A comprehensive treatment system for desulfurization of antimony ingot production

Abstract

The present application relates to the technical field of gas purification, in particular to a comprehensive desulfurization treatment system for antimony ingot production, which comprises a cyclone separator, an electrostatic precipitator, a spray tower, a desulfurization tower and a fan connected by pipelines in sequence, the desulfurization tower is filled with a desulfurizer, and the desulfurizer is made of modified kaolin, red mud, Na2CO3, CaSO4, CuO, ZnO, a pore expanding agent and water, and tests show that the comprehensive desulfurization treatment system has a good purification effect on sulfur-containing waste gas generated in the antimony ingot production process, especially for sulfur dioxide gas, and the removal rate can reach 100%.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of gas purification, in particular to a comprehensive desulfurization treatment system for antimony ingot production. BACKGROUND

[0002] With the development of science and technology, antimony is widely used in the production of various flame retardants, alloys, ceramics, glass, pigments, semiconductor components, medicines, etc., such as lead-antimony alloy plates used in lead-acid batteries, and welding materials made of antimony, lead and tin. Antimony compounds are also important additives of widely used chlorine-containing and bromine-containing flame retardants. In addition, antimony has a wide range of applications in emerging microelectronics technology, such as AMD graphics card manufacturing. Since the end of the 20th century, China has become the world's largest producer of antimony and its compounds.

[0003] Antimony ingot, commonly known as refined antimony, is mainly used as a hardening agent for alloys in the metallurgical and battery industries, and is also a raw material for producing antimony oxide. There is a large amount of sulfur element in antimony ore, so a large amount of sulfur-containing waste gas is often generated during the smelting of antimony and the production of antimony ingot. Direct discharge will have a very bad impact on the environment, so desulfurization treatment is generally required. At present, the desulfurization treatment mostly uses adsorbents for adsorption, and the general effect is not good. SUMMARY

[0004] The present application provides a comprehensive desulfurization treatment system for antimony ingot production.

[0005] The technical scheme adopted is as follows:

[0006] A comprehensive desulfurization treatment system for antimony ingot production, comprising a cyclone separator, an electrostatic precipitator, a spray tower, a desulfurization tower and a fan connected in sequence by pipelines, wherein the desulfurization tower is filled with a desulfurization agent, and the desulfurization agent is made of the following raw materials:

[0007] Modified kaolin, red mud, Na2CO3, CaSO4, CuO, ZnO, pore expander and water.

[0008] Further, the desulfurization agent is made of the following raw materials by weight:

[0009] Modified kaolin 80-100 parts, red mud 20-30 parts, Na2CO3 1-2 parts, CaSO4 1-2 parts, CuO 1-2 parts, ZnO 5-10 parts, pore expander 2-5 parts and water 250-300 parts.

[0010] Further, it further comprises a sedimentation tank, which is connected with the spray tower through a pipeline.

[0011] Further, it further comprises a regeneration tank, which is connected with the sedimentation tank through a pipeline.

[0012] Further, a micro-nano bubble generator is further included, which is communicated with a spraying head arranged above the inside of the spraying tower and a water tank through pipelines respectively, the water tank is filled with sodium hydroxide solution for spraying, and the water tank is communicated with the regeneration tank through a pipeline.

[0013] Further, the regeneration tank is filled with lime emulsion for sodium hydroxide regeneration, and a demister is arranged in the spraying tower and located above the spraying head.

[0014] Further, the preparation method of the modified kaolin is as follows:

[0015] The kaolin is added into mixed acid composed of concentrated sulfuric acid and concentrated nitric acid, heated to 80-90 DEG C, stirred for 2-4 h, filtered, and the obtained solid is washed with water and dried.

[0016] Further, the preparation method of the pore-expanding agent is as follows:

[0017] The peanut shell is dried, crushed, treated with phosphoric acid and sodium hydroxide solution in sequence, washed with water and dried, calcined at 500-600 DEG C for 1-2 h under inert gas protection to obtain powder, and the powder, water glass, ammonium oxalate and water are mixed uniformly and kept at 60-80 DEG C for 10-20 h.

[0018] Further, the mass ratio of the powder, water glass and ammonium oxalate is 5-10:1:1-3.

[0019] Further, the preparation method of the desulfurizer is as follows:

[0020] The modified kaolin, red mud, Na2CO3, CaSO4, CuO, ZnO and pore-expanding agent are added into water and beaten for 30-60 min, the slurry is granulated by spraying to form microspheres, and the microspheres are calcined at 800-900 DEG C for 1-3 h.

[0021] The beneficial effects of the present application are as follows:

[0022] The application provides a comprehensive desulfurization treatment system for antimony ingot production, wherein a cyclone separator and an electrostatic precipitator can remove most dust, a circulating spray system composed of a spray tower, a sedimentation tank, a regeneration tank and a micro-nano bubble generator can use spray liquid containing micro-nano bubbles to wet residual dust to make it gather, agglomerate and settle, and can recycle and regenerate the spray liquid to improve the utilization rate of the spray liquid, the circulating spray system can remove most sulfur-containing gas, a desulfurization tower can perform secondary desulfurization on the waste gas to further purify the waste gas, the desulfurizer used is modified kaolin and red mud as a base body, CuO and ZnO can generate various unstable sulfides with the sulfur-containing gas, the sulfides are decomposed to generate elemental sulfur to fix the sulfur element, and the pore richness of the desulfurizer is improved by the pore-expanding agent to increase the specific surface area, so that the desulfurizer can be more fully contacted with the waste gas, the sulfur-fixing and desulfurization performance is improved, and test results show that the comprehensive desulfurization treatment system has good purification effect on the sulfur-containing waste gas generated in the antimony ingot production process, and the removal rate of sulfur dioxide gas can reach 100%. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 FIG. 1 is a structural schematic diagram of a comprehensive desulfurization treatment system in Example 1 of the application;

[0024] The reference numerals in the figure represent the following respectively:

[0025] 1-cyclone separator, 2-electrostatic precipitator, 3-spray tower, 4-sedimentation tank, 5-regeneration tank, 6-micro-nano bubble generator, 7-desulfurization tower, 8-fan, 9-water tank, 10-sprayer, 11-demister. DETAILED DESCRIPTION

[0026] In the examples, the specific conditions not specified are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, and are all conventional products that can be purchased on the market.

[0027] Example 1

[0028] Reference Figure 1 A comprehensive desulfurization treatment system for antimony ingot production, comprising a cyclone separator (1), an electrostatic precipitator (2), a spray tower (3), a desulfurization tower (7) and a fan (8) sequentially connected by pipelines, the desulfurization tower (7) is filled with a desulfurizer, the filling volume of the desulfurizer is 2.5m 3 The desulfurizer is made of the following raw materials in parts by weight:

[0029] Modified kaolin 80 parts, red mud 20 parts, Na2CO3 1 part, CaSO4 1.5 parts, CuO 1 part, ZnO 5 parts, pore-expanding agent 5 parts, and water 250 parts.

[0030] The precipitation tank (4) is communicated with the spray tower (3) through a pipeline, one end of the pipeline is communicated with the bottom of the spray tower (3), and the other end extends into the precipitation tank (4);

[0031] When the waste gas is treated by the cyclone separator (1) and the electrostatic precipitator (2) and most of the dust is separated, the waste gas enters the spray tower (3), and the waste gas moves upward and is in contact with the downwardly sprayed spray liquid, and the following reactions occur:

[0032] 2NaOH + SO2 → NaSO3 + H2O

[0033] Na2SO3 + SO2 + H2O → 2NaHSO3

[0034] The spray liquid carrying the dust particles can be discharged into the precipitation tank (4) to precipitate the solid particles therein, and the dust can be further removed;

[0035] The regeneration tank (5) is communicated with the precipitation tank (4) through a pipeline, and the height of the regeneration tank (5) is slightly lower than that of the precipitation tank (4), so that the NaHSO3-containing spray liquid in the precipitation tank (4) can be directly discharged into the regeneration tank (5) through gravity;

[0036] The micro-nano bubble generator (6) is communicated with the nozzle (10) arranged at the upper part of the spray tower (3) and the water tank (9) through pipelines, the water tank (9) contains 5wt% sodium hydroxide solution for spraying, the water tank (9) is communicated with the regeneration tank (5) through a pipeline, the regeneration tank (5) contains lime emulsion for sodium hydroxide regeneration, and a demister (11) is arranged in the spray tower (3) and located above the nozzle (10);

[0037] The following reactions occur in the regeneration tank (5):

[0038] 2NaHSO3 + Ca(OH)2 → Na2SO3 + CaSO3↓ + 2H2O

[0039] Na2SO3 + Ca(OH)2 → 2NaOH + CaSO3↓

[0040] The regenerated spray liquid can be pumped into the water tank (9) through a pipeline for supplementing the spray liquid.

[0041] The preparation method of the modified kaolin is as follows:

[0042] 1kg of kaolin is added into 3L mixed acid composed of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:1, the temperature is increased to 80℃, and after stirring for 4h, the obtained solid is washed with water and dried at 80℃.

[0043] The preparation method of the reaming agent is as follows:

[0044] After drying and crushing peanut shell, 100 g of dry peanut shell powder is obtained, and then the peanut shell powder is soaked in phosphoric acid for desalting, and then soaked in 10 wt% sodium hydroxide solution for desilication, and then washed with water and dried, and then calcined at 550 DEG C for 1 h under nitrogen protection to obtain a powder, and then the powder, water glass, ammonium oxalate and water are uniformly mixed and then kept at 80 DEG C for 15 h, wherein the mass ratio of the powder, water glass and ammonium oxalate is 10:1:2.

[0045] The preparation method of the desulfurizer is as follows:

[0046] Modified kaolin, red mud, Na2CO3, CaSO4, CuO, ZnO and pore expanding agent are added into water and beaten for 50 min, and then the slurry is formed into microspheres with a particle size of 20-50 um by spray granulation, and then the microspheres are calcined at 900 DEG C for 2 h.

[0047] The operation process of the system is as follows:

[0048] The sulfur-containing and dust-containing waste gas generated during the production of antimony ingots is collected through a gas collecting pipeline and then enters a cyclone separator (1) and an electrostatic precipitator (2) at a flow rate of 5000 m 3 / h, most of the dust is separated out, and then the waste gas enters a spray tower (3), moves upward, and contacts with the downwardly sprayed spray liquid, the sulfur-containing gas such as SO2 is absorbed by the spray liquid and deposited in the bottom of the spray tower (3) together with the dust, the remaining waste gas continues to enter a desulfurization tower (7) to be desulfurized again, the liquid in the bottom of the spray tower (3) reaches a certain amount and is discharged into a sedimentation tank (4) to settle the solid particles therein, the supernatant in the sedimentation tank (4) is directly discharged into a regeneration tank (5), the regeneration tank (5) contains lime milk for regenerating sodium hydroxide, the spray liquid is regenerated to generate sodium hydroxide again, and the regenerated spray liquid can be pumped into a water tank (9) through a pipeline for supplementing the spray liquid, so that the spray liquid can be recycled, in the embodiment, an electromagnetic valve and a sampling valve for sampling detection are installed on the pipeline, and a water pump is arranged on the pipeline for conveying the spray liquid.

[0049] Example 2:

[0050] The desulfurizer is prepared from the following raw materials by weight:

[0051] Modified kaolin 100 parts, red mud 30 parts, Na2CO3 2 parts, CaSO4 2 parts, CuO 2 parts, ZnO 10 parts, pore expanding agent 5 parts and water 300 parts.

[0052] Example 3:

[0053] The desulfurizer is prepared from the following raw materials by weight:

[0054] Modified kaolin 80 parts, red mud 20 parts, Na2CO3 1 part, CaSO4 1 part, CuO 1 part, ZnO 5 parts, pore expanding agent 2 parts, water 250 parts.

[0055] Comparative Example 1:

[0056] The same as Example 1, except that the water tank (9) is directly communicated with the spray head (10) arranged at the upper part inside the spray tower (3) through a pipeline, the spraying liquid is directly pumped into the spray tower (3) by a water pump, and no micro-nano bubble generator is arranged.

[0057] Comparative Example 2:

[0058] The same as Example 1, except that the kaolin is not modified.

[0059] Comparative Example 3:

[0060] The same as Example 1, except that the desulfurizing agent does not contain a pore expanding agent.

[0061] Performance test:

[0062] After the waste gas with the components in Table 1 is treated by the systems in Examples 1-3 and Comparative Examples 1-4, the results with the components in Table 2 are obtained:

[0063] Table 1:

[0064] Content / (mg / m 3 )]]> Sulfur dioxide 8042 Sulfur trioxide 4480 Hydrogen sulfide 4508 Solid particles 15546

[0065] Table 2:

[0066] Sulfur dioxide Sulfur trioxide Hydrogen sulfide Solid particles Example 1 0 2.1 3.3 5.8 Example 2 0 2.6 3.5 6.2 Example 3 0 2.3 3.2 6.5 Comparative Example 1 1.1 5.2 4.9 9.1 Comparative Example 2 0.4 4.6 4.8 7.8 Comparative Example 3 0.9 5.4 5.2 7.6

[0067] From the above Table 1, it can be seen that the desulfurization comprehensive treatment system provided by the present application has a good purification effect on the sulfur-containing waste gas generated in the antimony ingot production process, especially for sulfur dioxide gas, and the removal rate can reach 100%.

[0068] The above examples are only used to illustrate the technical solutions of the present application, but not limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can be modified, or some technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. An antimony ingot production desulfurization integrated treatment system characterized by, It comprises a cyclone separator, an electrostatic precipitator, a spray tower, a desulfurizer filled with a desulfurizing agent made of the following raw materials, and a fan connected in sequence by pipelines. Modified kaolin, red mud, Na2CO3, CaSO4, CuO, ZnO, pore expander, and water; The modified kaolin is prepared by the following method: The kaolin is added into a mixed acid composed of concentrated sulfuric acid and concentrated nitric acid, heated to 80-90 DEG C, stirred for 2-4 hours, filtered, and the obtained solid is washed with water and dried; The pore expander is prepared by the following method: The peanut shell is dried, crushed, treated with phosphoric acid and sodium hydroxide solution in sequence, washed with water and dried, calcined at 500-600 DEG C for 1-2 hours under inert gas protection to obtain a powder, and the powder, water glass, ammonium oxalate, and water are mixed uniformly and kept at 60-80 DEG C for 10-20 hours; The mass ratio of the powder, water glass, and ammonium oxalate is 5-10:1:1-3; The desulfurizing agent is prepared by the following method: The modified kaolin, red mud, Na2CO3, CaSO4, CuO, ZnO, and pore expander are added into water, and the slurry is sprayed and granulated to form microspheres, which are calcined at 800-900 DEG C for 1-3 hours; It further comprises a sedimentation tank connected with the spray tower by a pipeline; It further comprises a regeneration tank connected with the sedimentation tank by a pipeline; It further comprises a micro-nano bubble generator connected with a spray head arranged at the upper part of the interior of the spray tower and a water tank by pipelines, the water tank contains sodium hydroxide solution for spraying, and the water tank is connected with the regeneration tank by a pipeline; The regeneration tank contains lime emulsion for sodium hydroxide regeneration, and a demister is arranged in the spray tower above the spray head.

2. The antimony ingot production desulfurization integrated treatment system according to claim 1, characterized in that, The desulfurizing agent is made of the following raw materials by weight: Modified kaolin 80-100 parts, red mud 20-30 parts, Na2CO3 1-2 parts, CaSO4 1-2 parts, CuO 1-2 parts, ZnO 5-10 parts, pore expander 2-5 parts, and water 250-300 parts.

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