Resource comprehensive utilization method of porphyry type copper ore

Abstract

The invention discloses a resource comprehensive utilization method of porphyry type copper ore, which comprises the following steps: grinding copper sulfide ore until-0.074 mm accounts for 70-80%, carrying out bulk flotation on copper sulfide ore and iron sulfide ore, and carrying out three times of concentration on copper-sulfur rough concentrate to obtain copper-sulfur bulk concentrate; the copper-sulfur bulk concentrate is subjected to copper-sulfur separation, concentrate obtained after copper-sulfur separation is subjected to two-time concentration, and a copper concentrate product is obtained; carrying out reverse flotation twice on tailings subjected to copper-sulfur separation to obtain a sulfur concentrate product; scavenging the copper-sulfur mixed tailings for three times to obtain the final flotation tailings; a sodium silicate solution is obtained from flotation tailings through a heating alkaline leaching method, and then a white carbon black product is prepared through a sulfuric acid precipitation method. According to the method, the bulk flotation-copper-sulfur separation process is combined with the heating alkaline leaching and sulfuric acid precipitation process, the three products including the copper concentrate, the sulfur concentrate and the white carbon black are obtained, the value of the products is increased, tailing discharge is reduced, and the development direction is pointed out for resource comprehensive utilization of the porphyry type copper ore.

Description

Technical Field

[0001] The invention belongs to the technical field of comprehensive utilization of mines, and specifically relates to a resource comprehensive utilization method of porphyry copper ore. Background Art

[0002] As we all know, copper ore is a very important non-ferrous metal mineral resource. my country is a major copper producer in the world, and also a major copper consumer and trader in the world. At present, copper mines attach great importance to the recovery of copper metal, but often ignore other valuable metals or non-metals associated with the ore. With the continuous development of science and technology, these other metals and non-metals can be prepared into products with higher value, which not only creates economic benefits, but also helps mines reduce the volume of tailings ponds, fix heavy metal ions in tailings, prevent secondary pollution, and comply with the sustainable development strategy. Therefore, it is very necessary to develop a method that can solve the above technical problems. Summary of the invention

[0003] The purpose of the present invention is to provide a comprehensive resource utilization method for porphyry copper ore.

[0004] The object of the present invention is achieved in that the method for comprehensive resource utilization of porphyry copper ore comprises pre-treatment, mixed flotation of copper and sulfur, flotation separation of copper and sulfur, and post-treatment steps, specifically comprising: A. Pretreatment: Grind the porphyry copper ore to be processed to -0.074mm, accounting for 70-80%, to obtain material a; B. Mixed flotation of copper and sulfur: 1) Add sodium sulfide to material a, stir for 2-4 minutes, then add butyl xanthate and methyl isobutyl carbinol (MIBC), stir for 0.5-1.5 minutes, and then flotate to obtain foam material b and tailings material c; 2) Material b is subjected to three-stage blank concentration to obtain copper-sulfur mixed concentrate d and concentrated tailings, and the concentrated tailings are returned to the previous step for circulation; C. Copper and sulfur separation: 1) Add lime to the copper-sulfur mixed concentrate d, control the pH value at 10-10.5, stir for 2-4 minutes, then add ethylthiocarbamate (Z-200) and methyl isobutyl carbinol (MIBC), stir for 1-3 minutes and then flotate to obtain copper rough concentrate e and sulfur rough concentrate f; 2) Add lime to the copper rough concentrate e for 2-3 times to obtain copper concentrate; 3) Add ethiocarbamate to the sulfur concentrate f and perform reverse flotation 2 to 3 times to obtain sulfur concentrate; D. Post-processing: 1) Add butyl xanthate and methyl isobutyl carbinol to the tailings material c, stir for 0.5-1.5 min, and then scavenge 2-3 times to obtain scavenge tailings g; 2) adding water and sodium hydroxide to the scavenging tailings g and placing it in a reactor for heating and leaching, and obtaining leachate h and leach residue i after solid-liquid separation; 3) Add electrolyte sodium sulfate to the leaching solution, add 8-12% sulfuric acid solution dropwise in a constant temperature water bath at a temperature of 70-90°C for reaction for 1-2 hours, and control the pH value at the end point of the reaction to be 6.5-7.5; after the reaction is completed, age for 1.5-2.5 hours at a constant temperature of 70-90°C, separate the solid and the liquid, repeatedly wash the obtained solid with water, and dry it to obtain hydrated silicon dioxide, i.e., white carbon black product.

[0005] The specific operations are as follows: 1. First, take 500g of the original copper sulfide ore and grind it to -0.074mm, accounting for 70-80%, to achieve the monomer dissociation of the mineral. Mix the ore with water and place it in a 1.5L flotation tank with a liquid-to-solid ratio of 2:1 to prepare for flotation; 2. First, mix and float copper sulfide and iron sulfide minerals. Before flotation, add 300-500 g / t of sodium sulfide, stir for 3 minutes, add 40-60 g / t of butyl xanthate and 20-40 g / t of methyl isobutyl carbinol, stir for 1 minute, and then start positive flotation. The flotation foam is the copper-sulfur mixed rough concentrate. The copper-sulfur mixed rough concentrate is blank-selected 2-3 times to obtain the copper-sulfur mixed concentrate. 3. The copper-sulfur mixed concentrate is separated again. Before flotation, 1000-2000 g / t of lime is added, the pH is controlled at 10-10.5, and the mixture is stirred for 3 minutes. Then, 20-40 g / t of ethylthiocarbamate and 10-30 g / t of methyl isobutyl carbinol are added. After stirring for 1 minute, positive flotation is started. The flotation foam is the copper rough concentrate. The copper rough concentrate is fined 2-3 times, and 300-500 g / t of lime is added during fined. A copper concentrate containing more than 20% copper can be obtained. The tailings separated from the copper-sulfur mixed concentrate are subjected to 2-3 reverse flotations. During the reverse flotation, 10-20 g / t of ethylthiocarbamate is added. The tailings from the reverse flotation are sulfur concentrates, and the sulfur grade in the sulfur concentrate can reach more than 45%. 4. The tailings of copper-sulfur mixed flotation are scavenged 2-3 times. During scavenging, 10-30 g / t of butyl xanthate and 10-20 g / t of methyl isobutyl carbinol are added. After stirring for 1 minute, flotation begins. The scavenged tailings are the final tailings of flotation, and the SiO2 content in the tailings is more than 60%; 5. Put the flotation tailings, water and sodium hydroxide into a reactor for heating leaching, the leaching temperature is 220°C, the reaction time is 120min, the alkali residue mass ratio is 2:1, the liquid-solid ratio is 5:1, cool to room temperature, and obtain the leaching residue and leachate after solid-liquid separation; 6. Take 100 ml of the leachate and place it in a beaker, place the beaker in a constant temperature water bath with a set temperature, add a certain amount of electrolyte sodium sulfate, and drop the prepared sulfuric acid solution at a certain stirring rate, control the pH of the reaction end point to be 7, the reaction time is 1-2h, and after the reaction is completed, age at a constant temperature for 2h, and separate the solid and liquid after the aging is completed; 7. Wash the solid repeatedly with water, and finally dry it in an oven at 100°C to obtain hydrated silicon dioxide, i.e., white carbon black product.

[0006] The present invention combines a mixed flotation-copper-sulfur separation process with a heated alkaline leaching and sulfuric acid precipitation process to obtain three products, namely, copper concentrate, sulfur concentrate, and white carbon black, which not only improves the value of the products, but also reduces tailings discharge, and points out the development direction for the comprehensive utilization of porphyry copper mines. The present invention grinds copper sulfide ore to -0.074mm, accounting for 70-80%, and firstly mixes and floats copper sulfide minerals and iron sulfide minerals according to the difference in the floatability of minerals in the ore, and the copper-sulfur rough concentrate is finely selected three times to obtain a copper-sulfur mixed concentrate; then the copper-sulfur mixed concentrate is separated from the copper-sulfur, and the copper-sulfur separated concentrate is finely selected twice to obtain a copper concentrate product; the copper-sulfur separated tailings are scavenged twice to obtain a sulfur concentrate product; the copper-sulfur mixed tailings are scavenged three times to obtain the final tailings of flotation; the flotation tailings are then subjected to a heated alkaline leaching method to obtain a sodium silicate solution, and then a sulfuric acid precipitation method is used to prepare a white carbon black product. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 It is a schematic diagram of the process flow of the present invention. DETAILED DESCRIPTION

[0008] 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.

[0009] The method for comprehensive resource utilization of porphyry copper ore of the present invention comprises pre-treatment, mixed flotation of copper and sulfur, flotation separation of copper and sulfur, and post-treatment steps, specifically comprising: A. Pretreatment: Grind the porphyry copper ore to be processed to -0.074mm, accounting for 70-80%, to obtain material a; B. Mixed flotation of copper and sulfur: 1) Add sodium sulfide to material a, stir for 2-4 minutes, then add butyl xanthate and methyl isobutyl carbinol (MIBC), stir for 0.5-1.5 minutes, and then flotate to obtain foam material b and tailings material c; 2) Material b is subjected to three-stage blank concentration to obtain copper-sulfur mixed concentrate d and concentrated tailings, and the concentrated tailings are returned to the previous step for circulation; C. Copper and sulfur separation: 1) Add lime to the copper-sulfur mixed concentrate d, control the pH value at 10-10.5, stir for 2-4 minutes, then add ethylthiocarbamate (Z-200) and methyl isobutyl carbinol (MIBC), stir for 1-3 minutes and then flotate to obtain copper rough concentrate e and sulfur rough concentrate f; 2) Add lime to the copper rough concentrate e for 2-3 times to obtain copper concentrate; 3) Add ethiocarbamate to the sulfur concentrate f and perform reverse flotation 2 to 3 times to obtain sulfur concentrate; D. Post-processing: 1) Add butyl xanthate and methyl isobutyl carbinol to the tailings material c, stir for 0.5-1.5 min, and then scavenge 2-3 times to obtain scavenge tailings g; 2) adding water and sodium hydroxide to the scavenging tailings g and placing it in a reactor for heating and leaching, and obtaining leachate h and leach residue i after solid-liquid separation; 3) Add electrolyte sodium sulfate to the leaching solution, add 8-12% sulfuric acid solution dropwise in a constant temperature water bath at a temperature of 70-90°C for reaction for 1-2 hours, and control the pH value at the end point of the reaction to be 6.5-7.5; after the reaction is completed, age for 1.5-2.5 hours at a constant temperature of 70-90°C, separate the solid and the liquid, repeatedly wash the obtained solid with water, and dry it to obtain hydrated silicon dioxide, i.e., white carbon black product.

[0010] B. The amount of sodium sulfide added in step 1) is 300-500 g / L.

[0011] B. The amount of butyl xanthate added in step 1) is 40-60 g / L.

[0012] B. The amount of methyl isobutyl carbinol added in step 1) is 10-30 g / L.

[0013] C. The amount of lime added in step 1) is 1000-2000 g / L; the amount of ethionamide added is 20-40 g / L; and the amount of methyl isobutyl carbinol added is 10-30 g / L.

[0014] C. The amount of lime added in step 2) is 300-500 g / L.

[0015] C. The amount of ethionamide added in step 3) is 10-20 g / L.

[0016] D. The amount of butyl xanthate added in step 1) is 10-30 g / L; the amount of methyl isobutyl carbinol added is 10-20 g / L.

[0017] D. The temperature of the heated leaching in step 2) is 200-240°C and the time is 100-150 minutes.

[0018] D. The drying in step 3) is carried out at 90-110°C.

[0019] The present invention is further described below with specific implementation cases: Example 1 Take 500g of porphyry copper sulfide ore (the original ore copper grade is 0.53%, the sulfur grade is 7.24%, the iron grade is 8.81%, the silicon dioxide grade is 70.81%, the copper in the ore is mainly in the form of independent minerals in chalcocite (57.24%), bornite (24.79%), chalcopyrite (5.33%), covellite (6.96%), arsenite (3.46%), arsenic copper sulfide (2.22%), and the gangue minerals are mainly silicate minerals mainly composed of quartz) and grind the ore to -0.074mm, accounting for 70%. Mix the ore with water and place it in a 1.5L flotation tank with a liquid-solid ratio of 2:1; first mix and float copper sulfide and iron sulfide minerals, add 400g / t of sodium sulfide before flotation, stir for 3min, and add butyl xanthate 50 g / t and 30g / t of methyl isobutyl carbinol, stir for 1 minute and start positive flotation. The flotation foam is the copper-sulfur mixed rough concentrate. The copper-sulfur mixed rough concentrate is blank-selected 3 times to obtain the copper-sulfur mixed concentrate. Then the copper-sulfur mixed concentrate is subjected to copper-sulfur flotation separation. The pulp of the copper-sulfur mixed concentrate is placed in a 0.5L flotation tank. Before flotation, 1500g / t of lime is added, the pH is controlled at 10-10.5, stirred for 3 minutes, and 300g / t of ethylthiocarbamate is added. g / t, stirred for 1 min, 20 g / t of methyl isobutyl carbinol was added, and flotation separation was started after stirring for 1 min. The flotation foam was the copper rough concentrate. The copper rough concentrate was refined 3 times, and 500 g / t of lime was added during the refinement to obtain a copper concentrate containing 23.19% copper, and the copper recovery rate reached 92%; the tailings of copper-sulfur separation were reversely floated twice, and 20 g / t of ethylthiocarbamate was added before reverse flotation. Reverse flotation was started after stirring for 1 min. The flotation tailings was the sulfur concentrate, which contained 48.55% sulfur, and the sulfur recovery rate reached 85%; the tailings of copper-sulfur mixed flotation were scavenged 3 times, 20 g / t of butyl xanthate was added during flotation, stirred for 1 min, 20 g / t of methyl isobutyl carbinol was added, and flotation was started after stirring for 1 min. The tailings after 3 flotations were the final tailings of flotation, and the tailings contained 83.74% silicon dioxide.

[0020] The flotation tailings, water and sodium hydroxide are placed in a reactor for heated leaching, the leaching temperature is 220℃, the reaction time is 120min, the alkali residue mass ratio is 2:1, the liquid-solid ratio is 5:1, and it is cooled to room temperature. After solid-liquid separation, the leaching residue and the leachate are obtained; 100ml of the leachate is placed in a beaker, and the beaker is placed in a constant temperature water bath at 80℃, 3% electrolyte sodium sulfate is added thereto, and 10% sulfuric acid solution is added dropwise at a certain stirring rate, and the pH at the end of the reaction is controlled to be 7; the reaction time is 1-2h, and the reaction is aged at a constant temperature for 2h after the reaction is completed. After the aging is completed, the solid and liquid are separated; the solid is repeatedly washed with water, and finally it is placed in an oven at 100℃ for drying to obtain hydrated silicon dioxide, i.e., white carbon black product. The specific surface area of ​​white carbon black is 211.28m 2 / g, the product can meet the highest category A grade product requirements in the national standard GB / T10722.

[0021] Example 2 Take 500g of porphyry copper sulfide ore (the original ore copper grade is 0.72%, the sulfur grade is 5.49%, the iron grade is 6.33%, the silicon dioxide grade is 65.72%, the copper in the ore is mainly in the form of independent minerals in chalcocite (45.19%), bornite (28.32%), chalcopyrite (21.75%), and the gangue minerals are mainly silicate minerals dominated by quartz) and grind the ore to -0.074mm, accounting for 75%. Mix the ore with water and place it in a 1.5L flotation tank with a liquid-solid ratio of 2:1; first mix and float copper sulfide and iron sulfide minerals. Before flotation, add 500g / t of sodium sulfide, stir for 3min, and add butyl xanthate 60 g / t and 30g / t of methyl isobutyl carbinol, stir for 1 minute and then start positive flotation. The flotation foam is the copper-sulfur mixed rough concentrate. The copper-sulfur mixed rough concentrate is blank-selected 3 times to obtain the copper-sulfur mixed concentrate. Then the copper-sulfur mixed concentrate is subjected to copper-sulfur flotation separation. The pulp of the copper-sulfur mixed concentrate is placed in a 0.5L flotation tank. Before flotation, 1200g / t of lime is added, the pH is controlled at 10-10.5, stirred for 3 minutes, 20g / t of ethylthiocarbamate is added, stirred for 1 minute, 20g / t of methyl isobutyl carbinol is added, stirred for 1 minute and then flotation separation is started. The flotation foam is the copper rough concentrate. The copper rough concentrate is selected twice. By adding 300g / t of lime during the selection, a copper concentrate containing 25.08% copper can be obtained, and the copper recovery rate reaches 94%; the tailings of copper-sulfur separation are reverse floated twice, and 20g / t of ethylthiocarbamate is added before reverse flotation. After stirring for 1min, reverse flotation begins. The flotation tailings are sulfur concentrate, which contains 47.27% sulfur and has a sulfur recovery rate of 80%; the tailings of copper-sulfur mixed flotation are scavenged three times, and 30g / t of butyl xanthate is added during flotation, and stirred for 1min. 20g / t of methyl isobutyl carbinol is added, and flotation begins after stirring for 1min. The tailings floated three times are the final tailings of flotation, and the tailings contain 76.74% silicon dioxide.

[0022] The flotation tailings, water and sodium hydroxide are placed in a reactor for heated leaching, the leaching temperature is 220℃, the reaction time is 120min, the alkali residue mass ratio is 2:1, the liquid-solid ratio is 5:1, and it is cooled to room temperature. After solid-liquid separation, the leaching residue and the leachate are obtained; 100ml of the leachate is placed in a beaker, and the beaker is placed in a constant temperature water bath at 80℃, 3% electrolyte sodium sulfate is added thereto, and 10% sulfuric acid solution is added dropwise at a certain stirring rate, and the pH at the end of the reaction is controlled to be 7; the reaction time is 1-2h, and the reaction is aged at a constant temperature for 2h after the reaction is completed. After the aging is completed, the solid and liquid are separated; the solid is repeatedly washed with water, and finally it is placed in an oven at 100℃ for drying to obtain hydrated silicon dioxide, i.e., white carbon black product. The specific surface area of ​​white carbon black is 195.71m 2 / g, the product can meet the highest category A grade product requirements in the national standard GB / T10722.

Claims

1. A method for comprehensive resource utilization of porphyry copper ore, characterized in that: The method for comprehensive resource utilization of porphyry copper ore includes pre-treatment, mixed flotation of copper and sulfur, flotation separation of copper and sulfur, and post-treatment steps, specifically including: A. Pretreatment: Grind the porphyry copper ore to be processed to -0.074mm, accounting for 70-80%, to obtain material a; B. Mixed flotation of copper and sulfur: 1) Add sodium sulfide to material a, stir for 2-4 minutes, then add butyl xanthate and methyl isobutyl carbinol (MIBC), stir for 0.5-1.5 minutes, and then flotate to obtain foam material b and tailings material c; 2) Material b is subjected to three-stage blank concentration to obtain copper-sulfur mixed concentrate d and concentrated tailings, and the concentrated tailings are returned to the previous step for circulation; C. Copper and sulfur separation: 1) Add lime to the copper-sulfur mixed concentrate d, control the pH value at 10-10.5, stir for 2-4 minutes, then add ethylthiocarbamate (Z-200) and methyl isobutyl carbinol (MIBC), stir for 1-3 minutes and then flotate to obtain copper rough concentrate e and sulfur rough concentrate f; 2) Add lime to the copper rough concentrate e for 2-3 times to obtain copper concentrate; 3) Add ethiocarbamate to the sulfur concentrate f and perform reverse flotation 2 to 3 times to obtain sulfur concentrate; D. Post-processing: 1) Add butyl xanthate and methyl isobutyl carbinol to the tailings material c, stir for 0.5-1.5 min, and then scavenge 2-3 times to obtain scavenge tailings g; 2) adding water and sodium hydroxide to the scavenging tailings g and placing them in a reactor for heating and leaching, and obtaining leachate h and leach residue i after solid-liquid separation; 3) Add electrolyte sodium sulfate to the leaching solution, add 8-12% sulfuric acid solution dropwise in a constant temperature water bath at a temperature of 70-90°C for reaction for 1-2 hours, and control the pH value at the end point of the reaction to be 6.5-7.5; after the reaction is completed, age for 1.5-2.5 hours at a constant temperature of 70-90°C, separate the solid and the liquid, repeatedly wash the obtained solid with water, and dry it to obtain hydrated silicon dioxide, i.e., white carbon black product.

2. The method for comprehensive resource utilization of porphyry copper ore according to claim 1, characterized in that: B. The amount of sodium sulfide added in step 1) is 300-500 g / L.

3. The method for comprehensive resource utilization of porphyry copper ore according to claim 1, characterized in that: B. The amount of butyl xanthate added in step 1) is 40-60 g / L.

4. The method for comprehensive resource utilization of porphyry copper ore according to claim 1, characterized in that: B. The amount of methyl isobutyl carbinol added in step 1) is 10-30 g / L.

5. The method for comprehensive resource utilization of porphyry copper ore according to claim 1, characterized in that: C. The amount of lime added in step 1) is 1000-2000 g / L; the amount of ethionamide added is 20-40 g / L; and the amount of methyl isobutyl carbinol added is 10-30 g / L.

6. The method for comprehensive resource utilization of porphyry copper ore according to claim 1, characterized in that: C. The amount of lime added in step 2) is 300-500 g / L.

7. The method for comprehensive resource utilization of porphyry copper ore according to claim 1, characterized in that: C. The amount of ethionamide added in step 3) is 10-20 g / L.

8. The method for comprehensive resource utilization of porphyry copper ore according to claim 1, characterized in that: D. The amount of butyl xanthate added in step 1) is 10-30 g / L; the amount of methyl isobutyl carbinol added is 10-20 g / L.

9. The method for comprehensive resource utilization of porphyry copper ore according to claim 1, characterized in that: D. The temperature of the heated leaching in step 2) is 200-240°C and the time is 100-150 minutes.

10. The method for comprehensive resource utilization of porphyry copper ore according to claim 1, characterized in that: D. The drying in step 3) is carried out at 90-110°C.

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