CN111455405B - Method and device for preparing high-purity indium by multi-unit series multi-stage electrolytic refining - Google Patents
Method and device for preparing high-purity indium by multi-unit series multi-stage electrolytic refining Download PDFInfo
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- CN111455405B CN111455405B CN202010518994.1A CN202010518994A CN111455405B CN 111455405 B CN111455405 B CN 111455405B CN 202010518994 A CN202010518994 A CN 202010518994A CN 111455405 B CN111455405 B CN 111455405B
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 107
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000007670 refining Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000003860 storage Methods 0.000 claims abstract description 51
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 49
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 14
- 230000012010 growth Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims description 89
- 239000003792 electrolyte Substances 0.000 claims description 31
- 238000004140 cleaning Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 108010010803 Gelatin Proteins 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 239000008273 gelatin Substances 0.000 claims description 7
- 229920000159 gelatin Polymers 0.000 claims description 7
- 235000019322 gelatine Nutrition 0.000 claims description 7
- 235000011852 gelatine desserts Nutrition 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 230000005674 electromagnetic induction Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000003723 Smelting Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000004807 localization Effects 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to the field of rare metal smelting, in particular to a method and a device for preparing high-purity indium by multi-unit serial multistage electrolytic refining, which comprises an electrolytic refining circulating system formed by communicating a storage tank before electrolysis, an electrolytic bath, a storage tank after electrolysis and a first circulating pump through pipelines and U-shaped tanks, and the high-purity indium with good quality consistency and purity of 8N is prepared by four steps of primary electrolysis, vacuum distillation, secondary electrolysis and single crystal growth through the electrolytic tank, so that a technical foundation and a material foundation are provided for the preparation of high-end products of indium phosphide materials in China.
Description
Technical Field
The invention relates to the field of rare metal smelting, in particular to a method and a device for preparing high-purity indium by multi-unit serial multistage electrolytic refining.
Background
In order to actively integrate with the construction of the national strategic emerging industry and industrial strong base engineering project, the localization of high-purity indium for producing indium phosphide in China is realized, and finally the localization of ultra-low dislocation indium phosphide for microelectronic national defense war industry, electronic lasers and 5G communication is realized, the autonomous supply of raw materials is realized, the short plates of an industrial chain are supplemented, the production cost is reduced, the localization substitution and autonomous controllability are realized (the current preparation of 8N high-purity indium for high-quality indium phosphide in China is 90% required to be imported from abroad). At present, the purity of the existing combined multi-unit high-purity indium preparation products in China can only reach 5-6N basically, although some manufacturers of 7-8 high-purity indium exist, the requirements of high-quality indium phosphide are difficult to meet due to low product yield and poor quality consistency, the quality influence of the raw material high-purity indium phosphide is difficult to reach the requirements in terms of the quality requirements of products such as dislocation density and carrier concentration in the process of preparing ultra-low dislocation indium phosphide semiconductor substrates, and the stability of the process is poor due to the influence of the raw material in the preparation process, so that the difficulty of large-scale preparation of the high-quality indium phosphide is increased. The technical method and the production equipment for preparing the high-purity indium by multi-unit serial multistage electrolytic refining are easier to realize industrial production, and the consistency of the product quality can be ensured, so that the technical and equipment related problems of the 8N high-purity indium for preparing the high-quality semiconductor material indium phosphide product in a large scale are solved.
Disclosure of Invention
The invention aims to provide a preparation method and equipment for preparing 8N high-purity indium for a high-quality indium phosphide substrate slice, so as to realize industrialized and large-scale production, and the prepared high-purity indium has good quality consistency and purity of 8N, and provides a technical foundation and a material foundation for preparing high-end products of indium phosphide materials in China.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The utility model provides a multi-unit series connection multistage electrolytic refining device, including the reservoir before the electrolysis, the electrolysis tank, the reservoir after the electrolysis, reservoir before the electrolysis communicates with the upper portion of electrolysis tank, reservoir after the electrolysis communicates with the lower part of electrolysis tank, form the difference in height each other, reservoir drain line mouth before the electrolysis and electrolysis tank inlet are in the coplanar, use U type groove intercommunication, reservoir bottom drain line mouth before the electrolysis sets up three at least drain pipes, install first current stabilizer in the drain pipe, electrolyte flows to U type groove through the drain pipe, get into the electrolysis tank by U type groove again, at least three drain pipe is installed to the lower part of electrolysis tank, communicate with the reservoir after the electrolysis through the pipeline, install the second current stabilizer between the pipeline, reservoir after the electrolysis and reservoir before the electrolysis communicate through the pipeline, install first circulating pump between two reservoir pipelines, reservoir before the electrolysis, the electrolysis tank, after the electrolysis reservoir, first circulating pump communicates through pipeline and U type groove and forms a refining circulation system.
Further, a movable cover plate is additionally arranged on the electrolytic tank, the movable cover plate is tightly attached to the edges of the U-shaped tank and the electrolytic tank, two rows of tooth grooves are symmetrically formed in the edges of the movable cover plate, and the size of each tooth groove is not smaller than that of a pole plate hanging lug.
Further, a plurality of holes are arranged on the movable cover plate.
Further, a bottom plate is additionally arranged at the upper part of the outlet pipe orifice of the electrolytic tank, the bottom plate is inclined in a slope shape at an angle of 0 .-15., an independent space is formed between the bottom plate and the bottom of the electrolytic tank, holes are formed in the bottom plate, and the arrangement mode of the holes is consistent with that of the movable cover plate.
Further, the shape of the bottom plate hole is inverted trapezoid.
Further, the number and the size of the liquid outlet pipe orifices at the bottom of the liquid storage tank and the liquid outlet pipe orifices at the bottom of the electrolytic tank are the same.
Further, a second circulating pump is arranged at intervals on the liquid outlet pipeline at the bottom of the electrolytic tank.
Further, a liquid inlet pipe arranged in the electrolytic liquid storage tank extends to the bottom of the electrolytic liquid storage tank.
The invention also provides a preparation method of the high-purity indium, which is used for preparing the 8N-grade high-purity indium and comprises the following steps of:
(1) Firstly, electrolytic refining, namely shearing a 4N refined indium material ingot into particles, cleaning, pouring the particles into a die to form an anode plate, pouring a titanium plate into a cathode, arranging the anode and the cathode In an electrolytic tank according to a cathode-anode distance of 20mm-25mm, adding high-grade pure NaCl and high-grade pure gelatin, preparing electrolyte with the concentration of In 3+ of 100g/L-120g/L, naCl of 70g/L-80g/L, pH of 2-2.5 In a liquid storage tank after electrolysis, and depositing indium at the cathode with the current density of 50A/m 2-60A/m2 to obtain 5N refined indium;
(2) Vacuum distillation, namely cleaning 5N-grade refined indium obtained by primary electrolytic refining, putting the cleaned refined indium into a cleaned vacuum furnace, using a high-purity quartz crucible, introducing 6N high-purity hydrogen and vacuumizing, keeping the pressure in the vacuum furnace at 1-5Pa, distilling at 850-950 ℃, regulating the constant temperature of current for 60-150 minutes, cutting off a power supply after the constant temperature is reached, stopping supplying cooling water and vacuumizing, and opening the vacuum furnace to take out the obtained 6N-grade refined indium and low-boiling-point substances;
(3) Performing secondary electrolytic refining, namely uniformly shearing 6N-grade refined indium obtained by vacuum distillation into particles In the step (1), cleaning and pouring, preparing electrolyte with the concentration of In 3+ of 80g/L-100g/L, naCl of 60g/L-70g/L, pH of 1.5-2.5 In a liquid storage tank after electrolysis by using high-grade pure sulfuric acid, cleaned refined indium, high-grade pure NaCl and high-grade pure gelatin, and depositing indium at a cathode by adopting the current density of 80-100A/m 2 to obtain 7N-grade refined indium;
(4) The single crystal growth, namely cleaning 7N-grade refined indium obtained by secondary refining, putting the cleaned refined indium into a single crystal furnace, sealing the single crystal furnace by using a high-purity quartz crucible, introducing 6N high-purity hydrogen and vacuumizing the single crystal furnace, and carrying out single crystal growth to obtain 8N-grade refined indium;
The electrolytic tanks used in the electrolytic refining in the steps (1) and (3) are any multi-unit serial multistage electrolytic refining device provided by the invention.
Preferably, in the electrolytic refining process, a refined indium material ingot is sheared into 1cm particles, refined indium is heated and poured in a mould to be molded, a filter paper bag is used for wrapping an anode with a polyester cloth bag, the refined indium is placed in a high-purity quartz crucible through vacuum distillation and single crystal growth, the inner wall of the quartz crucible is treated by a silicon-coated carbon film, the silicon-coated carbon film is heated in an electromagnetic induction mode, a three-channel high-temperature resistant nozzle is adopted for blowing argon for protection, oxygen and silane are combusted, and a silicon-carbon material generated by combustion is directly sprayed on the inner wall of the crucible.
The invention has the beneficial effects that:
1. the high-purity cleaning liquid is adopted to carry out physical and chemical cleaning according to strict operation steps, and the operation of each unit in the working flow is carried out in an ultra-clean working area, so that excellent preconditions are created for the preparation of high-purity indium;
2. According to different characteristics of the refined indium containing impurity types and the content, adopting a more scientific and reasonable process flow, removing corresponding impurities in each production unit as far as possible in a targeted manner, and strictly optimizing materials for each component, a heat transfer mode and various parameters in the control process flow;
3. the self-made electrolytic refining device is adopted, so that the material transmission is improved to the greatest extent from the aspect of the structural design of equipment, the fluid transmission tends to flow regularly in the electrolytic refining liquid exchange process, a rapid and stable transmission system is formed, and the electrolytic refining unit is ensured to exert the purification effect as much as possible;
4. Different process control parameters are adopted in the two-stage electrolytic refining, so that the impurity removal is more flexible and targeted;
5. Compared with the prior widely adopted process for purifying indium by low-temperature distillation and then high-temperature distillation, the invention preferably and only uses low-temperature distillation in the vacuum distillation unit, and aims to reduce the pollution caused by the volatilization and condensation processes of indium caused by high-temperature distillation, in particular to reduce the difficulty in indium extraction caused by the adhesion of indium in the hearth and the condensation chamber of the vacuum furnace, and has the further effect of being easier to realize industrialized flow operation.
Drawings
FIG. 1 is a schematic top view of an electrorefining apparatus;
FIG. 2 is a schematic side view of an electrorefining apparatus;
FIG. 3 is a schematic diagram of a floor hole;
FIG. 4 is a flow chart of a process for preparing 8N high purity indium;
The electrolytic solution storage tank comprises a storage tank before electrolysis, a U-shaped tank, a storage tank after electrolysis, a 4-electrolytic tank, a 5-first current stabilizer, a 51-second current stabilizer, a 6-first circulating pump, a 61-second circulating pump, a 7-movable cover plate, an 8-tooth socket, a 9-hole, a 10-bottom plate, an 11-independent space, a 12-bottom plate hole, a 13-pipeline, a 131-electrolytic solution storage tank liquid outlet pipe, a 132-electrolytic solution tank liquid outlet pipe, a 133-electrolytic solution storage tank liquid outlet pipe, a 134-electrolytic solution storage tank liquid inlet pipe.
Detailed Description
In each working procedure, strict physical and chemical cleaning and cleaning are adopted before refined indium enters an electrolytic refining unit, a vacuum distillation unit and a single crystal growth unit, and the specific operation is that the refined indium is sequentially cleaned by using high-grade pure dilute nitric acid, high-grade pure dilute hydrochloric acid, high-grade pure water with the purity of 18 megaresistivity, high-grade pure methanol for dehydration and high-purity nitrogen with the purity of more than 5N respectively in a super clean working area (if no special explanation exists, the cleaning treatment is carried out by using the mode for cleaning materials and equipment in the invention, and the cleaning is hereinafter referred to as cleaning);
the vacuum furnace high-purity quartz crucible, the inner wall of the furnace, the electrolytic tank, the monocrystal growth crucible, the quartz tube and other components in contact with indium are strictly cleaned, and the electrolytic refining is carried out in an ultra-clean working area by adopting the self-made specific electrolytic tank.
The multi-unit serial multistage electrolytic refining device comprises a pre-electrolytic liquid storage tank 1, an electrolytic tank 4 and a post-electrolytic liquid storage tank 3, wherein the pre-electrolytic liquid storage tank 1 is communicated with the upper part of the electrolytic tank 4, the post-electrolytic liquid storage tank 3 is communicated with the lower part of the electrolytic tank 4, a height difference is formed between the pre-electrolytic liquid storage tank 1 and the electrolytic tank, the outlet of a pre-electrolytic liquid storage tank 131 is in the same plane with the inlet of the electrolytic tank, a U-shaped tank 2 is used for communicating, at least three liquid outlet pipes 131 are arranged at the outlet of the bottom of the pre-electrolytic liquid storage tank, a first current stabilizer 5 is arranged in the liquid outlet pipe, the electrolyte flows to the U-shaped tank 2 through the liquid outlet pipes 131, then enters the electrolytic tank 4 through the U-shaped tank 2, the electrolyte automatically flows out and gradually enters the electrolytic tank through the flowing transmission of the bottom of the U-shaped tank, the electrolyte gradually flows into the electrolytic tank through the flat plate, and a stable current stabilizing system of the electrolyte is created due to the fact that the electrolyte is more stable and the electrolyte is deposited in a non-turbulent flow system is generated.
At least three liquid outlet pipes 132 are arranged at the lower part of the electrolytic tank 4 and are communicated with the electrolytic rear liquid storage tank 3 through pipelines, a second current stabilizer 51 is arranged between the pipelines, the electrolytic rear liquid storage tank 3 and the electrolytic front liquid storage tank 1 are communicated through the pipelines, a first circulating pump 6 is arranged between the two liquid storage tank pipelines, and the electrolytic front liquid storage tank 1, the electrolytic tank 4, the electrolytic rear liquid storage tank 3 and the first circulating pump 6 are communicated through the pipelines and the U-shaped tank to form an electrolytic refining circulating system.
As shown in figure 1, the electrolytic cell is additionally provided with a steady flow movable cover plate 7, the movable cover plate 7 is tightly attached to the edges of the U-shaped cell 2 and the electrolytic cell 4, and the ideal state is seamless connection, so that the movable cover plate can be covered with anti-corrosion rubber or silica gel. The edges of the steady flow movable cover plate 7 are provided with tooth grooves 8 which are regularly arranged, the size of the tooth grooves 8 is preferably that the polar plate hanging lugs are completely placed, and the effect is to regulate the arrangement of the cathode and anode polar plates, so that the same polar distance and the cathode and anode polar distance are controlled to be in a specified value. The flow stabilizing movable cover plate is regularly provided with a plurality of holes which are arranged in a straight line between the cathode and the anode plates, and the function of the holes is to regulate the flow direction of electrolyte entering the electrolytic tank, and the regulated electrolyte uniformly flows between the cathode and the anode plates from top to bottom.
As shown in FIG. 2, the bottom plate 10 is additionally arranged on the electrolytic tank, the bottom plate 10 is inclined to the liquid outlet in a slope shape (0 .-15.) and is arranged above the liquid outlet at the bottom of the electrolytic tank 4, and holes 12 of the bottom plate are arranged on the plate in a manner consistent with the holes 9 on the movable cover plate 7. The mounting bottom plate has the function that electrolyte fluid flowing out of the liquid storage tank before electrolysis through the flow stabilizing device is regarded as laminar flow movement, and the fluid flowing in laminar flow movement is separated into one layer after flowing through each row of holes until the fluid at the uppermost layer flows out through the last row of holes, and the holes of the bottom plate correspond to the holes of the cover plate, so that smooth running of laminar flow is ensured. Secondly, an independent space 11 is separated at the lower part of the electrolytic tank, so that the independent space becomes an extension part of a liquid inlet of the circulating pump. The electrolyte in the independent space is pumped by the circulating pump to generate acting force which promotes fluid transmission, the suction force of the laminar flow close to the pump end is stronger than the suction force of the laminar flow far from the pump end, and the suction force overcomes the friction force to further promote the uniform motion of each layer of fluid.
As shown in fig. 3, the bottom plate 10 has a certain thickness, the shape of the bottom plate hole 12 is in an inverted trapezoid shape with a large upper part and a small lower part, the function of adopting the design is to form a force expansion on the pumping action of a pump, and the problem to be solved is to transfer floccules formed in the electrolytic process, so that the floccules can be better transferred to the rear section along with fluid, further the floccules are prevented from being deposited on a cathode plate and an anode plate, the purity reduction caused by the rising of indium inclusion deposited on the cathode plate is reduced, and the anode passivation caused by the rising of the potential of the anode plate is avoided.
The outlet of the electrolytic tank 4 is provided with two liquid outlet modes in combination with the industrial operation site of the electrolytic refining indium. Firstly, the number of the self-flow outlets and the number of the self-flow liquid outlet pipes 132 are equal to the number of the liquid outlet pipes 131 at the bottom of the liquid storage tank before electrolysis (namely, the number of the self-flow liquid inlet pipes), in order to realize that the liquid inlet amount is equal to the liquid outlet amount in the stable electrolysis process and ensure that the liquid exchange of an electrolysis system is smoothly carried out, the sizes of the liquid outlet pipes are equal, secondly, the liquid outlet pipes of a second circulating pump 61 are arranged, the number of the liquid outlet pipes of the second circulating pump 61 are arranged between the liquid outlet pipes 132 at intervals, and the effect is to suck the impurities which are generated in the electrolysis process and are not easy to remove along with the self-flow, improve the environment of an electrolyte system and lead the electrolytic deposition indium to tend to stable benign operation. The electrolyte flowing out in the two liquid outlet modes is connected to a liquid storage tank after electrolysis through a liquid conveying pipeline.
The liquid inlet and outlet of the liquid storage tank after electrolysis adopts a mode of lower inlet and upper outlet, namely, a liquid inlet pipe 134 arranged in the liquid storage tank after electrolysis extends to a position below the liquid level and close to the bottom of the liquid storage tank, a liquid outlet pipe 133 of the liquid storage tank after electrolysis is arranged at the upper part of the tank body, the contact area between the liquid storage tank and air in the transmission of the electrolyte is reduced by lower inlet and upper outlet, the acid volatilization caused by the generation of bubbles in the electrolyte is reduced, and the working environment of operators is improved. The liquid storage tank after electrolysis also has the function of being used as a liquid preparation barrel, namely, according to the change of the electrolysis process, the adjustment of electrolyte components, such as the adjustment of indexes of In 3+ concentration, naCl concentration, pH value, gelatin content and the like, is realized at the position within the specified operation parameters, so that the electrolysis process tends to be stable.
The electrolytic tank prepared by the method is used for the step of electrolytic refining in the preparation process of 8N high-purity indium, and the specific preparation steps are as follows:
1. High purity indium was prepared using 4N refined indium as shown in the process flow diagram. Comprises the operation procedures of electrolytic refining, vacuum distillation and single crystal growth;
2. the method uses dilute hydrochloric acid prepared from analytical grade hydrochloric acid to wash the outsourced refined indium, and the cleaning equipment is a high-pressure water flow jet type cleaning machine. Dehydrating the water after the flushing by using high-grade pure methanol and drying the water by using high-purity nitrogen with the purity of more than 5N for later use;
3. Cutting the refined indium ingot into particles with the diameter of about 1 cm and cleaning;
4. Cleaning a die for pouring the anode plate and a titanium plate serving as a cathode;
5. heating and pouring the cleaned refined indium in a mould to form, and wrapping the anode with a filter paper bag and a polyester cloth bag;
6. The electrolytic tank is cleaned after the inside of the electrolytic tank is cleaned, and then the anode and the cathode are arranged in the electrolytic tank (3) according to the anode-cathode distance of 20mm-25mm, preferably 22mm;
7. The refined indium which is well washed by the dissolution of the high-grade pure sulfuric acid is added with the high-grade pure NaCl and the high-grade pure gelatin, and the electrolyte with the concentration of In 3+ of 100g/L-120g/L, naCl of 70g/L-80g/L, pH of 2-2.5 is prepared In a post-electrolysis liquid storage tank (16). At this time, the electrolyte contains more metal impurities with the equal electrode potential of Pb, sn, sb, cu, ni, ag higher than that of indium, the electrifying current density is 50A/m 2-60A/m2, and the indium is deposited on the cathode, preferably fixed at 56A/m 2. The pH value of the electrolyte is lower, so that part of indissolvable metals and oxides in the anode plate are promoted to enter the electrolyte, further, a weaker electric field formed by low-density current is adopted, most of metal impurities with electrode potential higher than that of indium are sunk into anode mud near the anode, and the other small part of impurities are deposited on the cathode along with the indium due to the weaker electric field, so that the electrolyte is purified, the impurities deposited on the cathode are deposited on the cathode together with the indium, and are easier to remove in the next step of vacuum distillation. In the process, because refined indium contains relatively more impurities, floccules are easy to form between the cathode and the anode plates, and the floccules can adsorb impurities in the electrolyte and adhere to the cathode and the anode plates, so that the smooth operation of electrolysis is affected. Therefore, once the abnormal conditions such as the rise of the cell voltage or (and) the non-densification of indium deposited at the cathode are found, on the basis of tight analysis, a second circulating pump before opening a liquid outlet pipe orifice of the electrolytic cell can be used for promoting the discharge of the electrolyte faster than the self-flowing, and the operations such as acid regulation and liquid preparation, current density regulation and the like can be carried out in the liquid storage tank after the electrolysis.
8. And cleaning refined indium obtained after the primary electrolytic refining is finished.
9. The process of cleaning the refined indium is carried out by putting the refined indium into a vacuum furnace, coating silicon carbon film on the inner wall of the crucible in an ultra-clean working area by using a high-purity quartz crucible, cleaning, and coating the silicon carbon film by using a three-channel high-temperature resistant nozzle to spray argon for protection, burning oxygen and silane, and directly spraying silicon carbon material generated by burning on the inner wall of the crucible, and heating by using an electromagnetic induction mode.
10. Filling materials, sealing a vacuum furnace, then starting to introduce 6N high-purity hydrogen and vacuumizing, starting cooling circulating water when the vacuum degree meets the process requirement, closing a heating power switch, adjusting power control equipment to gradually increase the furnace temperature to the distillation temperature (850-950 ℃), keeping the pressure in the vacuum furnace at 1-5Pa, adjusting the constant temperature of current for 60-150 minutes, and preferably adjusting the constant temperature of current to fix for 100 minutes. The 6N high-purity hydrogen is introduced to keep the vacuum furnace in a reducing atmosphere, so that the indium is prevented from being oxidized by oxygen in the air under the high-temperature condition, the oxidized indium can be reduced, and simultaneously, volatile substances such As AsH 3 and the like which are easy to react with H 2 and the like in the indium can be generated, so that the effect of further purifying the indium is achieved. The operation belongs to common low temperature Duan Zhengliu for purifying indium by vacuum distillation, only the section of distillation is selected, the aim of the invention is to reduce the pollution caused by the evaporation and condensation process of indium by using the distillation of a high temperature section (1050 ℃ to 1075 ℃) while achieving the impurity removal effect, in particular to reduce the difficulty in indium extraction caused by the adhesion of indium in a vacuum furnace hearth and a condensation chamber, and the further achieved effect is to shorten the stroke and the distillation time of indium, shorten or avoid the contact of indium with other substances, and also to realize the industrialized flow operation more easily.
11. And after the constant temperature time is reached, modulating the current and the voltage to the zero point, switching off the power switch, cooling, and simultaneously enabling the vacuum pump to continue to work. Stopping supplying cooling water and vacuumizing when the temperature is reduced to below 100 ℃, and opening a vacuum furnace to take out refined indium and low boiling point substances;
12. Cutting the obtained refined indium into particles with the diameter of about 1cm, and finishing cleaning;
13. heating and pouring the cleaned refined indium in a cleaned mould to form, and wrapping the anode with a filter paper bag and a polyester cloth bag;
14. Preparing electrolyte with the concentration of In 3+ being 80g/L-100g/L, naCl being 60g/L-70g/L, pH being 1.5-2.5 by using high-grade pure sulfuric acid, washed refined indium, high-grade pure NaCl and high-grade pure gelatin In a post-electrolysis liquid storage tank, wherein the electrolyte contains more metal impurities with the equal electrode potential of Al, zn, ga, fe being lower than that of indium, and the current density is 80-100A/m 2 for depositing indium on a cathode, preferably fixed to be 100A/m 2. The process uses a stronger electric field formed by higher-density current, metal impurities with positive electrode potential compared with indium sink into anode mud near the anode, one part of the metal impurities with negative electrode potential compared with indium enter electrolyte, the other part of the metal impurities are deposited on the cathode together with indium, and the impurities deposited on the cathode are easier to remove in the next step of monocrystal growth. The secondary electrolytic refining can also refer to the primary electrolytic refining to perform quick liquid exchange and perform acid adjustment and liquid preparation in a liquid storage tank after electrolysis, or adjust the current density according to actual conditions, so as to ensure the smooth performance of electrolytic deposition of indium.
15. Before the refined indium obtained by secondary electrolytic refining is washed and put into a single crystal furnace, the single crystal furnace finishes the silicon-coated carbon film and washing in an ultra-clean working area by using a high-purity quartz crucible;
16. Filling materials, sealing the single crystal furnace, then starting to introduce 6N high-purity hydrogen and vacuumizing, starting cooling circulating water when the vacuum degree meets the process requirement, closing a heating power switch, adjusting power control equipment, and gradually raising the furnace temperature to the temperature of the indium single crystal pulling temperature to start pulling single crystals. The 6N high-purity hydrogen is introduced to keep the vacuum furnace in a reducing atmosphere, so that the indium is prevented from being oxidized by oxygen in the air in a molten state, the oxidized indium can be reduced, and simultaneously, the indium can be further purified by the aid of the indium. The operation belongs to a common operation procedure for purifying indium by using a single crystal growth technology, and in the process of using the operation as a purification unit, the operation steps are strict, the growth process is ensured to be in a protective and reducing atmosphere, the indium stroke is reduced as much as possible, the silicon-carbon plating barrier is used, and the introduction of impurities caused by contact with an object is further avoided.
17. And (3) finishing pulling the single crystal, detecting the crystal bar, cutting off the unqualified section, returning to a vacuum furnace return refining system for refining again, or selling as a 6-7N product, and obtaining the high-purity indium with the purity of 8N and above in the qualified section.
Claims (7)
1. The preparation method of the high-purity indium is characterized by comprising the following steps of:
(1) Firstly, electrolytic refining, namely shearing a 4N refined indium material ingot into particles, cleaning, pouring the particles into a die to form an anode plate, pouring a titanium plate into a cathode, arranging the anode and the cathode In an electrolytic tank according to a cathode-anode distance of 20mm-25mm, adding high-grade pure NaCl and high-grade pure gelatin, preparing electrolyte with the concentration of In 3+ of 100g/L-120g/L, naCl of 70g/L-80g/L, pH of 2-2.5 In a liquid storage tank after electrolysis, and depositing indium at the cathode with the current density of 50A/m 2-60A/m2 to obtain 5N refined indium;
(2) Vacuum distillation, namely cleaning 5N-grade refined indium obtained by primary electrolytic refining, putting the cleaned refined indium into a cleaned vacuum furnace, using a high-purity quartz crucible, introducing 6N high-purity hydrogen and vacuumizing, keeping the pressure in the vacuum furnace at 1-5Pa, distilling at 850-950 ℃, regulating the constant temperature of current for 60-150 minutes, cutting off a power supply after the constant temperature is reached, stopping supplying cooling water and vacuumizing, and opening the vacuum furnace to take out the obtained 6N-grade refined indium and low-boiling-point substances;
(3) Performing secondary electrolytic refining, namely uniformly shearing 6N-grade refined indium obtained by vacuum distillation into particles In the step (1), cleaning and pouring, preparing electrolyte with the concentration of In 3+ of 80g/L-100g/L, naCl of 60g/L-70g/L, pH of 1.5-2.5 In a liquid storage tank after electrolysis by using high-grade pure sulfuric acid, cleaned refined indium, high-grade pure NaCl and high-grade pure gelatin, and depositing indium at a cathode by adopting the current density of 80-100A/m 2 to obtain 7N-grade refined indium;
(4) The single crystal growth, namely cleaning 7N-grade refined indium obtained by secondary refining, putting the cleaned refined indium into a single crystal furnace, sealing the single crystal furnace by using a high-purity quartz crucible, introducing 6N high-purity hydrogen and vacuumizing the single crystal furnace, and carrying out single crystal growth to obtain 8N-grade refined indium;
the electrolytic tanks used in the electrolytic refining in the steps (1) and (3) are multi-unit serial multistage electrolytic refining devices;
The multi-unit serial multistage electrolytic refining device comprises a front electrolytic liquid storage tank, an electrolytic tank and a rear electrolytic liquid storage tank, wherein the front electrolytic liquid storage tank is communicated with the upper part of the electrolytic tank, the rear electrolytic liquid storage tank is communicated with the lower part of the electrolytic tank, a height difference is formed between the front electrolytic liquid storage tank and the lower part of the electrolytic tank, the liquid outlet pipe opening of the front electrolytic liquid storage tank and the liquid inlet of the electrolytic tank are arranged on the same plane, the U-shaped tank is used for communication, at least three liquid outlet pipes are arranged at the liquid outlet pipe opening of the bottom of the front electrolytic liquid storage tank, a first current stabilizer is arranged in the liquid outlet pipe, electrolyte flows to the U-shaped tank through the liquid outlet pipes, then enters the electrolytic tank from the U-shaped tank, at least three liquid outlet pipes are arranged at the lower part of the electrolytic tank, the second current stabilizer is communicated with the rear electrolytic liquid storage tank through the pipelines, a first circulating pump is arranged between the two liquid storage tank pipelines, and the front electrolytic liquid storage tank, the first electrolytic tank, the rear electrolytic tank and the first circulating pump are communicated with the U-shaped tank through the pipelines to form a refining circulating system;
the movable cover plate is arranged on the electrolytic tank and is tightly attached to the U-shaped tank and the edge of the electrolytic tank, two rows of tooth grooves are symmetrically arranged on the edge of the movable cover plate, and the size of each tooth groove is not smaller than that of a pole plate hanging lug;
The movable cover plate is provided with a plurality of holes.
2. The method of claim 1, wherein a bottom plate is additionally arranged at the upper part of the outlet pipe opening of the electrolytic tank, the bottom plate is inclined in a slope shape by 0-15 degrees, an independent space is formed between the bottom plate and the bottom of the electrolytic tank, and holes are formed in the bottom plate and are arranged in a mode consistent with the movable cover plate.
3. The method of claim 2, wherein the floor aperture is inverted trapezoidal in shape.
4. The method of claim 1, wherein the pre-electrolysis reservoir bottom outlet and the electrolysis reservoir bottom outlet are the same in number and size.
5. The method according to claim 1, wherein the bottom outlet pipe of the electrolytic cell is provided with a second circulation pump at intervals.
6. The method of claim 1, wherein the feed tube disposed within the post-electrolysis reservoir extends to the bottom of the post-electrolysis reservoir.
7. The method of claim 1, wherein in the electrolytic refining process, refined indium material ingots are sheared into 1cm particles, refined indium is heated and poured into a mold for molding, a filter paper bag is used for wrapping an anode with a polyester cloth bag, the refined indium is placed in a high-purity quartz crucible for vacuum distillation and single crystal growth, the inner wall of the quartz crucible is treated by a silicon-coated carbon film, the silicon-coated carbon film is heated in an electromagnetic induction mode, a three-channel high-temperature resistant nozzle is adopted for blowing argon protection, oxygen and silane are combusted, and silicon carbon materials generated by combustion are directly sprayed on the inner wall of the crucible.
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