Process for comprehensive utilization of oxygen-sulfur mixed zinc concentrate

Abstract

The application discloses a comprehensive utilization process of oxygen-sulfur mixed zinc concentrate. The comprehensive utilization process of the oxygen-sulfur mixed zinc concentrate comprises pretreatment, main reaction and post-treatment steps, and specifically comprises the following steps: slurry is prepared from the oxygen-sulfur mixed concentrate to be treated, and ultrasonic dispersion is performed to obtain material a; an oxygen-sulfur separation agent JH-3000 is added into the material a to perform stirring reaction, and the upper foam of the solution is scraped off gradually during the reaction to obtain foam b and slurry c; solid-liquid filtration is performed on the foam b, and the zinc sulfide product and slurry d are obtained after the solid-liquid separation of the foam b, and the slurry d and the slurry c are combined to obtain the zinc oxide product; the zinc oxide product is slurry-prepared; acid is added for adjustment, and then acid leaching is performed, the leaching liquid e is purified and electro-deposited to obtain zinc ingots; the zinc sulfide product is prepared after ore blending, and then roasting and sulfuric acid leaching are performed, and solid-liquid separation is performed to obtain leaching liquid g and leaching residue h; the leaching liquid g is purified and electro-deposited to obtain zinc ingots; and the flue gas of the roasting is prepared into sulfuric acid through an acid preparation system.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of metallurgical chemical industry, and particularly relates to a comprehensive utilization process of oxygen-sulfur mixed zinc concentrate. BACKGROUND

[0002] Lanping lead-zinc mine has the first single-body production in China and the fifth largest lead-zinc mine production resource in the world. After years of “rich mining and poor abandonment”, 4000 tons of low-grade oxygen-sulfur mixed lead-zinc ore (Zn grade 6.5%, Pb grade 1.58%, zinc metal amount 213560 tons, lead metal amount 49200 tons) are stacked in the mining area, accounting for one third of the current geological reserves. The mine has not been effectively developed due to the large processing difficulty and low grade.

[0003] On the basis of years of research in the early stage, the oxygen-sulfur mixed concentrate obtained by mixed flotation of low-grade oxygen-sulfur mixed stacked ore has good economic efficiency and process stability. The smelting application of the mixed concentrate has two key technical difficulties: (1) it is difficult to enter the existing smelting process due to the oxygen-sulfur mixture; (2) the existing beneficiation technology is difficult to separate oxygen and sulfur after mixed flotation, and the oxidized ore is wrapped with sulfide by reagent. Therefore, it is necessary to develop a method to solve the above technical problems. SUMMARY

[0004] The purpose of the present application is to provide a comprehensive utilization process of oxygen-sulfur mixed zinc concentrate.

[0005] The purpose of the present application is achieved in that A, pretreatment: the oxygen-sulfur mixed concentrate to be treated is slurried and ultrasonic dispersed to obtain material a;

[0006] B, main reaction: the material a is added with a complex dispersing agent for stirring reaction, and the upper foam of the solution is scraped out during the reaction to obtain foam b and slurry c;

[0007] C, post-treatment:

[0008] 1) the foam b is subjected to solid-liquid filtration, and the zinc sulfide product and slurry d are obtained after the foam b is subjected to solid-liquid separation, and the slurry d and the slurry c are combined to obtain the zinc oxide product;

[0009] 2) the zinc oxide product is slurried to obtain the slurry d;

[0010] 3) the slurry d is adjusted to pH 0.5-1 after acid addition, and then subjected to acid leaching, and the leaching liquid e and the leaching residue f are obtained after solid-liquid separation;

[0011] 4) the leaching liquid e is subjected to purification and electrodeposition to obtain zinc ingot;

[0012] 5) the zinc sulfide product is blended and then subjected to roasting and sulfuric acid leaching, and the leaching liquid g and the leaching residue h are obtained after solid-liquid separation;

[0013] 6) The leaching solution g is purified and electrowon to obtain zinc ingots; the roasting flue gas is prepared into sulfuric acid through an acid preparation system.

[0014] The specific operation is as follows:

[0015] (1) The oxygen-sulfur mixed concentrate is slurried, the slurry concentration is 20-40%, and ultrasonic dispersion is performed;

[0016] (2) The oxygen-sulfur separation reagent is added during the ultrasonic dispersion process in step (1) to fully react with the oxygen-sulfur mixed concentrate slurry, air is introduced, the air introduction amount is 30-200 L / min / kg of ore, the separation reagent addition amount is 0.1%-2% of the mass of the concentrate in the slurry, the reaction time is 5-40 min, the reaction temperature is 20℃-50℃, the stirring speed is 400-800 r / min, and the upper foam is scraped off gradually during the reaction until no foam is generated;

[0017] (3) The foam obtained in step (2) and the remaining slurry are respectively subjected to solid-liquid separation, the foam product after solid-liquid separation is the zinc sulfide product, and the remaining slurry is the zinc oxide product;

[0018] (4) The zinc oxide product obtained in step (2) is slurried, and the liquid-solid ratio is 0.5:1-2:1;

[0019] (5) Sulfuric acid solution is added to the slurry obtained in step (4), the solution can be waste electrolyte, waste acid, waste acid, etc., the acidity is 50-200 g / L, the acid addition time is 5-30 min, and the final liquid-solid ratio is 4:1-8:1;

[0020] (6) The slurry obtained in step (5) is supplemented with acid until the pH is 0.5-1, and then stirred and leached, the leaching time is 1-3 h, the leaching temperature is 40-80℃, the stirring speed is 300-700 r / min, and the leaching is completed after solid-liquid separation;

[0021] (7) The leaching solution obtained in step (6) is subjected to conventional purification and electrowinning to obtain zinc ingots;

[0022] (8) The zinc sulfide product obtained in step (7) is mixed with a conventional zinc sulfide concentrate, the mixture is mixed to a zinc grade of 46-48% and a sulfur content of 26-30%, and then roasted in a fluidized bed furnace at 900-960℃, and then subjected to sulfuric acid leaching, the leaching liquid-solid ratio is 3:1-8:1, the leaching time is 1h-4h, the leaching temperature is 60-90℃, and then subjected to solid-liquid separation, and the obtained filtrate is purified and electrowon to obtain zinc ingots.

[0023] Technical principles: The complex dispersant of the application is compounded by glyceryl trioleate, glyceryl monostearate, trimethylolpropane trioleate and sorbitan monostearate. The dispersant has low surface energy. After adding to the ore pulp, the dispersant can disperse the mineral processing reagent on the surface of the mineral. The mineral processing reagent migrates to the surface of the dispersant, changes the stable state of the mineral processing reagent, reduces the adhesion of the mineral processing reagent, and then makes the mineral processing reagent more easily dispersed from the surface of the mineral.

[0024] Because the mixed concentrate after mixed flotation contains both zinc sulfide and zinc oxide, and the surface of the oxidized ore is also wrapped with the reagent, it is impossible to use conventional methods for oxygen-sulfur separation. The affinity of the mixed flotation reagent to the sulfide ore is stronger than that to the oxidized ore. Therefore, after the dispersant is used, the adhesion of the mineral processing reagent is reduced. Under the condition of suitable addition amount, the dispersant preferentially disperses the reagent on the surface of the zinc oxide, while the mineral processing reagent remains on the surface of the sulfide ore, thereby realizing the separation of zinc oxide and zinc sulfide. DETAILED DESCRIPTION

[0025] The application will be further described below in conjunction with examples, but in no way limits the application. Any transformation or replacement based on the teaching of the application belongs to the protection scope of the application.

[0026] The comprehensive utilization process of the oxygen-sulfur mixed zinc concentrate of the application includes pretreatment, main reaction and post-treatment steps, specifically including:

[0027] A, pretreatment: the oxygen-sulfur mixed concentrate to be treated is slurried and ultrasonically dispersed to obtain material a;

[0028] B, main reaction: the material a is added with the complex dispersant for stirring reaction, and the upper foam of the solution is scraped out during the reaction to obtain foam b and slurry c;

[0029] C, post-treatment:

[0030] 1) the foam b is subjected to solid-liquid filtration, and the zinc sulfide product and slurry d are obtained after the foam b is subjected to solid-liquid separation, and the slurry d and the slurry c are combined to obtain the zinc oxide product;

[0031] 2) the zinc oxide product is slurried to obtain the slurry d;

[0032] 3) the slurry d is adjusted to pH 0.5-1 after acid addition and then subjected to acid leaching, and the leaching liquid e and the leaching residue f are obtained after solid-liquid separation;

[0033] 4) the leaching liquid e is subjected to purification and electrodeposition to obtain zinc ingot;

[0034] 5) the zinc sulfide product is blended and then subjected to roasting and sulfuric acid leaching, and the leaching liquid g and the leaching residue h are obtained after solid-liquid separation;

[0035] 6) The leaching solution g is purified and electrowon to obtain zinc ingots; the roasting flue gas is prepared into sulfuric acid through an acid preparation system.

[0036] The concentration of the pulp after sizing in step A is 20-40%.

[0037] The amount of oxygen-sulfur mixed zinc concentrate oxygen-sulfur separation agent added in step B is 0.1-2% of the mass of the concentrate in material a.

[0038] The temperature of the reaction in step B is 20-50℃, the reaction time is 5-40 min, and the stirring speed is 400-800 r / min.

[0039] The liquid-solid ratio of the pulp after sizing in step 2 of step C is 0.5:1-2:1.

[0040] The acid in step 3 of step C is sulfuric acid solution, waste electrolyte, waste acid, or waste acid, with an acidity of 50-200 g / L, an acid supplementing time of 5-30 min, and a final liquid-solid ratio of 4:1-8:1.

[0041] The temperature of the acid leaching in step 3 of step C is 40-80℃, and the acid leaching time is 1-3 h.

[0042] After the ore is prepared in step 5 of step C, the zinc sulfide product is prepared to a zinc grade of 46-48% and a sulfur content of 26-30%, and then enters a fluidized bed furnace for roasting at 900-960℃.

[0043] The temperature of the sulfuric acid leaching in step 5 of step C is 60-90℃, and the time is 1-4 h.

[0044] The following specific implementation cases will further illustrate the present application:

[0045] Example 1

[0046] (1) Take 1000g of oxygen-sulfur mixed concentrate, mix it with 2000g of water, and then perform ultrasonic dispersion, while passing air at a flow rate of 50L / min; add 5g of a compounded dispersant, and the reaction time is 20min, the reaction temperature is 25℃, and the stirring speed is 500r / min; during the reaction, the foam on the surface of the slurry is scraped off gradually until no more foam is produced; the mass ratio of glyceryl trioleate, glyceryl monostearate, trimethylolpropane trioleate, and sorbitan monostearate in the compounded dispersant is 5:2:4:2.

[0047] The scraped foam and the remaining slurry are subjected to solid-liquid separation, respectively, to obtain zinc oxide and zinc sulfide products; the two products are sent for analysis, and the obtained zinc oxide product has a grade of 24.19% and contains 0.63% zinc sulfide, and the obtained zinc sulfide product has a grade of 32.84% and contains 1.69% zinc oxide.

[0048] (2) Take 200 g of the zinc oxide product obtained in step (2), add 200 ml of water to make a slurry, and after the slurry is made, slowly add 800 ml of zinc electrowinning waste electrolyte with a acidity of 160 g / L to the slurry, and the adding time is 8 min;

[0049] (3) Add concentrated sulfuric acid to the slurry of step (3) until the pH is 0.5, and then start leaching, the leaching time is 2 h, the leaching temperature is 60°C, and the stirring speed is 500 r / min. After leaching is completed, solid-liquid separation is performed, and sample analysis is performed, and the leaching rate of zinc oxide is calculated to be 96.13%.

[0050] Example 2

[0051] (1) Take 1000 g of oxygen-sulfur mixed concentrate, mix with 2000 g of water, and then pass air with a flow rate of 20 L / min. Add 50 g of a compounded dispersant. The reaction time is 30 min, the reaction temperature is 25°C, and the stirring speed is 600 r / min. During the reaction, the foam on the surface of the slurry is scraped off gradually until no more foam is generated. The mass ratio of glyceryl trioleate, glyceryl monostearate, trimethylolpropane trioleate, and sorbitan monostearate in the compounded dispersant is 7:2:6:1.

[0052] (2) The scraped foam and the remaining slurry are subjected to solid-liquid separation respectively, thereby obtaining zinc oxide product and zinc sulfide product. The two products are sent for analysis, and the grade of the obtained zinc oxide product is 23.52% and contains 6.17% of zinc sulfide, and the grade of the obtained zinc sulfide is 31.08% and contains 7.75% of zinc oxide, and the separation effect is not ideal.

[0053] (3) Take 200 g of the zinc oxide product obtained in step (2), add 200 ml of water to make a slurry, and after the slurry is made, slowly add 800 ml of zinc electrowinning waste electrolyte with a acidity of 160 g / L to the slurry, and the adding time is 8 min;

[0054] (4) Add concentrated sulfuric acid to the slurry of step (3) until the pH is 0.5, and then start leaching, the leaching time is 2 h, the leaching temperature is 60°C, and the stirring speed is 500 r / min. After leaching is completed, solid-liquid separation is performed, and sample analysis is performed, and the leaching rate of zinc oxide is calculated to be 96.13%.

[0055] Example 3

[0056] (1) take 1000g oxygen sulfur mixed concentrate, add 2000g water mixed evenly, then carry out ultrasonic dispersion, air is introduced during the dispersion process, the air flow is 80L / min; add 7g compound dispersant; reaction time 30min, reaction temperature 25℃, stirring speed 500r / min, the surface foam of the slurry is scraped out gradually during the reaction until no foam is generated; the mass ratio of glyceryl trioleate, glyceryl monostearate, trimethylolpropane trioleate and sorbitan monostearate in the compound dispersant is 3:1:2:5.

[0057] The scraped foam and the remaining slurry are respectively subjected to solid-liquid separation, thereby obtaining zinc oxide product and zinc sulfide product; the above two products are sent for analysis, the grade of the obtained zinc oxide product is 24.22%, containing 0.68% of zinc sulfide, the grade of the obtained zinc sulfide is 33.97%, containing 1.43% of zinc oxide;

[0058] (2) take 200g of the zinc oxide product obtained in step (2), add 200ml water to make a slurry, then slowly add 800ml of zinc electrowinning waste electrolyte with a acidity of 180g / L into the slurry, the adding time is 8min;

[0059] (3) add concentrated sulfuric acid to the slurry of step (3) until pH=0.5, then start leaching, the leaching time is 1.5h, the leaching temperature is 60℃, the stirring speed is 500r / min, after leaching, the slurry is subjected to solid-liquid separation and sampling analysis, and the leaching rate of zinc oxide is calculated to be 95.94%.

[0060] Example 4

[0061] (1) take 1000g oxygen sulfur mixed concentrate, add 2000g water mixed evenly, then carry out ultrasonic dispersion, air is introduced during the dispersion process, the air flow is 50L / min; add 12g compound dispersant; reaction time 25min, reaction temperature 30℃, stirring speed 600r / min, the surface foam of the slurry is scraped out gradually during the reaction until no foam is generated; the mass ratio of glyceryl trioleate, glyceryl monostearate, trimethylolpropane trioleate and sorbitan monostearate in the compound dispersant is 6:3:4:3.

[0062] The scraped foam and the remaining slurry are respectively subjected to solid-liquid separation, thereby obtaining zinc oxide product and zinc sulfide product; the above two products are sent for analysis, the grade of the obtained zinc oxide product is 24.76%, containing 0.94% of zinc sulfide, the grade of the obtained zinc sulfide is 33.85%, containing 1.56% of zinc oxide;

[0063] (2) take 200g zinc oxide product obtained in step (2), add 200ml water to make slurry, after the completion of the slurry, slowly add 800ml zinc electrowinning waste electrolyte with acidity 140g / L to the slurry, the adding time is 8min;

[0064] (3) add concentrated sulfuric acid to the slurry of step (3), until pH=0.5, then start leaching, leaching time is 3h, leaching temperature is 70℃, stirring speed is 500r / min, after the completion of leaching, solid-liquid separation and sample analysis, the leaching rate of zinc oxide is calculated to be 95.82%.

[0065] Example 5

[0066] (1) take 1000g oxygen-sulfur mixed concentrate, add 2000g water to mix evenly, then perform ultrasonic dispersion, and air is introduced during the dispersion process, the air flow is 50L / min; add 18g of compound dispersant; the reaction time is 20min, the reaction temperature is 25℃, the stirring speed is 600r / min, and the foam on the surface of the slurry is scraped off gradually during the reaction until no foam is generated; the mass ratio of glyceryl trioleate, glyceryl monostearate, trimethylolpropane trioleate and sorbitan monostearate in the compound dispersant is 6:4:5:3.

[0067] The scraped foam and the remaining slurry are respectively subjected to solid-liquid separation, thereby obtaining zinc oxide product and zinc sulfide product; the above two products are sent for analysis, and the grade of the obtained zinc oxide product is 23.57%, and the content of zinc sulfide is 1.51%, the grade of the obtained zinc sulfide is 32.14%, and the content of zinc oxide is 2.21%;

[0068] (2) take 200g zinc oxide product obtained in step (2), add 200ml water to make slurry, after the completion of the slurry, slowly add 800ml zinc electrowinning waste electrolyte with acidity 160g / L to the slurry, the adding time is 10min;

[0069] (3) add concentrated sulfuric acid to the slurry of step (3), until pH=0.5, then start leaching, leaching time is 2h, leaching temperature is 60℃, stirring speed is 500r / min, after the completion of leaching, solid-liquid separation and sample analysis, the leaching rate of zinc oxide is calculated to be 95.67%.

Claims

1. A comprehensive utilization process of oxygen-sulfur mixed zinc concentrate, characterized in that, The comprehensive utilization process of the oxygen-sulfur mixed zinc concentrate comprises pretreatment, main reaction and post-treatment steps, and specifically comprises: A. Pretreatment: slurry adjustment is performed on the oxygen-sulfur mixed concentrate to be treated, and ultrasonic dispersion is performed to obtain material a; B. Main reaction: a compound dispersant is added to the material a for stirring reaction, and the upper foam of the solution is scraped off during the reaction to obtain foam b and slurry c; C. Post-treatment: 1) solid-liquid filtration is performed on the foam b, and the zinc sulfide product and slurry d are obtained after the solid-liquid separation of the foam b, and the slurry d and the slurry c are combined to obtain the zinc oxide product; 2) slurry adjustment is performed on the zinc oxide product to obtain the slurry d; 3) after the pH is adjusted to 0.5-1 by adding acid, acid leaching is performed on the slurry d, and the leaching liquid e and the leaching residue f are obtained after the solid-liquid separation; 4) the zinc ingot is obtained after purification and electrodeposition of the leaching liquid e; 5) after ore blending, roasting and sulfuric acid leaching are performed on the zinc sulfide product, the leaching liquid g and the leaching residue h are obtained after the solid-liquid separation; 6) the zinc ingot is obtained after purification and electrodeposition of the leaching liquid g; the flue gas obtained after roasting is used to prepare sulfuric acid by an acid preparation system; The comprehensive utilization process of the oxygen-sulfur mixed zinc concentrate is characterized in that the compound dispersant is obtained by compounding glycerol trioleate, glycerol monostearate, trimethylolpropane trioleate and sorbitan monostearate, and the mass ratio of the glycerol trioleate, the glycerol monostearate, the trimethylolpropane trioleate and the sorbitan monostearate is (3-6):(1-4):(2-5):(1-3).

2. The comprehensive utilization process of oxygen-sulfur mixed zinc concentrate according to claim 1, characterized in that, The concentration of the slurry after slurry adjustment in the A step is 20-40%.

3. The comprehensive utilization process of oxygen-sulfur mixed zinc concentrate according to claim 1, characterized in that, The adding amount of the oxygen-sulfur separation agent of the oxygen-sulfur mixed zinc concentrate in the B step is 0.1-2% of the mass of the concentrate in the material a.

4. The comprehensive utilization process of oxygen-sulfur mixed zinc concentrates according to claim 1, characterized in that, The temperature of the reaction in the B step is 20-50 DEG C, the reaction time is 5-40 min, and the stirring speed is 400-800 r / min.

5. The comprehensive utilization process of oxygen-sulfur mixed zinc concentrates according to claim 1, characterized in that, The liquid-solid ratio of the slurry adjustment in the C step 2) is 0.5:1-2:

1.

6. The comprehensive utilization process of oxygen-sulfur mixed zinc concentrates according to claim 1, characterized in that, The acid in the C step 3) is sulfuric acid solution, waste electrolyte, waste acid or waste acid, the acidity is 50-200 g / L, the acid supplementing time is 5-30 min, and the terminal liquid-solid ratio is 4:1-8:

1.

7. The comprehensive utilization process of oxygen-sulfur mixed zinc concentrates according to claim 1, characterized in that, The temperature of the acid leaching in the C step 3) is 40-80 DEG C, and the acid leaching time is 1-3 h.

8. The comprehensive utilization process of oxygen-sulfur mixed zinc concentrates according to claim 1, characterized in that, In the C step 5), after ore blending, the zinc sulfide product is blended to have a zinc grade of 46-48% and sulfur content of 26-30%, and then is fed into a boiling furnace for roasting at 900-960 DEG C.

9. The comprehensive utilization process of oxygen-sulfur mixed zinc concentrates according to claim 1, characterized in that, In the C step 5), the temperature of the sulfuric acid leaching is 60-90 DEG C, and the time is 1-4 h.