Resource comprehensive utilization method of quartz vein type lead-zinc sulfide ore

Abstract

The invention discloses a resource comprehensive utilization method of quartz vein type lead-zinc sulfide ore, which comprises the following steps: grinding lead-zinc ore until-0.074 mm accounts for 70-80%, carrying out flotation on the lead sulfide ore according to floatability difference of minerals in the ore, and carrying out fine selection on lead rough concentrate for 2-3 times to obtain lead concentrate; flotation of zinc sulfide minerals is conducted on tailings obtained after flotation of the lead sulfide minerals, and zinc concentrate is obtained after 2-3 times of concentration of zinc rough concentrate; flotation of iron sulfide minerals is conducted on tailings obtained after flotation of the zinc sulfide minerals, and iron sulfide rough concentrate is subjected to 2-3 times of concentration to obtain sulfur concentrate; a sodium silicate solution is obtained from tailings subjected to flotation of iron sulfide by adopting a heating alkaline leaching method, and then a white carbon black product is prepared by adopting a sulfuric acid precipitation method. According to the method, the preferential flotation technology is combined with the heating alkaline leaching and sulfuric acid precipitation technology, the lead concentrate, the zinc concentrate, the sulfur concentrate, the white carbon black and other products 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 quartz vein type lead-zinc sulfide 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 quartz vein type lead-zinc sulfide ore. Background Art

[0002] As we all know, lead-zinc ore is a very important non-ferrous metal mineral resource. my country is a major producer of lead and zinc in the world, and it is also a major consumer and trader of lead and zinc in the world. With the intensive mining over the years, my country's high-quality lead and zinc resources have been exhausted, and the grade of the original ore has gradually become impoverished. Therefore, the comprehensive utilization of lead-zinc mineral resources has increasingly become a key factor affecting my country's entire lead and zinc industry. At present, lead-zinc mines attach great importance to the recovery of lead and zinc metals, but often ignore other 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, and fixes heavy metal ions in tailings to prevent secondary pollution, which is in line with the sustainable development strategy. Therefore, it is very necessary to develop a product that can solve the above technical problems. Summary of the invention

[0003] The object of the present invention is to provide a method for comprehensive resource utilization of quartz vein type lead-zinc sulfide ore.

[0004] The object of the present invention is achieved in that the resource comprehensive utilization method of the quartz vein type lead-zinc sulfide ore comprises the steps of pre-treatment, lead selection, zinc selection, sulfur selection and post-treatment, specifically comprising: A. Pretreatment: Grind the quartz vein type lead-zinc sulfide ore to be treated to -0.074mm, accounting for 70-80%, to obtain material a; B. Select lead: 1) Add zinc sulfate to material a, stir for 2-4 minutes, then add 25# black medicine, stir for 0.5-1.5 minutes, and then flotate to obtain lead concentrate b and lead tailings c; 2) The lead concentrate b is subjected to blank concentration 2 to 3 times to obtain lead concentrate; C. Select zinc: 1) Add lime to the lead tailings c, control the pH at 10-10.5 and stir for 2-4 minutes, then add copper sulfate and stir for 2-4 minutes, then add butyl xanthate and 2# oil, stir for 0.5-1.5 minutes and then flotate to obtain zinc concentrate d and zinc tailings e; 2) adding lime to the zinc rough concentrate d and concentrating it 2 to 3 times to obtain zinc concentrate; D. Sulfur selection: 1) Add copper sulfate to the zinc tailings e, stir for 2-4 minutes, then add butyl xanthate and 2# oil, stir for 0.5-1.5 minutes, and then flotate to obtain the iron sulfide concentrate f and sulfur tailings g; 2) The iron sulfide crude concentrate is subjected to blank cleaning 2 to 3 times to obtain sulfide concentrate; E. Post-processing: 1) adding water and sodium hydroxide to the sulfur-selected tailings g and performing heating leaching in a reactor, and obtaining a leachate h and a leach residue i after solid-liquid separation; 2) 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.

[0005] The specific operations are as follows: 1. First, take 500g of the raw ore of sulfide lead-zinc 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, and prepare for flotation; 2. Float the lead sulfide minerals first. Before flotation, add 1000~2000g / t of zinc sulfate, stir for 3 minutes, and add 25 # Black powder 50g / t, after stirring for 1min, positive flotation begins. The flotation foam is the lead concentrate. The lead concentrate is blanked for 2-3 times to obtain a lead concentrate containing more than 60% lead. 3. Select the lead tailings and then float the zinc sulfide minerals. Before flotation, add 1000~2000g / t of lime, control the pH at 10~10.5, stir for 3 minutes, add 100~300g / t of copper sulfate, stir for 3 minutes, add 100g / t of butyl xanthate and 2 # Oil 30g / t, after stirring for 1min, positive flotation begins. The flotation foam is the zinc concentrate. The zinc concentrate is beneficiated 2~3 times. When beneficiating, 300~500g / t of lime is added to obtain zinc concentrate containing more than 50% zinc. 4. Select zinc tailings and then float iron sulfide minerals. Before flotation, add 100-300 g / t of copper sulfate, stir for 3 minutes, add 100 g / t of butyl xanthate and 2 # Oil 30g / t, after stirring for 1min, positive flotation begins. The flotation foam is the rough iron sulfide concentrate. The rough iron sulfide concentrate is blank-selected 2 to 3 times to obtain a sulfur concentrate with a sulfur content of more than 45%; 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 the preferential flotation process with the process of heated alkali leaching and sulfuric acid precipitation to obtain four qualified products, namely, lead concentrate, zinc concentrate, sulfur concentrate and white carbon black, which not only improves the value of the products, but also reduces the tailings discharge, and points out the development direction for the comprehensive utilization of quartz vein type lead-zinc sulfide ore. The lead-zinc ore is crushed to -0.074mm, accounting for 70-80%. According to the difference in the floatability of minerals in the ore, the lead sulfide mineral is first floated, and the lead rough concentrate is selected 2-3 times to obtain the lead concentrate; the tailings of the floated lead sulfide mineral are then floated to zinc sulfide minerals, and the zinc rough concentrate is selected 2-3 times to obtain the zinc concentrate; the tailings of the floated zinc sulfide mineral are then floated to iron sulfide minerals, and the iron sulfide rough concentrate is selected 2-3 times to obtain the sulfur concentrate; the tailings of the floated iron sulfide mineral are then heated and alkali leached to obtain the sodium silicate solution, and then the sulfuric acid precipitation method is used to prepare the white carbon black product. DETAILED DESCRIPTION

[0007] 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.

[0008] The resource comprehensive utilization method of the quartz vein type lead-zinc sulfide ore of the present invention comprises the steps of pre-treatment, lead selection, zinc selection, sulfur selection and post-treatment, specifically comprising: A. Pretreatment: Grind the quartz vein type lead-zinc sulfide ore to be treated to -0.074mm, accounting for 70-80%, to obtain material a; B. Select lead: 1) Add zinc sulfate to material a, stir for 2-4 minutes, then add 25# black medicine, stir for 0.5-1.5 minutes, and then flotate to obtain lead concentrate b and lead tailings c; 2) The lead concentrate b is subjected to blank concentration 2 to 3 times to obtain lead concentrate; C. Select zinc: 1) Add lime to the lead tailings c, control the pH at 10-10.5 and stir for 2-4 minutes, then add copper sulfate and stir for 2-4 minutes, then add butyl xanthate and 2# oil, stir for 0.5-1.5 minutes and then flotate to obtain zinc concentrate d and zinc tailings e; 2) adding lime to the zinc rough concentrate d and concentrating it 2 to 3 times to obtain zinc concentrate; D. Sulfur selection: 1) Add copper sulfate to the zinc tailings e, stir for 2-4 minutes, then add butyl xanthate and 2# oil, stir for 0.5-1.5 minutes, and then flotate to obtain the iron sulfide concentrate f and sulfur tailings g; 2) The iron sulfide crude concentrate is subjected to blank cleaning 2 to 3 times to obtain sulfide concentrate; E. Post-processing: 1) adding water and sodium hydroxide to the sulfur-selected tailings g and performing heating leaching in a reactor, and obtaining a leachate h and a leach residue i after solid-liquid separation; 2) 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.

[0009] In step B 1), the amount of zinc sulfate added is 1000-2000 g / t.

[0010] In step B 1), the amount of 25# black medicine added is 40~60g / t.

[0011] C. The amount of lime added in step 1) is 1000~2000g / t.

[0012] C. The amount of copper sulfate added in step 1) is 100-300 g / t.

[0013] In step C 1), the amount of butyl xanthate added is 80~120g / t; the amount of 2# oil added is 20~40g / t.

[0014] D. In step 1), the amount of copper sulfate added is 100-300 g / t.

[0015] D. In step 1), the amount of butyl xanthate added is 80-120 g / t; the amount of 2# oil added is 20-40 g / t.

[0016] In step E, the temperature of heating and leaching in 1) is 200-240°C, and the time is 100-150 minutes.

[0017] In step E 2), the drying is carried out in an oven at 90-110°C.

[0018] The present invention is further described below with specific implementation cases: Example 1 Take 500g of quartz vein type lead-zinc sulfide ore (the original ore lead grade is 2.81%, the zinc grade is 3.57%, the sulfur grade is 8.75%, the iron grade is 7.31%, the silicon dioxide grade is 57.29%, the lead mainly exists in the form of galena, the zinc mainly exists in the form of sphalerite, the iron mainly exists in the form of pyrite, and the gangue minerals are mainly silicate minerals such as 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; float the lead sulfide mineral first, add 1600g / t of zinc sulfate before flotation, stir for 3min, add 25 # Black medicine 50g / t, after stirring for 1min, positive flotation begins. The flotation foam is the lead concentrate. The lead concentrate is blank selected 2~3 times to obtain a lead concentrate containing 65.48% lead, and the lead recovery rate reaches 94%; select the lead tailings and then float zinc sulfide minerals. Before flotation, add 2000g / t of lime, control the pH at 10~10.5, stir for 3min, add 250g / t of copper sulfate, stir for 3min, add 80g / t of butyl xanthate and 2 # Oil 30g / t, after stirring for 1min, positive flotation begins. The flotation foam is the zinc concentrate. The zinc concentrate is refined 2~3 times. When selecting, 300~500g / t of lime is added to obtain a zinc concentrate containing 52.26% zinc, and the zinc recovery rate reaches 90%. The zinc tailings are then floated for iron sulfide minerals. Before flotation, 150g / t of copper sulfate is added, stirred for 3min, and 100g / t of butyl xanthate and 2 # Oil 30g / t, after stirring for 1min, positive flotation begins. The flotation foam is the rough iron sulfide concentrate. The rough iron sulfide concentrate is blank selected 2~3 times to obtain a sulfur concentrate containing 47.49% sulfur, and the sulfur recovery rate reaches 80%; 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 slag 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 slag and leaching Liquid; take 100ml of the leaching solution and place it in a beaker, place the beaker in a constant temperature water bath at 80℃, add 3% electrolyte sodium sulfate, and add 10% sulfuric acid solution at a certain stirring rate, and control the pH of the reaction end point 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 placed in an oven at 100℃ for drying to obtain hydrated silicon dioxide, that is, white carbon black product. The specific surface area of ​​white carbon black is 195.67m 2 / g, the product can meet the highest category A grade product requirements in the national standard GB / T10722.

[0019] Example 2 Take 500g of quartz vein type lead-zinc sulfide ore (the original ore lead grade is 5.32%, the zinc grade is 8.50%, the sulfur grade is 13.18%, the iron grade is 12.79%, the silicon dioxide grade is 62.11%, the lead mainly exists in the form of galena, the zinc mainly exists in the form of sphalerite, the iron mainly exists in the form of pyrite, and the gangue minerals are mainly silicate minerals such as quartz) and grind the ore to -0.074mm, accounting for 80%. Mix the ore with water and place it in a 1.5L flotation tank with a liquid-solid ratio of 2:1; float the lead sulfide mineral first, add 2000g / t of zinc sulfate before flotation, stir for 3min, add 25 # Black powder 60g / t, after stirring for 1min, positive flotation begins. The flotation foam is the lead concentrate. The lead concentrate is blank selected 2~3 times to obtain a lead concentrate containing 67.13% lead, and the lead recovery rate reaches 95%; select the lead tailings and then float zinc sulfide minerals. Before flotation, add 2500g / t of lime, control the pH at 10~10.5, stir for 3min, add 250g / t of copper sulfate, stir for 3min, add 100g / t of butyl xanthate and 2 # Oil 30g / t, after stirring for 1min, positive flotation begins. The flotation foam is the zinc concentrate. The zinc concentrate is refined 2~3 times. During the refinement, 300~500g / t of lime is added to obtain a zinc concentrate containing 54.36% zinc, and the zinc recovery rate reaches 92%. The zinc tailings are then floated for iron sulfide minerals. Before flotation, 200g / t of copper sulfate is added, stirred for 3min, and 100g / t of butyl xanthate and 2 # Oil 30g / t, after stirring for 1min, positive flotation begins. The flotation foam is the rough iron sulfide concentrate. The rough iron sulfide concentrate is blank selected 2~3 times to obtain a sulfur concentrate containing 46.08% sulfur, and the sulfur recovery rate reaches 83%; 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 slag 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 slag and leaching Liquid; take 100ml of the leaching solution and place it in a beaker, place the beaker in a constant temperature water bath at 80℃, add 3% electrolyte sodium sulfate, and add 10% sulfuric acid solution at a certain stirring rate, and control the pH of the reaction end point 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 placed in an oven at 100℃ for drying to obtain hydrated silicon dioxide, that is, white carbon black product. The specific surface area of ​​white carbon black is 217.31m 2 / g, the product meets the highest category A grade product requirements in the national standard GB / T10722.

Claims

1. A method for comprehensive resource utilization of quartz vein type lead-zinc sulfide ore, characterized in that: The resource comprehensive utilization method of the quartz vein type lead-zinc sulfide ore includes pre-treatment, lead selection, zinc selection, sulfur selection and post-treatment steps, specifically including: A. Pretreatment: Grind the quartz vein type lead-zinc sulfide ore to be treated to -0.074mm, accounting for 70-80%, to obtain material a; B. Select lead: 1) Add zinc sulfate to material a, stir for 2-4 minutes, then add 25# black medicine, stir for 0.5-1.5 minutes, and then flotate to obtain lead concentrate b and lead tailings c; 2) The lead concentrate b is subjected to blank concentration 2 to 3 times to obtain lead concentrate; C. Select zinc: 1) Add lime to the lead tailings c, control the pH at 10-10.5 and stir for 2-4 minutes, then add copper sulfate and stir for 2-4 minutes, then add butyl xanthate and 2# oil, stir for 0.5-1.5 minutes and then flotate to obtain zinc concentrate d and zinc tailings e; 2) adding lime to the zinc rough concentrate d and concentrating it 2 to 3 times to obtain zinc concentrate; D. Sulfur selection: 1) Add copper sulfate to the zinc tailings e, stir for 2-4 minutes, then add butyl xanthate and 2# oil, stir for 0.5-1.5 minutes, and then flotate to obtain the iron sulfide concentrate f and sulfur tailings g; 2) The iron sulfide crude concentrate is subjected to blank cleaning 2 to 3 times to obtain sulfide concentrate; E. Post-processing: 1) adding water and sodium hydroxide to the sulfur-selected tailings g and performing heating leaching in a reactor, and obtaining a leachate h and a leach residue i after solid-liquid separation; 2) 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.

2. The method for comprehensive resource utilization of quartz vein type lead-zinc sulfide ore according to claim 1, characterized in that: In step B 1), the amount of zinc sulfate added is 1000-2000 g / t.

3. The method for comprehensive resource utilization of quartz vein type lead-zinc sulfide ore according to claim 1, characterized in that: In step B 1), the amount of 25# black medicine added is 40~60g / t.

4. The method for comprehensive resource utilization of quartz vein type lead-zinc sulfide ore according to claim 1, characterized in that: C. The amount of lime added in step 1) is 1000~2000g / t.

5. The method for comprehensive resource utilization of quartz vein type lead-zinc sulfide ore according to claim 1, characterized in that: C. The amount of copper sulfate added in step 1) is 100-300 g / t.

6. The method for comprehensive resource utilization of quartz vein type lead-zinc sulfide ore according to claim 1, characterized in that: In step C 1), the amount of butyl xanthate added is 80~120g / t; the amount of 2# oil added is 20~40g / t.

7. The method for comprehensive resource utilization of quartz vein type lead-zinc sulfide ore according to claim 1, characterized in that: D. In step 1), the amount of copper sulfate added is 100-300 g / t.

8. The method for comprehensive resource utilization of quartz vein type lead-zinc sulfide ore according to claim 1, characterized in that: D. In step 1), the amount of butyl xanthate added is 80-120 g / t; the amount of 2# oil added is 20-40 g / t.

9. The method for comprehensive resource utilization of quartz vein type lead-zinc sulfide ore according to claim 1, characterized in that: In step E, the temperature of heating and leaching in 1) is 200-240°C, and the time is 100-150 minutes.

10. The method for comprehensive resource utilization of quartz vein type lead-zinc sulfide ore according to claim 1, characterized in that: In step E 2), the drying is carried out in an oven at 90-110°C.