Method for producing refined antimony through electrolysis of high-copper-lead-antimony alloy

Abstract

The invention relates to a method for producing refined antimony through electrolysis of a high-copper-lead-antimony alloy, and belongs to the technical field of metallurgical engineering. The method comprises the following steps that (1) the high-copper-lead-antimony alloy is subjected to liquation to remove copper; the copper-removed lead-antimony alloy is obtained; (2) carrying out vacuum distillation on the copper-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 residue is silver alloy and is conveyed to a silver recovery system to recover silver; (3) the volatile matter 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 refined antimony can be directly obtained by utilizing the high-copper-lead-antimony alloy, and the method is environment-friendly, energy-saving, short in process and simple and convenient to operate, so that the method is more convenient for industrial popularization and application.

Description

Technical Field

[0001] The present application relates to the technical field of metallurgical engineering, and particularly to a method for electrolytic production of refined antimony from a high-copper lead-antimony alloy. Background Art

[0002] Since lead ores often contain antimony as an associated element, and antimony ores often contain lead as an associated element, such as jamesonite, a large amount of Pb-Sb alloy is produced during the smelting of lead and antimony. Antimony is an essential basic raw material for the development of contemporary society, mainly used in high-tech fields such as batteries, electronic information, and optoelectronic guidance. Realizing the recycling of lead-antimony alloys is an important way to achieve the regeneration of antimony resources, with extremely high environmental, economic, and social benefits.

[0003] The existing treatment methods for lead-antimony alloys include molten salt electrolysis, vacuum distillation, crystallization, liquidation, and centrifugal segregation. Among them, molten salt electrolysis has problems such as high requirements for equipment and side reactions that reduce the purity of cathode products; vacuum distillation has the problem that the separation is not complete in one distillation and multiple distillations are required, resulting in high energy consumption; crystallization has problems such as a large amount of soot and a large amount of manual work; liquidation has the problem of a large amount of slag; and centrifugal segregation has high requirements for equipment. Further, it is not convenient to obtain refined antimony using the above methods.

[0004] In the prior art, the method for separating and recovering antimony from a lead-antimony alloy with the publication number CN117887980A distills the lead-antimony alloy under low pressure and high temperature conditions to obtain lead and antimony mixed metal vapors. The obtained metal vapors are subjected to nine-stage stepwise variable-temperature gas-liquid separation. The separated liquid phase is refluxed to the molten lead-antimony alloy for further distillation and gas-liquid separation. During this process, distillation, gas-liquid separation, and liquid phase reflux are carried out simultaneously; lead-antimony alloy is obtained in the first to eighth gas-liquid separation stages, and crude antimony is obtained in the ninth gas-liquid separation stage. This method realizes the direct production of crude antimony using lead-antimony alloys, but the problem is that the control of the nine-stage stepwise variable-temperature gas-liquid separation process is relatively cumbersome. Summary of the Invention

[0005] To solve or partially solve the problems existing in the related art, the present application provides a method for electrolytic production of refined antimony from a high-copper lead-antimony alloy. Using this method, refined antimony can be directly prepared, and the whole method is simple to operate and more convenient for industrial promotion and application.

[0006] A method for electrolytic production of refined antimony from a high-copper lead-antimony alloy in the present application includes the following steps:

[0007] (1) Liquidation to remove copper

[0008] The high-copper lead-antimony alloy is subjected to liquidation to remove copper; a copper-removed lead-antimony alloy and copper-removed slag are obtained;

[0009] (2) Vacuum distillation

[0010] The copper-lead-antimony alloy is subjected to vacuum distillation to obtain a residue silver alloy, a volatile lead-antimony-bismuth alloy, and an arsenic-antimony alloy adhering to the furnace wall; the residue silver alloy is sent to a silver recovery system for silver recovery;

[0011] (3) Primary electrolysis

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

[0013] Among them, the electrolysis control conditions are: the electrolysis system is HF-H2SO4-SbF3, Sb 3+ 80 - 100 g / L, NH4 + 40 - 50 g / L, F - 75 - 85 g / L, H2SO4 280 - 320 g / L; the current density is 200 - 220 A / m -2 , the electrolysis period is 48 - 96 h, the electrolysis temperature is 30 - 35 °C, the interelectrode distance is 65 - 75 mm, and the 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 electrolysis antimony anode slime;

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

[0017] Furthermore, the process conditions for vacuum distillation in step (2) are: the vacuum degree is 10 - 15 Pa, the distillation temperature is 690 - 720 °C, and the distillation time is 4 - 6 h.

[0018] The beneficial effects of this application are:

[0019] The method for electrolytic production of refined antimony from high-copper lead-antimony alloy in the present application aims at refractory high-copper lead-antimony alloy. Firstly, copper in the alloy is removed by liquation to obtain de-coppered lead-antimony alloy. The de-coppered lead-antimony alloy is further separated from silver metal through vacuum distillation to obtain volatile lead-antimony-bismuth alloy. The volatile lead-antimony-bismuth alloy produces crude antimony through primary electrolysis, and refined antimony is prepared from the crude antimony through secondary electrolysis. This method realizes the direct production of refined antimony from high-copper lead-antimony alloy, is environmentally friendly and energy-saving, has a short process, is easy to operate, and is thus more convenient for industrial promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] By describing the exemplary embodiments of the present application in more detail in conjunction with the drawings, the above and other objects, features, and advantages of the present application will become more apparent. Among them, in the exemplary embodiments of the present application, the same reference numerals generally represent the same components.

[0021] Figure 1 It is a process flow schematic diagram in the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[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, 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] A method for electrolytic production of refined antimony from high-copper lead-antimony alloy in this example has a process flow as Figure 1 shown, including the following steps:

[0025] (1) Liquation to remove copper

[0026] The high-copper lead-antimony alloy is subjected to liquation to remove copper, obtaining de-coppered lead-antimony alloy and copper removal slag. The main chemical composition analysis table is shown in Table 1:

[0027] Table 1

[0028]

[0029] (2) Vacuum distillation

[0030] The de-coppered lead-antimony alloy is subjected to vacuum distillation to obtain residue silver alloy, volatile lead-antimony-bismuth alloy, and arsenic-antimony alloy attached to the furnace wall;

[0031] Among them, the process conditions for vacuum distillation are: vacuum degree is 10 Pa, distillation temperature is 690 °C, and distillation time is 6 h;

[0032] The residue, which is a silver alloy, is sent to the silver recovery system for silver recovery; the furnace wall attachment, which is an arsenic-antimony alloy, can be sold directly; the volatile matter, which is a lead-antimony-bismuth alloy, is sent to the subsequent electrolysis process; the results of vacuum distillation are shown in Table 2:

[0033] Table 2

[0034]

[0035] (3) Primary electrolysis

[0036] The volatile matter is subjected to primary electrolysis to obtain refined antimony and primary electrolysis antimony anode slime; the refined antimony is sold directly, and the primary electrolysis antimony anode slime is returned to the silver system for silver recovery;

[0037] Among them, the electrolysis control conditions are: the electrolysis system is HF-H2SO4-SbF3, Sb 3+ 80 g / L, NH 4+ 40 g / L, F - 75 g / L, H2SO4 280 g / L; the current density is 200 A·m -2 , the electrolysis period is 48 h, the electrolysis temperature is 35 °C, the pole pitch is 65 mm, and the cathode uses a stainless steel plate.

[0038] After primary electrolysis, the main component analysis of the obtained product is 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 electrolysis antimony anode plates; the refined antimony is sold directly, and the secondary electrolysis antimony anode plates are returned to the silver system for silver recovery;

[0043] Among them, the electrolysis control conditions are: the electrolysis system is HF-H2SO4-SbF3, Sb 3+ 110 g / L, NH4 + 50 g / L, F - 85 g / L, H2SO4 350 g / L; the current density is 300 A / m -2 , the electrolysis period is 48 h, the electrolysis temperature is 40 °C, the pole pitch is 65 mm, and the cathode uses a stainless steel plate.

[0044] After secondary electrolysis, the main component analysis of the obtained product is shown in Table 4:

[0045] Table 4

[0046]

[0047] Example 2

[0048] A method for electrolytic production of refined antimony from a high-copper lead-antimony alloy in this embodiment, the process flow is as Figure 1 shown, including the following steps:

[0049] (1) Liquation to remove copper

[0050] Liquate the high-copper lead-antimony alloy to remove copper; obtain copper-removed lead-antimony alloy and copper-removed slag; the main chemical composition analysis table is shown in Table 5:

[0051] Table 5

[0052]

[0053] (2) Vacuum distillation

[0054] Vacuum distill the copper-removed lead-antimony alloy to obtain a residue silver alloy, a volatile lead-antimony-bismuth alloy, and an arsenic-antimony alloy adhering to the furnace wall;

[0055] Among them, the process conditions for vacuum distillation are: vacuum degree is 12.5 Pa, distillation temperature is 705 °C, and distillation time is 5 h;

[0056] The residue is a silver alloy and sent to the silver recovery system to recover silver; the arsenic-antimony alloy adhering to the furnace wall can be sold directly; the volatile matter is a lead-antimony-bismuth alloy and sent to the subsequent electrolysis process; the vacuum distillation results are shown in Table 6:

[0057] Table 6

[0058]

[0059] (3) Primary electrolysis

[0060] Electrolyze the volatile matter once to obtain refined antimony and primary electrolysis antimony anode mud; the refined antimony is sold directly, and the primary electrolysis 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+ 90 g / L, NH 4+ 45 g / L, F - 80 g / L, H2SO4 300 g / L; current density 210 A·m -2 , electrolysis cycle 72 h, electrolysis temperature 32.5 °C, electrode spacing 70 mm, and the cathode is made of stainless steel plate.

[0062] After primary electrolysis, the component analysis of the obtained product 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 the anode plate of secondary electrolysis antimony; the refined antimony is sold directly, and the anode plate of secondary electrolysis antimony is returned to the silver system for silver recovery;

[0067] Among them, the electrolysis control conditions are: the electrolysis system is HF-H2SO4-SbF3, Sb 3+ 115 g / L, NH4 + 55 g / L, F - 90 g / L, H2SO4 360 g / L; the current density is 310 A·m -2 , the electrolysis cycle is 72 h, the electrolysis temperature is 37.5 °C, the electrode spacing is 70 mm, and the cathode is made of stainless steel plate.

[0068] After secondary electrolysis, the main component analysis of the obtained product is shown in Table 8:

[0069] Table 8

[0070]

[0071] Example 3

[0072] A method for electrolytic production of refined antimony from high-copper lead-antimony alloy in this example, the process flow is as Figure 1 shown, including the following steps:

[0073] (1) Liquation to remove copper

[0074] The high-copper lead-antimony alloy is subjected to liquation to remove copper; the copper-removed lead-antimony alloy and copper-removing slag are obtained; the main chemical composition analysis table is shown in Table 9:

[0075] Table 9

[0076]

[0077] (2) Vacuum distillation

[0078] The copper-removed lead-antimony alloy is subjected to vacuum distillation to obtain the residue silver alloy, the volatile lead-antimony-bismuth alloy and the arsenic-antimony alloy attached to the furnace wall;

[0079] Among them, the process conditions of vacuum distillation are: the vacuum degree is 15 Pa, the distillation temperature is 720 °C, and the distillation time is 4 h;

[0080] The residue is the silver alloy sent to the silver recovery system for silver recovery; the furnace wall attachment is the arsenic-antimony alloy, which can be sold directly; the volatile matter is the lead-antimony-bismuth alloy sent to the subsequent electrolysis process; the vacuum distillation results are shown in Table 10:

[0081] Table 10

[0082]

[0083] (3) Primary electrolysis

[0084] Volatiles are subjected to primary electrolysis to obtain refined antimony and primary electrolysis antimony anode slime; the refined antimony is directly sold, and the primary electrolysis antimony anode slime is returned to the silver system for silver recovery;

[0085] Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 90 g / L, NH 4+ 50 g / L, F - 85 g / L, H2SO4 320 g / L; current density 220 A·m -2 , electrolysis cycle 96 h, electrolysis temperature 30 °C, electrode distance 75 mm, and the cathode is made of stainless steel plate.

[0086] After primary electrolysis, the main component analysis of the obtained product is shown in Table 11:

[0087] Table 11

[0088]

[0089] (4) Secondary electrolysis

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

[0091] Among them, the electrolysis control conditions are: electrolysis system HF-H2SO4-SbF3, Sb 3+ 120 g / L, NH4 + 60 g / L, F - 95 g / L, H2SO4 370 g / L; current density 320 A·m -2 , electrolysis cycle 96 h, electrolysis temperature 35 °C, electrode distance 75 mm, and the cathode is made of stainless steel plate.

[0092] After secondary electrolysis, the main component analysis of the obtained product is shown in Table 12:

[0093] Table 12

[0094]

[0095] The embodiments of the present application have been described above. The above description is exemplary and not exhaustive, and is also not limited to the disclosed embodiments. Many modifications and variations are obvious to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The choice of terms used herein is intended to best explain the principles of the embodiments, practical applications, or improvements to technologies in the market, or to enable other ordinary skill in the art to understand the embodiments disclosed herein.

Claims

1. A method for electrolytically producing refined antimony from a high copper-lead-antimony alloy, characterized in that, It includes the following steps: (1) Copper removal by liquation Perform copper removal by liquation on the high-copper lead-antimony alloy to obtain a copper-removed lead-antimony alloy and copper-removed slag; (2) Vacuum distillation Perform vacuum distillation on the copper-removed lead-antimony alloy to obtain a residue silver alloy, a volatile lead-antimony-bismuth alloy, and an arsenic-antimony alloy adhering to the furnace wall; the residue, which is the silver alloy, is sent to the silver recovery system for silver recovery; (3) Primary electrolysis Perform primary electrolysis on the volatile matter to obtain crude antimony and primary electrolysis antimony anode slime; Among them, the electrolysis control conditions are: the electrolysis system is HF-H2SO4-SbF3, and Sb 3+ is 80-100 g / L, NH4 + is 40-50 g / L, F - is 75-85 g / L, H2SO4 is 280-320 g / L; the current density is 200-220 A / m -2 , the electrolysis cycle is 48-96 h, the electrolysis temperature is 30-35 °C, the electrode spacing is 65-75 mm, and the cathode uses a stainless steel plate; (4) Secondary electrolysis Perform secondary electrolysis on the crude antimony to obtain refined antimony and secondary electrolysis antimony anode slime; Among them, the electrolysis control conditions are: the electrolysis system is HF-H2SO4-SbF3, and Sb 3+ is 110-120 g / L, NH4 + is 50-60 g / L, F - is 85-95 g / L, H2SO4 is 350-370 g / L; the current density is 300-320 A / m -2 , the electrolysis period is 48-96 h, the electrolysis temperature is 35-40 °C, the interpolar distance is 65-75 mm, and the cathode uses a stainless steel plate.

2. The method for electrolytic production of refined antimony from a high copper-lead-antimony alloy according to claim 1, characterized in that, The process conditions for vacuum distillation in step (2) are as follows: the vacuum degree is 10 - 15 Pa, the distillation temperature is 690 - 720 °C, and the distillation time is 4 - 6 h.

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