CN108179441A - A kind of production method of high purity antimony - Google Patents

A kind of production method of high purity antimony Download PDF

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Publication number
CN108179441A
CN108179441A CN201711434031.8A CN201711434031A CN108179441A CN 108179441 A CN108179441 A CN 108179441A CN 201711434031 A CN201711434031 A CN 201711434031A CN 108179441 A CN108179441 A CN 108179441A
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CN
China
Prior art keywords
antimony
high purity
ion exchange
production method
purity antimony
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201711434031.8A
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Chinese (zh)
Inventor
韦竣严
韦建初
兰岱龙
何正军
陆宏卫
曹应科
卢忠讲
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Guangxi Sheng Fu Antimony Industry Polytron Technologies Inc
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Guangxi Sheng Fu Antimony Industry Polytron Technologies Inc
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Application filed by Guangxi Sheng Fu Antimony Industry Polytron Technologies Inc filed Critical Guangxi Sheng Fu Antimony Industry Polytron Technologies Inc
Priority to CN201711434031.8A priority Critical patent/CN108179441A/en
Publication of CN108179441A publication Critical patent/CN108179441A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/22Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06Operating or servicing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses a kind of production methods of high purity antimony, it is characterised in that:After antimony sulfate powder is completely dissolved, first using the method for diaphragm electro-deposition being recycled to prepare high purity antimony in stainless steel surface after being forced through ion exchange resin progress solution deep purification, include the following steps:(1) pH value of antimony sulfate solution is adjusted, repressurization carries out the impurity in ion exchange depth purification antimony sulfate solution by ion exchange column;(2) anode is done using 99.99% high purity antimony through step (1) purified antimony sulfate solution, doing cathode using pretreated stainless steel base carries out diaphragm electrolysis deposition, prepares high purity antimony.The present invention overcomes the difficulty of purification in high purity antimony preparation process, depth removal impurity is with obvious effects, and easy to operate and service speed is fast.Metallic antimony purity is made and may be up to 99.999%.

Description

A kind of production method of high purity antimony
Technical field
The invention belongs to the technologies of wet method electrolysis high purity antimony, are related to a kind of production method of high purity antimony.
Technical background
High purity antimony is chiefly used in semi-conducting material, is semicon industry, scientific research, the indispensable raw material of military project.At present, Most of method of most of production high purity antimonies is smelting or chemical deposition etc., and equipment scale is big, complicated for operation, and product Purity also cannot be guaranteed.High purity antimony made from the method refining of in the past few years also useful electrolysis, it is easy to operate compared to for smelting, Purity also has promotion, but still there are problems that not removing impurity metallic elements in antimony, and the quality of product is not also high, production speed Degree is slow.
Invention content
It is insufficient present in existing electrolysis tech the invention reside in solving, a kind of production method of high purity antimony is provided.
The technique prepares high purity antimony using solution purification joint pressurized membrane electrolytic refining process, includes the following steps:
(1) after antimony sulfate is completely dissolved, adjust pH value to 4~6, by force (forcing) pump be forced through ion exchange column carry out from Son exchanges, the impurity in deep purifying antimony sulfate solution;
(2) anode is done using 99.99% high purity antimony in the antimony sulfate solution purified through step (1), it is pretreated Stainless steel base does cathode and carries out diaphragm electrolysis deposition high purity antimony;
(3) material that step (2) prepares on stainless steel base is removed and both obtains high purity antimony material.
In step (1) during deep purifying used ion exchange column for two series connection equipped with ion exchange resin from Sub- exchange column, ion exchange resin selection D851 resin cations and WDA918 chelating resins.
The pressure value that force (forcing) pump pressurizes in step (1) is 0.12~0.20MPa.
The condition that the method for electrolytic deposition substantially obtains high purity antimony in stainless steel described in step (2) is:Current density 3 ~10A/dm2, 25~45 DEG C of electrolysis temperature obtains high purity antimony material at 3~10 hours cathodes of electrolysis time.
In step (2), the pretreatment of the stainless steel base by pretreatment is divided into following steps:
The polishing pre-treatment of a body of stainless steel:By stainless steel base respectively with 200 mesh, 350 mesh, 560 mesh, 800 mesh, 1000 mesh Abrasive paper for metallograph is polishing to surface-brightening no marking.
B oil removal treatments:Using NaOH solution and a small amount of emulsifier NP, TX or OP are added in, being heated to 80~100 DEG C makes Saponification half an hour occurs for grease, and the formula of solution is:NaOH70g/L, emulsifier 2g/L.
C acid-wash activations:Acid-wash activation is carried out to the stainless steel after oil removing, the formula of pickling is 25g/L hydrochloric acid solutions.
Diaphragm used in step (2) interval membrane electroplating is homogeneous-phase anion film, effectively obstructs impurity cationic on cathode Deposition, diaphragm are mounted on film frame and are placed in cathodic region.
Metallic antimony purity made from the above method is 99.999%, and the complete impulse- free robustness of metallic antimony smooth surface.
Beneficial effects of the present invention are:The present invention prepares high purity antimony using solution purification process integration electro-deposition refining, molten The impurity-eliminating effect of liquid is apparent, and operability is strong, and speed of production is fast.It solves the purity problem of metallic antimony, avoids because doping is led The product physical property of cause declines, and performance is low, the very long situation of production procedure.Diaphragm electrolysis deposition operation process is simple, The product antimony purity of preparation can reach 99.999%.
Specific embodiment
It is handled in the following ways in the preparation method of the present invention:
The pressurization of joint ion exchange resin recycles the method for diaphragm electro-deposition in stainless steel surface after carrying out solution deep purification Prepare high purity antimony.
1st, used ion exchange column is two ion exchanges equipped with ion exchange resin connected during deep purifying Column combination, ion exchange resin selection D851 resin cations and WDA918 chelating resins both ion exchange resin.With 99.99% high purity antimony does anode, and pretreated stainless steel base does cathode and carries out diaphragm electrolysis deposition, prepares high purity antimony.
2nd, the pretreatment of the stainless steel base of pretreatment is divided into following steps:
The polishing pre-treatment of a body of stainless steel:By stainless steel base respectively with 200 mesh, 350 mesh, 560 mesh, 800 mesh, 1000 mesh Abrasive paper for metallograph is polishing to surface-brightening no marking.
B oil removal treatments:Using NaOH solution and a small amount of emulsifier NP, TX or OP are added in, being heated to 80~100 DEG C makes Saponification half an hour occurs for grease, and the formula of solution is:NaOH70g/L, emulsifier 2g/L.
C acid-wash activations:Acid-wash activation is carried out to the stainless steel after oil removing, the formula of pickling is 25g/L hydrochloric acid solutions.
3rd, diaphragm plating diaphragm used is homogeneous-phase anion film, effectively obstructs impurity cationic and is deposited on cathode, every Film is mounted in cathodic region.
Example one:Antimony sulfate solution adjusts pH value of solution=5 using dilute sulfuric acid, and solution is passed sequentially through equipped with D851 cation trees The ion exchange column of fat and WDA918 chelating resins, cycle removal of impurities is for 24 hours.The front and rear solution of purification is analyzed through ICPMS, impurity content As shown in table 1:
Impurity analysis in 1 purified solution of table
Example two:Anode is done with 99.99% high purity antimony, pretreated stainless steel base does cathode and carries out diaphragm electrolysis Deposition, electrodeposition condition:Current density 3A/dm2, 25 DEG C of electrolysis temperature obtains high purity antimony material at 3 hours cathodes of electrolysis time Material, analyzes electrodeposited material with GDMS, and total purity of high purity antimony is as shown in table 2 for 99.9991% impurity content:
The impurity analysis of 2 product of table
Element Content/ppm Element Content/ppm Element Content/ppm Element Content/ppm
Na 0.01 Si < 1.0 S 0.130 Cr 0.020
Fe 1.500 Ni 0.600 Co 0.650 Cu 1.500
Zn 0.008 Se < 0.05 As 1.500 Zr < 0.005
Mo 0.650 Ag 0.500 Cd 0.530 In < 0.005
Sn 0.110 Sb 0.024 W < 0.005 Re < 0.005
Pb 0.560 Bi < 0.005 Th < 0.001 U < 0.001
Anode is done with 99.99% high purity antimony, pretreated stainless steel base does cathode and carries out diaphragm electrolysis deposition, electricity Sedimentary condition:Current density 10A/dm2, 45 DEG C of electrolysis temperature obtains high purity antimony material at 10 hours cathodes of electrolysis time, uses GDMS analyzes electrodeposited material, and total purity of high purity antimony is as shown in table 3 for 99.9994% impurity content:
3 product impurity analysis of table
Element Content/ppm Element Content/ppm Element Content/ppm Element Content/ppm
Na 0.010 Si < 0.5 S 0.110 Cr 0.020
Fe 1.400 Ni 0.600 Co 0.080 Cu 0.400
Zn 0.007 Se < 0.05 As 0.900 Zr < 0.005
Mo 0.450 Ag 0.460 Cd 0.530 In < 0.005
Sn 0.110 Sb 0.010 W < 0.005 Re < 0.005
Pb 0.360 Bi < 0.005 Th < 0.001 U < 0.001
The present invention prepares high purity antimony using solution purification process integration electro-deposition refining, and the impurity-eliminating effect of solution is apparent, can Strong operability, speed of production is fast, and the antimony purity produced can reach 99.999%.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, without departing from the principle of the present invention, several improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (9)

1. a kind of production method of high purity antimony, it is characterised in that:After antimony sulfate powder is completely dissolved, first using be forced through from Subtree fat carry out solution deep purification after recycle diaphragm electrolysis deposition method prepare high purity antimony in stainless steel surface, including with Lower step:(1) pH value of antimony sulfate solution is adjusted, repressurization carries out ion exchange depth by ion exchange column and purifies antimony sulfate Impurity in solution;(2) anode is done using 99.99% high purity antimony through step (1) purified antimony sulfate solution, using pre- place Stainless steel base after reason does cathode and carries out diaphragm electrolysis deposition, prepares high purity antimony.
2. a kind of production method of high purity antimony according to claim 1, it is characterised in that:The deep purifying is by sulfuric acid Antimony solution passes through the ion exchange column of two series connection.
3. a kind of production method of high purity antimony according to claim 2, it is characterised in that:It is equipped in the ion exchange column Ion exchange resin, ion exchange resin select D851 resin cations and the filling of WDA918 chelating resins.
4. a kind of production method of high purity antimony according to claim 1, it is characterised in that:In the diaphragm electrolysis deposition Diaphragm is homogeneous-phase anion film.
5. a kind of production method of high purity antimony according to claim 1, it is characterised in that:The pressurization carries out deep purifying It is that antimony sulfate solution was pressurizeed film using force (forcing) pump, accelerates purification speed, pressure value is 0.12~0.20MPa.
6. a kind of production method of high purity antimony according to claim 1 or 2, it is characterised in that:The diaphragm electrolysis deposition Method the condition of high purity antimony obtained on stainless steel base be:3~10A/dm of current density2, 25~45 DEG C of electrolysis temperature, electricity It solves and high purity antimony material is obtained at 3~10 hours time cathode.
7. a kind of production method of high purity antimony according to claim 1, it is characterised in that:The stainless base steel of the pretreatment The pretreatment of body is divided into following steps:
The polishing pre-treatment of a body of stainless steel:By stainless steel base respectively with 200 mesh, 350 mesh, 560 mesh, 800 mesh, 1000 mesh metallographics Sand paper is polishing to surface-brightening no marking;
B oil removal treatments:Using NaOH solution and a small amount of emulsifier NP, TX or OP are added in, heating temperature, which rises to 80~100 DEG C, makes oil Saponification half an hour occurs for fat;
C acid-wash activations:Acid-wash activation is carried out to the stainless steel after oil removing, the formula of pickling is 25g/L hydrochloric acid solutions.
8. a kind of production method of high purity antimony according to claim 1, it is characterised in that:The adjusting antimony sulfate solution PH value size is 4~6.
9. a kind of production method of high purity antimony according to claim 7, it is characterised in that:The NaOH solution it is a concentration of 70g/L, a concentration of 2g/L of emulsifier, the emulsifier use NP, TX or OP.
CN201711434031.8A 2017-12-26 2017-12-26 A kind of production method of high purity antimony Pending CN108179441A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112048736A (en) * 2020-09-03 2020-12-08 武汉拓材科技有限公司 Method for preparing high-density rod-shaped antimony

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101818365A (en) * 2009-09-23 2010-09-01 兰州理工大学 Method for preparing nano stibium powder
CN104746105A (en) * 2015-04-14 2015-07-01 锡矿山闪星锑业有限责任公司 Device and method for separating antimony-containing alloy
CN105200453A (en) * 2015-10-23 2015-12-30 有研亿金新材料有限公司 Preparation process of electrolytic refined high-purity manganese
CN107385482A (en) * 2017-06-21 2017-11-24 陈桂芳 A kind of surface treatment method of kitchen stainless steel table top

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101818365A (en) * 2009-09-23 2010-09-01 兰州理工大学 Method for preparing nano stibium powder
CN104746105A (en) * 2015-04-14 2015-07-01 锡矿山闪星锑业有限责任公司 Device and method for separating antimony-containing alloy
CN105200453A (en) * 2015-10-23 2015-12-30 有研亿金新材料有限公司 Preparation process of electrolytic refined high-purity manganese
CN107385482A (en) * 2017-06-21 2017-11-24 陈桂芳 A kind of surface treatment method of kitchen stainless steel table top

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112048736A (en) * 2020-09-03 2020-12-08 武汉拓材科技有限公司 Method for preparing high-density rod-shaped antimony

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Application publication date: 20180619

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