Method for producing refined antimony by electrolyzing high-arsenic lead-antimony alloy

Abstract

The invention relates to a method for producing refined antimony through electrolysis of a high-arsenic lead-antimony alloy, and belongs to the technical field of metallurgical engineering. The method comprises the following steps: (1) melting the high-arsenic lead-antimony alloy, adding sodium hydroxide, and stirring to remove arsenic; the arsenic-removed lead-antimony alloy is obtained; (2) carrying out vacuum distillation on the arsenic-removed lead-antimony alloy to obtain a residual silver alloy, a volatile matter lead-antimony-bismuth alloy and a furnace wall attachment arsenic-antimony alloy; the residual silver alloy is conveyed to a silver recovery system to recover silver; and (3) the volatile matter lead-antimony-bismuth alloy is subjected to primary electrolysis, and crude antimony and primary electrolytic antimony anode slime are obtained. And (4) the crude antimony is subjected to secondary electrolysis, and refined antimony and secondary electrolytic antimony anode slime are obtained. According to the method, the high-arsenic lead-antimony alloy is utilized, refined antimony can be directly obtained, the process is short, the technology is environmentally friendly, energy consumption is low, operation is easy and convenient, and therefore industrial application and popularization are more convenient.

Description

Technical Field

[0001] The present application relates to the field of metallurgical engineering technology, and in particular to a method for producing refined antimony by electrolysis of a high-arsenic lead-antimony alloy. Background Art

[0002] Because lead ores are often associated with antimony, and antimony ores are often associated with lead, such as brittle sulfur lead antimony ore, large amounts of Pb-Sb alloys are produced during the smelting process of lead and antimony. Antimony is an essential raw material for the development of modern society, primarily used in high-tech fields such as batteries, electronic information, and optoelectronic guidance. Recycling lead-antimony alloys is an important way to regenerate antimony resources, with significant environmental, economic, and social benefits.

[0003] Existing methods for processing lead-antimony alloys include molten salt electrolysis, vacuum distillation, crystallization, smelting, and centrifugal segregation. Molten salt electrolysis has high equipment requirements and can cause side reactions that reduce the purity of the cathode product. Vacuum distillation suffers from incomplete separation in a single distillation, requiring multiple distillations and high energy consumption. Crystallization is associated with high dust production and labor requirements. Smelting produces large amounts of slag. Centrifugal segregation also requires high equipment requirements. Furthermore, none of these methods can easily produce refined antimony.

[0004] The prior art, published under the publication number CN117887980A, "A Method for Separating and Recovering Antimony from Lead-Antimony Alloy," distills the lead-antimony alloy under low-pressure, high-temperature conditions to produce a mixed metal vapor of lead and antimony. The resulting metal vapor is then subjected to nine stages of step-by-step temperature-variable gas-liquid phase separation. The resulting liquid phase is then refluxed into the lead-antimony alloy melt for further distillation and gas-liquid phase separation. During this process, distillation, gas-liquid phase separation, and liquid phase reflux occur simultaneously. The lead-antimony alloy is obtained in the first through eighth gas-liquid phase separation stages, and crude antimony is obtained in the ninth gas-liquid phase separation stage. This method utilizes the lead-antimony alloy to directly produce crude antimony, but suffers from the cumbersome control of the nine-stage step-by-step temperature-variable gas-liquid phase separation process. Summary of the Invention

[0005] In order to solve or partially solve the problems existing in the related art, the present application provides a method for producing refined antimony by electrolysis of high-arsenic lead-antimony alloy. Refined antimony can be directly prepared by this method, and the entire method is simple to operate and more convenient for industrial promotion and application.

[0006] A method for producing refined antimony by electrolysis of a high-arsenic lead-antimony alloy in this application comprises the following steps:

[0007] (1) Adding alkali to remove arsenic

[0008] After melting the high-arsenic lead-antimony alloy, adding sodium hydroxide and stirring to remove arsenic; obtaining the dearsenicized lead-antimony alloy;

[0009] (2) Vacuum distillation

[0010] The dearsenicized lead-antimony alloy is vacuum distilled to obtain residual silver alloy, volatile lead-antimony-bismuth alloy and arsenic-antimony alloy attached to the furnace wall; the residual silver alloy is sent to the silver recovery system to recover silver;

[0011] (3) Primary electrolysis

[0012] The volatile matter is subjected to primary electrolysis to obtain crude antimony and primary electrolytic antimony anode mud;

[0013] Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 80-100g / L, NH4 + 40-50g / L, F - 75-85g / L, H2SO4 280-320g / L; current density 200-220Am -2 , electrolysis cycle 48-96h, electrolysis temperature 30-35℃, interelectrode distance 65-75mm, cathode is made of stainless steel plate;

[0014] (4) Secondary electrolysis

[0015] The crude antimony is subjected to secondary electrolysis to obtain refined antimony and secondary electrolytic antimony anode mud;

[0016] Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 110-120g / L, NH4 + 50-60g / L, F - 85-95g / L, H2SO4 350-370g / L; current density 300-320Am -2 , electrolysis cycle 48-96h, electrolysis temperature 35-40℃, inter-electrode distance 65-75mm, cathode is made of stainless steel plate.

[0017] Furthermore, the process conditions of the vacuum distillation in step (2) are: vacuum degree of 10-15 Pa, distillation temperature of 600-650° C., and distillation time of 4-6 h.

[0018] The beneficial effects of this application are:

[0019] The method for producing refined antimony by electrolysis of high-arsenic lead-antimony alloys disclosed in this application targets difficult-to-treat high-arsenic lead-antimony alloys. Arsenic is first removed from the alloy by adding alkali. The resulting dearsenicized lead-antimony alloy is then subjected to vacuum distillation to further separate metals such as copper and silver from antimony, thereby producing a volatile lead-antimony-bismuth alloy. This volatile lead-antimony-bismuth alloy is then electrolyzed once to produce crude antimony. The crude antimony is ultimately electrolyzed twice to produce refined antimony. This method utilizes high-arsenic lead-antimony alloys to directly produce refined antimony. It features a short process, environmentally friendly technology, low energy consumption, and simple operation, making it more suitable for industrial promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The above and other objects, features and advantages of the present application will become more apparent through a more detailed description of exemplary embodiments of the present application in conjunction with the accompanying drawings, wherein the same reference numerals generally represent the same components in the exemplary embodiments of the present application.

[0021] Figure 1 It is a schematic diagram of the process flow in this application. DETAILED DESCRIPTION

[0022] The embodiments of the present application will be described in more detail below with reference to the examples. Although the embodiments of the present application are shown in the examples, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided to make the present application more thorough and complete, and to fully convey the scope of the present application to those skilled in the art.

[0023] Example 1

[0024] In this embodiment, a method for producing refined antimony by electrolysis of high-arsenic lead-antimony alloy is described as follows: Figure 1 As shown, the following steps are included:

[0025] (1) Adding alkali to remove arsenic

[0026] After melting the high-arsenic lead-antimony alloy, sodium hydroxide was added and stirred to remove arsenic; the dearsenicized lead-antimony alloy and arsenic alkali slag were obtained. The main chemical composition analysis table of the arsenic alkali slag is shown in Table 1:

[0027] Table 1

[0028]

[0029] (2) Vacuum distillation

[0030] The dearsenicized lead-antimony alloy is subjected to vacuum distillation to obtain a residual silver alloy, a volatile lead-antimony-bismuth alloy and an arsenic-antimony alloy attached to the furnace wall;

[0031] The process conditions of vacuum distillation are as follows: vacuum degree of 10 Pa, distillation temperature of 600 °C, and distillation time of 6 h;

[0032] The residual silver alloy is sent to the silver recovery system to recycle silver; the arsenic antimony alloy attached to the furnace wall can be sold directly; the volatile lead antimony bismuth alloy is sent to the subsequent electrolysis process; the vacuum distillation results are shown in Table 2:

[0033] Table 2

[0034]

[0035] (3) Primary electrolysis

[0036] The volatiles are subjected to a primary electrolysis to obtain crude antimony and primary electrolytic antimony anode mud; the crude antimony is subjected to a secondary electrolysis, and the primary electrolytic antimony anode mud is returned to the silver system to recover silver;

[0037] Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 80g / L, NH4 + 40g / L, F - 75g / L, H2SO4 280g / L; current density 200Am -2 , electrolysis cycle 48h, electrolysis temperature 35℃, inter-electrode distance 65mm, cathode is made of stainless steel plate.

[0038] After one electrolysis, the main components of the product are analyzed as shown in Table 3:

[0039] Table 3

[0040]

[0041] (4) Secondary electrolysis

[0042] The crude antimony is subjected to secondary electrolysis to obtain refined antimony and secondary electrolytic antimony anode mud; the refined antimony is sold directly, and the secondary electrolytic antimony anode mud is returned to the silver system for silver recovery;

[0043] Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 110g / L, NH4 + 50g / L, F - 85g / L, H2SO4 350g / L; current density 300Am -2 , electrolysis cycle 48h, electrolysis temperature 40℃, inter-electrode distance 65mm, cathode is made of stainless steel plate.

[0044] After the secondary electrolysis, the main components of the obtained product are analyzed as shown in Table 4:

[0045] Table 4

[0046]

[0047] Example 2

[0048] In this embodiment, a method for producing refined antimony by electrolysis of high-arsenic lead-antimony alloy is described as follows: Figure 1 As shown, the following steps are included:

[0049] (1) Adding alkali to remove arsenic

[0050] After melting the high-arsenic lead-antimony alloy, sodium hydroxide was added and stirred to remove arsenic; the dearsenicized lead-antimony alloy and arsenic alkali slag were obtained. The main chemical composition analysis table of the arsenic alkali slag is shown in Table 5:

[0051] Table 5

[0052]

[0053] (2) Vacuum distillation

[0054] The dearsenicized lead-antimony alloy is subjected to vacuum distillation to obtain a residual silver alloy, a volatile lead-antimony-bismuth alloy and an arsenic-antimony alloy attached to the furnace wall;

[0055] The process conditions of vacuum distillation are as follows: vacuum degree of 12.5 Pa, distillation temperature of 625 °C, and distillation time of 5 h;

[0056] The residual silver alloy is sent to the silver recovery system to recycle silver; the arsenic antimony alloy attached to the furnace wall can be sold directly; the volatile lead antimony bismuth alloy is sent to the subsequent electrolysis process; the vacuum distillation results are shown in Table 6:

[0057] Table 6

[0058]

[0059] (3) Primary electrolysis

[0060] The volatiles are subjected to a primary electrolysis to obtain crude antimony and primary electrolytic antimony anode mud; the crude antimony is subjected to a secondary electrolysis, and the primary electrolytic antimony anode mud is returned to the silver system to recover silver;

[0061] Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 90g / L, NH4 + 45g / L, F - 80g / L, H2SO4 300g / L; current density 210Am -2 , electrolysis cycle 72h, electrolysis temperature 32.5℃, inter-electrode distance 70mm, cathode made of stainless steel plate.

[0062] After one electrolysis, the product composition analysis is shown in Table 7:

[0063] Table 7

[0064]

[0065] (4) Secondary electrolysis

[0066] The crude antimony is subjected to secondary electrolysis to obtain refined antimony and secondary electrolytic antimony anode mud; the refined antimony is sold directly, and the secondary electrolytic antimony anode mud is returned to the silver system for silver recovery;

[0067] Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 110-120g / L, NH4 + 55g / L, F - 90g / L, H2SO4 360g / L; current density 310Am -2 , electrolysis cycle 72h, electrolysis temperature 37.5℃, inter-electrode distance 70mm, cathode made of stainless steel plate.

[0068] After the secondary electrolysis, the main components of the obtained product are analyzed as shown in Table 8:

[0069] Table 8

[0070]

[0071] Example 3

[0072] In this embodiment, a method for producing refined antimony by electrolysis of high-arsenic lead-antimony alloy is described as follows: Figure 1 As shown, the following steps are included:

[0073] (1) Adding alkali to remove arsenic

[0074] After melting the high-arsenic lead-antimony alloy, sodium hydroxide was added and stirred to remove arsenic; the dearsenicized lead-antimony alloy and arsenic alkali slag were obtained. The arsenic alkali slag was taken out, and the main chemical composition analysis table is shown in Table 9:

[0075] Table 9

[0076]

[0077] (2) Vacuum distillation

[0078] The dearsenicized lead-antimony alloy is subjected to vacuum distillation to obtain a residual silver alloy, a volatile lead-antimony-bismuth alloy and an arsenic-antimony alloy attached to the furnace wall;

[0079] The process conditions of vacuum distillation are as follows: vacuum degree of 15 Pa, distillation temperature of 650 °C, and distillation time of 4 h;

[0080] The residual silver alloy is sent to the silver recovery system to recycle silver; the arsenic antimony alloy attached to the furnace wall can be sold directly; the volatile lead antimony bismuth alloy is sent to the subsequent electrolysis process; the vacuum distillation results are shown in Table 10:

[0081] Table 10

[0082]

[0083] (3) Primary electrolysis

[0084] The volatiles are subjected to a primary electrolysis to obtain crude antimony and primary electrolytic antimony anode mud; the crude antimony is subjected to a secondary electrolysis, and the primary electrolytic antimony anode mud is returned to the silver system to recover silver;

[0085] Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 100g / L, NH4 + 50g / L, F - 85g / L, H2SO4 320g / L; current density 220Am -2 , electrolysis cycle 96h, electrolysis temperature 30℃, inter-electrode distance 65mm, cathode is made of stainless steel plate.

[0086] After one electrolysis, the main components of the product obtained are analyzed as shown in Table 11:

[0087] Table 1

[0088]

[0089] (4) Secondary electrolysis

[0090] The crude antimony is subjected to secondary electrolysis to obtain refined antimony and secondary electrolytic antimony anode mud; the refined antimony is sold directly, and the secondary electrolytic antimony anode mud is returned to the silver system for silver recovery;

[0091] Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 120g / L, NH4 + 60g / L, F - 95g / L, H2SO4 370g / L; current density 320Am -2 , electrolysis cycle 96h, electrolysis temperature 35℃, inter-electrode distance 65mm, cathode is made of stainless steel plate.

[0092] After the secondary electrolysis, the main components of the obtained product are analyzed as shown in Table 12:

[0093] Table 12

[0094]

[0095] The embodiments of the present application have been described above. The above description is illustrative and not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is selected to best explain the principles of the embodiments, their practical applications, or improvements to the technology in the market, or to enable other persons skilled in the art to understand the embodiments disclosed herein.

Claims

1. A method for producing refined antimony by electrolysis of high-arsenic lead-antimony alloy, characterized in that: The following steps are involved: (1) Adding alkali to remove arsenic After melting the high-arsenic lead-antimony alloy, adding sodium hydroxide and stirring to remove arsenic; obtaining the dearsenicized lead-antimony alloy; (2) Vacuum distillation The dearsenicized lead-antimony alloy is vacuum distilled to obtain residual silver alloy, volatile lead-antimony-bismuth alloy and arsenic-antimony alloy attached to the furnace wall; the residual silver alloy is sent to the silver recovery system to recover silver; (3) Primary electrolysis The volatile matter is subjected to primary electrolysis to obtain crude antimony and primary electrolytic antimony anode mud; Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 80-100g / L, NH4 + 40-50g / L, F - 75-85g / L, H2SO4 280-320g / L; current density 200-220Am -2 , electrolysis cycle 48-96h, electrolysis temperature 30-35℃, interelectrode distance 65-75mm, cathode is made of stainless steel plate; (4) Secondary electrolysis The crude antimony is subjected to secondary electrolysis to obtain refined antimony and secondary electrolytic antimony anode mud; Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 110-120g / L, NH4 + 50-60g / L, F - 85-95g / L, H2SO4 350-370g / L; current density 300-320Am -2 , electrolysis cycle 48-96h, electrolysis temperature 35-40℃, inter-electrode distance 65-75mm, cathode is made of stainless steel plate.

2. The method for producing refined antimony by electrolysis of a high-arsenic lead-antimony alloy according to claim 1, characterized in that: The process conditions of the vacuum distillation in step (2) are: vacuum degree of 10-15 Pa, distillation temperature of 600-650° C., and distillation time of 4-6 h.

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