CN-122010175-A - Method for comprehensively recycling high-low boiling substances and waste acid in high-purity antimony production process

Abstract

The invention discloses a method for comprehensively recycling high-low boiling substances and waste acid in a high-purity antimony production process, and relates to the field of nonferrous metal smelting. According to the method, high-low boiling substances produced in the preparation process of high-purity antimony are mixed with waste acid produced by cleaning equipment, the mixed solution is sprayed into a roasting tower through compressed air for roasting, the roasted flue gas sequentially passes through a settling chamber, a bag dust collector and a two-stage water spray absorption tower to respectively produce antimony white and hydrochloric acid, the produced antimony white can be directly sold or used as an antimony smelting raw material, and the byproduct hydrochloric acid can be used as acid for wet smelting or further concentrated into 35-38% concentrated hydrochloric acid. The method can realize the cascade recycling of high-low boiling substances and antimony and chlorine in waste acid, has the characteristics of high recycling level and no generation of a large amount of waste water, and has good economic value and environmental protection benefit.

Inventors

• LI XUESHAN
• FENG YU
• SHAN XUESONG
• WANG LEI
• LI JIAYOU
• ZHAO HAINING
• YUAN LINGLING
• XU XINMIAO
• WANG RUN
• LIU TONGLE
• WANG WENJIA

Assignees

• 山东恒邦冶炼股份有限公司

Dates

Publication Date

20260512

Application Date

20260130

Claims (8)

1. 1. The method for comprehensively recycling the high-low boiling point substances and the waste acid in the production process of the high-purity antimony is characterized by comprising the following steps of: (1) Mixing, namely mixing high-low boiling substances containing antimony trichloride, which are produced in the production process of high-purity antimony, with hydrochloric acid-containing waste acid, which is produced by cleaning equipment, wherein the mixing volume ratio of the high-low boiling substances to the waste acid is 1:0.3-1:1, and the mixing time is 0.5-1 h; (2) Atomizing and roasting, namely atomizing the mixed solution obtained in the step (1), spraying the atomized mixed solution into a roasting tower, roasting at the temperature of 500-700 ℃ to convert antimony in the high-low boiling point substances into antimony oxide, and releasing hydrogen chloride gas; (3) Collecting antimony white, namely sequentially carrying out sedimentation separation and cloth bag dust removal on the flue gas containing the antimony oxide dust generated in the step (2), and collecting to obtain an antimony white product; (4) And (3) absorption acid production and tail gas treatment, namely introducing the tail gas containing hydrogen chloride gas after dust removal in the step (3) into at least one stage of water spray absorption tower for absorption to obtain byproduct hydrochloric acid, and then carrying out alkali liquor absorption treatment on the tail gas after water absorption and then discharging.
2. 2. The method for comprehensively recycling high-low boiling point substances and waste acid in the production process of high-purity antimony according to claim 1, wherein in the step (2), the roasting is performed under a micro negative pressure condition, and the pressure in the roasting tower is-50 Pa to-100 Pa.
3. 3. The method for comprehensively recycling high-low boiling substances and waste acid in the high-purity antimony production process according to claim 1 or 2 is characterized in that in the step (2), atomization is achieved by scattering the mixed solution into fine mist drops through compressed air, the pressure of the inlet liquid of the mixed solution is 0.1-0.3 MPa, and the pressure of the compressed air is 0.3-0.6 MPa.
4. 4. The method for comprehensively recycling high and low boiling substances and waste acid in the high-purity antimony production process according to claim 1 or 2, wherein in the step (2), the heat source of the roasting tower is selected from electric heating, gas heating or water gas heating.
5. 5. The method for comprehensively recycling high-low boiling substances and waste acid in the high-purity antimony production process according to claim 1 or 2, wherein in the step (3), the sedimentation separation is performed in a sedimentation chamber, the inlet temperature of the flue gas is controlled to be 300-350 ℃, and the outlet temperature is controlled to be 120-150 ℃.
6. 6. The method for comprehensively recycling high-low boiling substances and waste acid in the production process of high-purity antimony according to claim 1 or 2, wherein in the step (3), the bag-type dust removal is performed in a bag dust collector, the inlet temperature of the flue gas is controlled to be 120-150 ℃, and the outlet temperature is controlled to be 100-120 ℃.
7. 7. The method for comprehensively recycling high-low boiling point substances and waste acid in the production process of high-purity antimony according to claim 5, wherein the sedimentation chamber is made of stainless steel resistant to chloride corrosion.
8. 8. The method for comprehensively recycling high-low boiling substances and waste acid in the high-purity antimony production process according to claim 1 or 2, wherein in the step (4), two-stage serial water spray absorption towers are adopted for absorption, and the concentration of byproduct hydrochloric acid is 18% -22%.

Description

Method for comprehensively recycling high-low boiling substances and waste acid in high-purity antimony production process Technical Field The invention belongs to the technical field of nonferrous metal hydrometallurgy and secondary resource comprehensive utilization, and in particular relates to a comprehensive recovery and resource utilization method for high-low boiling substances and cleaning waste acid which are byproducts generated in the production process of a high-purity antimony chemical method. Background Gao Chunti (purity not less than 5N) is a key material in the high and new technical fields of infrared detectors, semiconductor substrates and the like. At present, the large-scale production of high-purity antimony mainly adopts a chemical method, and the core process comprises the steps of chlorination, multistage rectification purification, hydrogen reduction and the like of an antimony raw material. In this process, the rectification step produces a certain amount of low-boiling and high-boiling impurity fractions (collectively referred to as high-boiling and low-boiling impurities), which are mainly composed of antimony trichloride (SbCl 3) and contain a small amount of impurities such as arsenic. Meanwhile, during the start-up, stop-down and maintenance of the production device, equipment such as a rectifying tower, a reaction kettle and the like are required to be cleaned, so that waste acid containing hydrochloric acid (HCl) and soluble antimony salt is produced. At present, the main stream treatment modes of the two wastes in the industry are respectively treated, and inherent technical path dependence is formed. For high-low boiling substances, a hydrolysis process is generally adopted, namely water is added to enable the high-low boiling substances to generate antimony oxychloride (SbOCl) to be precipitated, the antimony oxychloride is sold as a low-value intermediate product, and a large amount of acid wastewater rich in hydrochloric acid and antimony salt is generated in the hydrolysis process, so that complex subsequent neutralization treatment is required. For the cleaning waste acid, an alkali liquor direct neutralization method is generally adopted, the acid in the waste acid is neutralized and then discharged, and chlorine element is not utilized, but is converted into chloride ions in the waste water, so that the environmental load is increased. The prior art scheme has the structural defects of quite remarkable first, incomplete resource recovery and low value although the operation is relatively simple. The antimony is recovered only in the form of antimony oxychloride, and can be converted into metallic antimony or antimony oxide by further treatment of downstream factories, so that the economic benefit is poor, and the chlorine element is not recovered at all and runs off along with the wastewater. Second, the environmental pollution pressure is high. Whether hydrolysis or neutralization, a large amount of salt-containing or acid wastewater to be disposed of is inevitably generated, the treatment cost is high, and the environmental risk is high. Thirdly, the process flow is essentially waste by waste, and the actual clean production and resource circulation are not realized. In the face of the above problems, the conventional improvement ideas are mostly optimized along the prior art paths, such as searching for a higher value utilization path of antimony oxychloride, improving hydrolysis process to reduce waste water, or evaporating and concentrating waste acid, etc. These ideas do not break through the traditional thought-setting and technical framework of treating two wastes separately as independent problems. Therefore, the industry has a long-term lack of a technical proposal capable of fundamentally solving the contradiction of high-valued recovery of antimony and chlorine resources and mass production of wastewater. The development of a brand new clean production technology capable of cooperatively treating two wastes and realizing the complete recovery of valuable elements and near-zero discharge of wastewater becomes a technical problem which is urgent to be solved in the field, and has great significance for improving the sustainable development capability of the whole high-purity antimony industry. Disclosure of Invention The invention aims to thoroughly overcome the structural defects of low resource recovery rate, poor product value and serious secondary pollution in the prior art, and provides a comprehensive recycling method for high-low boiling substances and waste acid, which has novel conception, synergistic process, high recycling level and environmental friendliness. In order to achieve the purpose, the invention abandons the traditional thought of separately treating two wastes and creatively provides a brand new technical concept of combining two into one and cooperatively converting. The method is characterized in that high-low boiling point substa