of the copper-molybdenum collector through intermolecular cross-linking. It has good selectivity for copper sulfide minerals represented by chalcopyrite and molybdenite, and has a significant collection effect, and is particularly suitable for mixed flotation separation of copper-molybdenum minerals.

[0012] The advantages of the present invention are: 1. The added cross-linking agent forms a buffer salt, which reacts with the hydroxyl group of the target molecule to form an ester bond. It has stable chemical properties, high flotation activity, strong adaptability to the pH value of the medium, and strong capture ability for copper sulfide minerals. 2. Adding cross-linking agent to hydrocarbon oil can make the molecules of saturated hydrocarbon and unsaturated hydrocarbon oriented isomerized, increase the contact angle between hydrocarbon compounds and selected minerals, change the carrier potential at the same time, strengthen the adsorption force between selected minerals and collectors, and enhance the collection ability of reagents for molybdenum sulfide minerals; 3. Good degradability after production and use, it will naturally degrade after being stored in the tailings pond for a certain period of time, and it is environmentally friendly; 4. Low cost and easy to put into industrial scale production; 5. The production process does not produce three wastes, does not cause secondary pollution, and is environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is a schematic diagram of the copper-molybdenum mixed flotation process of the present invention. DETAILED DESCRIPTION

[0014] 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.

[0015] The copper-molybdenum high-efficiency mixed flotation separation collector of the present invention is synthesized using dithiocarbonate and mixed hydrocarbon oil as raw materials.

[0016] The mass ratio of the dithiocarbonate to the mixed hydrocarbon oil is (3-3.5): (1.5-2).

[0017] The dithiocarbonate is prepared by using methyl isobutyl carbinol, CS2 and NaOH as raw materials.

[0018] The mass ratio of NaOH, methyl isobutyl carbinol and CS2 in the dithiocarbonate is (2.5-3):1:(1.5-2).

[0019] The mixed hydrocarbon oil is a mixture of diesel, kerosene and biodiesel.

[0020] The mass ratio of the diesel, kerosene and biodiesel is 4:2:1.

[0021] The method for preparing the copper-molybdenum high-efficiency mixed flotation separation collector of the present invention comprises the following steps: A. Add water to reaction tank No. 1, and add sodium hydroxide at a temperature of 30-40°C under stirring to prepare sodium hydroxide solution a; then add methyl isobutyl carbinol solution at a temperature of 30-40°C, and stir for 30-40 minutes to obtain material b; B. Feed material b into the No. 2 reaction tank, control the temperature at 5-10°C, add carbon disulfide, and then control the temperature at 10-20°C and stir the reaction for 20-30 minutes to obtain material c; C. Feed material c into the No. 3 reaction tank, add mixed hydrocarbon oil, control the temperature at 20-30°C, stir and react for 20-30 minutes to obtain material d; D. Feed material d into the No. 4 reaction tank, add the cross-linking agent 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide / N-hydroxysuccinimide (EDC / NHS), control the temperature to 30-40°C and stir the reaction for 10-20 minutes to obtain material e, which is the target copper-molybdenum high-efficiency mixed flotation separation collector.

[0022] In step A, the mass ratio of water, sodium hydroxide and methyl isobutyl carbinol is (240~275):(2.5~3):1.

[0023] In step B, the mass ratio of carbon disulfide and material b is (1.5~2):1.

[0024] The application of the present invention is the application of the copper-molybdenum high-efficiency mixed flotation separation collector in the copper-molybdenum mineral mixed flotation separation process.

[0025] The present invention is further described below with specific implementation cases: Example 1

[0026] raw material: Sodium hydroxide analytical grade Aladdin Reagent (Shanghai) Co., Ltd. Content ≥ 99%; Methyl isobutyl carbinol analytical grade Sinopharm Chemical Reagent Co., Ltd. content ≥99%; Diesel oil analytical grade Shanghai MacLean Biochemical Technology Co., Ltd. Kerosene analytical pure Sinopharm Chemical Reagent Co., Ltd. Biodiesel analytical grade Sinopharm Chemical Reagent Co., Ltd. EDC / NHS analytical grade Aladdin Reagent (Shanghai) Co., Ltd. content ≥99%; Carbon disulfide analytical grade Sinopharm Chemical Reagent Co., Ltd. content ≥ 99%; operate: Step 1: Preheat the reaction tank to keep it at a constant temperature of 35°C, place 1 kg of water in the reaction tank, and slowly stir and add sodium hydroxide. Keep the temperature in the reaction tank at 35°C, slowly add 5% concentration of methyl isobutyl carbinol, and stir for 30 minutes until it is completely dissolved to obtain material b.

[0027] Step 2: Cool the No. 2 reaction tank to 10°C, feed material b into the No. 2 reaction tank, slowly add carbon disulfide after stirring, and stir at a constant temperature of 10°C for 30 minutes to obtain material c; In the third step, material c is fed into the No. 3 reaction tank, and after stirring, hydrocarbon oil emulsified solution (diesel: kerosene = 2:1) is slowly added, and stirred for 30 minutes to obtain material d; In the fourth step, material d was fed into the No. 4 reaction tank, and after stirring, the cross-linking agent EDC / NHS was slowly added and stirred for 20 minutes to obtain material e as the final product.

[0028] Product application results: A local research institute conducted a closed-circuit test of copper-molybdenum mixed flotation of a small copper-molybdenum-sulfur mixed ore as a copper-molybdenum collector. The original ore had a Cu grade of 0.28% and a Mo grade of 0.011%. The flotation effect was determined as follows: Calculate the effective solid content of the finished product to prepare a (w / w) aqueous solution, take the white milky liquid, add 40 g / t, add it to a 1.5L flotation tank, according to Figure 1 The process was tested in a closed circuit, and the copper recovery rate of the foam product was 82.61%, the copper grade was 21.01%, the molybdenum recovery rate was 79.24%, the molybdenum grade was 0.75%, the Cu grade in the tailings was 0.045%, and the molybdenum grade was 0.002%, which is better than the current mixing of xanthate and diesel.

[0029] Example 2 raw material: Sodium hydroxide 300kg (content 99% w / w, pure 297kg) Methyl isobutyl carbinol 150kg (content 99% w / w, pure 148.5kg) 100kg diesel (content 99% w / w, equivalent to 99kg pure) Kerosene 50kg (content 99% w / w, pure 49.5kg) Biodiesel 25kg (content 99% w / w, pure 24.75kg) EDC / NHS 200kg (content 99% w / w, pure 198kg) Carbon disulfide 200kg (content 99% w / w, pure 198kg) operate: Step 1: Preheat the reaction tank to keep it at a constant temperature of 35°C, place enough aqueous solution in the reaction tank, and slowly stir and add sodium hydroxide, keep the temperature in the reaction tank at 35°C, slowly add methyl isobutyl carbinol, and stir for 30 minutes until it is completely dissolved to obtain material b, wherein sodium hydroxide: methyl isobutyl carbinol: water = 2:1:45.

[0030] The second step is to cool the No. 2 reaction tank to 10°C, feed material b into the No. 2 reaction tank, slowly add carbon disulfide after stirring, and stir at a constant temperature of 10°C for 30 minutes to obtain material c, wherein material b: carbon disulfide = 2:1.5.

[0031] In the third step, material c is fed into the No. 3 reaction tank, and after stirring, hydrocarbon oil emulsified solution (diesel: kerosene = 2:1) is slowly added, and stirred for 30 minutes to obtain material d; In the fourth step, material d was fed into the No. 4 reaction tank, and after stirring, the cross-linking agent EDC / NHS was slowly added and stirred for 20 minutes to obtain material e as the final product.

[0032] Product application results: It was used as a copper-molybdenum mixed flotation collector in a local porphyry copper-molybdenum-sulfur mixed ore plant to measure the flotation effect Calculated based on the effective solid content of the finished product, a (w / w) aqueous solution is prepared, and a white milky liquid is added in an amount of 45 g / t, added to the slurry mixing barrel, stirred for 6 minutes, and then fed into the flotation machine for aeration flotation for 5 minutes. The foam product can obtain a copper concentrate with a copper grade of 25.14% and a recovery rate of 91.26%, of which the copper concentrate contains 0.86% molybdenum. The molybdenum recovery rate is 87.43%. It is better than the xanthate and kerosene collectors currently used in the concentrator.

[0033] Example 3 raw material: Sodium hydroxide 400kg (content 99% w / w, pure 396kg) Methyl isobutyl carbinol 200kg (content 99% w / w, pure 198kg) 200kg diesel (content 99% w / w, equivalent to 198kg pure diesel) Kerosene 150kg (content 99% w / w, pure 148.5kg) Biodiesel 100kg (content 99% w / w, equivalent to 99kg pure) EDC / NHS 300kg (content 99%w / w, pure 297kg) 300kg of carbon disulfide (content 99% w / w, pure 297kg) operate: Step 1: Preheat the reaction tank to keep it at a constant temperature of 35°C, place enough aqueous solution in the reaction tank, and slowly stir and add sodium hydroxide, keep the temperature in the reaction tank at 35°C, slowly add methyl isobutyl carbinol, and stir for 30 minutes until it is completely dissolved to obtain material b, wherein sodium hydroxide: methyl isobutyl carbinol: water = 2:1:45.

[0034] The second step is to cool the No. 2 reaction tank to 10°C, feed material b into the No. 2 reaction tank, slowly add carbon disulfide after stirring, and stir at a constant temperature of 10°C for 30 minutes to obtain material c, wherein material b: carbon disulfide = 2:1.

[0035] In the third step, material c is fed into the No. 3 reaction tank, and after stirring, hydrocarbon oil emulsified solution (diesel: kerosene: biodiesel = 2:1.5:1) is slowly added, and stirred for 30 minutes to obtain material d; In the fourth step, material d was fed into the No. 4 reaction tank, and after stirring, the cross-linking agent EDC / NHS was slowly added and stirred for 20 minutes to obtain material e as the final product.

[0036] Product application results: It was used as a copper-molybdenum mixed flotation collector in a local porphyry copper-molybdenum-sulfur mixed ore plant to measure the flotation effect Calculated based on the effective solid content of the finished product, a (w / w) aqueous solution is prepared, and a white milky liquid is added in an amount of 33g / t, added to the slurry mixing barrel, stirred for 5 minutes, and then fed into the flotation machine for aeration flotation for 5 minutes. The foam product can obtain a copper concentrate with a copper grade of 26.28% and a recovery rate of 88.98%, wherein the copper concentrate contains 0.79% molybdenum. The molybdenum recovery rate is 84.79%. It is better than the xanthate and diesel collector currently used in the concentrator.

[0037] Example 4 raw material: Sodium hydroxide 400kg (content 99% w / w, pure 396kg) Methyl isobutyl carbinol 100kg (content 99% w / w, pure 99kg) 200kg diesel (content 99% w / w, equivalent to 198kg pure diesel) Kerosene 100kg (content 99% w / w, equivalent to 99kg pure) Biodiesel 40kg (content 99% w / w, pure 39.6kg) EDC / NHS 400kg (content 99%w / w, pure 396kg) Carbon disulfide 200kg (content 99% w / w, pure 198kg) operate: Step 1: Preheat the reaction tank to keep it at a constant temperature of 35°C, place enough aqueous solution in the reaction tank, and slowly stir and add sodium hydroxide, keep the temperature in the reaction tank at 35°C, slowly add methyl isobutyl carbinol, and stir for 30 minutes until it is completely dissolved to obtain material b, wherein sodium hydroxide: methyl isobutyl carbinol: water = 4:1:57.4.

[0038] The second step is to cool the No. 2 reaction tank to 10°C, feed material b into the No. 2 reaction tank, slowly add carbon disulfide after stirring, and stir at a constant temperature of 10°C for 30 minutes to obtain material c, wherein material b: carbon disulfide = 3.5:1.

[0039] In the third step, material c is fed into the No. 3 reaction tank, and after stirring, hydrocarbon oil emulsified solution (diesel: kerosene: biodiesel = 10:5:2) is slowly added, and stirred for 30 minutes to obtain material d; In the fourth step, material d was fed into the No. 4 reaction tank, and after stirring, the cross-linking agent EDC / NHS was slowly added and stirred for 20 minutes to obtain material e as the final product.

[0040] Product application results: It was used as a copper-molybdenum mixed flotation collector in a local porphyry copper-molybdenum-sulfur mixed ore plant to measure the flotation effect Calculated based on the effective solid content of the finished product, a (w / w) aqueous solution is prepared, and a white milky liquid is added in an amount of 40g / t, added to the slurry mixing barrel, stirred for 4 minutes, and then fed into the flotation machine for aeration flotation for 5 minutes. The foam product can obtain a copper concentrate with a copper grade of 23.15% and a recovery rate of 87.48%, wherein the copper concentrate contains 0.84% ​​molybdenum. The molybdenum recovery rate is 89.97%. It is better than the xanthate and diesel collector currently used in the concentrator.

[0041] Example 5 raw material: Sodium hydroxide 400kg (content 99% w / w, pure 396kg) Methyl isobutyl carbinol 200kg (content 99% w / w, pure 198kg) 200kg diesel (content 99% w / w, equivalent to 198kg pure diesel) Kerosene 150kg (content 99% w / w, pure 148.5kg) Biodiesel 40kg (content 99% w / w, pure 39.6kg) EDC / NHS 300kg (content 99%w / w, pure 297kg) 300kg of carbon disulfide (content 99% w / w, pure 297kg) operate: Step 1: Preheat the reaction tank to keep it at a constant temperature of 35°C, place enough aqueous solution in the reaction tank, and slowly stir and add sodium hydroxide, keep the temperature in the reaction tank at 35°C, slowly add methyl isobutyl carbinol, and stir for 30 minutes until it is completely dissolved to obtain material b, wherein sodium hydroxide: methyl isobutyl carbinol: water = 2:1:45.

[0042] The second step is to cool the No. 2 reaction tank to 10°C, feed material b into the No. 2 reaction tank, slowly add carbon disulfide after stirring, and stir at a constant temperature of 10°C for 30 minutes to obtain material c, wherein material b: carbon disulfide = 2:1.

[0043] In the third step, material c is fed into the No. 3 reaction tank, and after stirring, hydrocarbon oil emulsified solution (diesel: kerosene: biodiesel = 20:15:4) is slowly added, and stirred for 30 minutes to obtain material d; In the fourth step, material d was fed into the No. 4 reaction tank, and after stirring, the cross-linking agent EDC / NHS was slowly added and stirred for 20 minutes to obtain material e as the final product.

[0044] Product application results: It was used as a copper-molybdenum mixed flotation collector in a local porphyry copper-molybdenum-sulfur mixed ore plant to measure the flotation effect Calculated based on the effective solid content of the finished product, a (w / w) aqueous solution is prepared, and a white milky liquid is added in an amount of 33g / t, added to the slurry mixing barrel, stirred for 5 minutes, and then fed into the flotation machine for aeration flotation for 5 minutes. The foam product can obtain a copper concentrate with a copper grade of 25.45% and a recovery rate of 83.31%, wherein the copper concentrate contains 0.85% molybdenum. The molybdenum recovery rate is 80.62%. It is better than the xanthate and diesel collector currently used in the concentrator.

Claims

1. A copper-molybdenum high-efficiency mixed flotation separation collector, characterized in that: The copper-molybdenum high-efficiency mixed flotation separation collector is synthesized using dithiocarbonate and mixed hydrocarbon oil as raw materials.

2. The copper-molybdenum high-efficiency mixed flotation separation collector according to claim 1, characterized in that: The mass ratio of the dithiocarbonate to the mixed hydrocarbon oil is (3-3.5): (1.5-2).

3. The copper-molybdenum high-efficiency mixed flotation separation collector according to claim 1 or 2, characterized in that: The dithiocarbonate is prepared by using methyl isobutyl carbinol, CS2 and NaOH as raw materials.

4. The copper-molybdenum high-efficiency mixed flotation separation collector according to claim 1 or 2, characterized in that: The mass ratio of the dithiocarbonate is NaOH, methyl isobutyl carbinol and CS2 is (2.5-3):1:(1.5-2).

5. The copper-molybdenum high-efficiency mixed flotation separation collector according to claim 4, characterized in that: The mixed hydrocarbon oil is diesel, kerosene and biodiesel.

6. The copper-molybdenum high-efficiency mixed flotation separation collector according to claim 5, characterized in that: The mass ratio of the diesel, kerosene and biodiesel is 4:2:

1.

7. A method for preparing a copper-molybdenum high-efficiency mixed flotation separation collector according to any one of claims 1 to 6, characterized in that: The following steps are involved: A. Add water to reaction tank No. 1, and add sodium hydroxide at a temperature of 30-40°C under stirring to prepare sodium hydroxide solution a; then add methyl isobutyl carbinol solution at a temperature of 30-40°C, and stir for 30-40 minutes to obtain material b; B. Feed material b into the No. 2 reaction tank, control the temperature at 5-10°C, add carbon disulfide, and then control the temperature at 10-20°C and stir the reaction for 20-30 minutes to obtain material c; C. Feed material c into the No. 3 reaction tank, add mixed hydrocarbon oil, control the temperature at 20-30°C, stir and react for 20-30 minutes to obtain material d; D. Feed material d into the No. 4 reaction tank, add the cross-linking agent 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide / N-hydroxysuccinimide (EDC / NHS), control the temperature to 30-40°C and stir the reaction for 10-20 minutes to obtain material e, which is the target copper-molybdenum high-efficiency mixed flotation separation collector.

8. The preparation method according to claim 7, characterized in that: In step A, the mass ratio of water, sodium hydroxide and methyl isobutyl carbinol is (240~275):(2.5~3):

1.

9. The preparation method according to claim 7, characterized in that: In step B, the mass ratio of carbon disulfide and material b is (1.5~2):

1.

10. An application of the copper-molybdenum high-efficiency mixed flotation separation collector according to any one of claims 1 to 6, characterized in that: The application of the copper-molybdenum high-efficiency mixed flotation separation collector in the copper-molybdenum mineral mixed flotation separation process.

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