CN114380323A - Method for recovering indium from indium phosphide - Google Patents
Method for recovering indium from indium phosphide Download PDFInfo
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- CN114380323A CN114380323A CN202210129275.XA CN202210129275A CN114380323A CN 114380323 A CN114380323 A CN 114380323A CN 202210129275 A CN202210129275 A CN 202210129275A CN 114380323 A CN114380323 A CN 114380323A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention discloses a method for recovering indium from indium phosphide, which comprises the steps of uniformly mixing indium phosphide powder and iron powder, heating for high-temperature solid-phase reaction, cooling to chlorination reaction temperature after the high-temperature solid-phase reaction is finished, introducing hydrogen chloride gas for chlorination to volatilize indium chloride gas, and condensing and recovering the obtained indium chloride gas. The method can effectively treat the harmful gas containing phosphorus generated in the decomposition and chlorination processes of the indium phosphide, can obviously improve the recovery rate of the indium and the purity of the indium chloride, has high recovery and utilization rate of the whole process resources, and is environment-friendly.
Description
Technical Field
The invention relates to a method for recovering indium phosphide, in particular to a method for recovering indium in indium phosphide, and belongs to the field of metal indium recovery.
Background
Indium is called as vitamin of alloy, the indium alloy can be used as a brazing solder, the indium is a new important additive element of lead-free solder, and the development trend of the lead-free solder in the world is favorable for the application of the indium brazing solder. The indium alloy can be made into special alloy by utilizing the characteristic of low melting point of the indium alloy and is used for a circuit breaking protection device of a fire-fighting system and a thermal control device of an automatic control system, the service life of the bearing alloy made by adding a small amount of indium is 4-5 times that of the common bearing alloy, and the indium alloy can also be used for dental medical treatment, anticorrosive decoration parts of steel and nonferrous metal, plastic metallization and the like.
Because indium has stronger corrosion resistance and light reflection capability, the indium can be made into a reflector on a warship or a passenger ship. Indium is sensitive to neutron radiation and can be used as a monitoring dose material in the atomic energy industry, and the indium currently used in the atomic energy industry is approximately similar to the indium used in the electronic industry.
The indium can be used as an additive in a storage battery and as a corrosion inhibitor in a mercury-free alkaline battery, so that the battery can become a green and environment-friendly product. The use of indium in protection against fogging is increasing and indium coatings were initially used in the automobile industry, with the possibility of spreading in the industrial and high-end civil construction industry. The japanese sony corporation invented a new cathode with indium instead of scandium, so that the cost per gun is reduced to about one tenth of that of the scandium-doped gun. Therefore, the application development prospect of indium is remarkable in the aspects of high power output and long service life of the television.
Indium phosphide is produced by a heating reaction of metallic indium and red phosphorus in a quartz tube, and an indium phosphide semiconductor material has a wide bandgap structure and electrons pass through an InP material at a high speed, which means that a device made of such a material can amplify a signal of a higher frequency or a shorter wavelength. Therefore, the satellite signal receiver and the satellite signal amplifier manufactured by the indium phosphide chip can work at extremely high frequency above 100GHz, have very wide bandwidth, are less influenced by the outside and have very high stability. Therefore, indium phosphide is a more advanced semiconductor material than gallium arsenide, and is likely to push the satellite communication industry to a higher frequency band. However, as the use of indium phosphide is more and more widespread, the indium phosphide waste materials are more and more abundant, and the large amount of electronic waste containing indium phosphide not only has serious influence on the environment, but also wastes precious indium resources, so that the recovery of indium phosphide becomes a preferable scheme for treating the waste materials.
In the prior art, certain phosphorus pollution can be caused when indium element in indium phosphide is recovered, and phosphine is generated particularly when a chlorination method is adopted for recovery. Phosphine is a highly toxic and flammable gas, can rapidly cause death, and can cause multiple pollution of air, soil and water when discharged into the environment. Therefore, how to treat phosphorus without harm in the process of recovering indium from indium phosphide has attracted more and more attention and research.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for recovering indium phosphide, which can effectively avoid phosphorus-containing harmful gas generated in the processes of decomposition and chlorination of indium phosphide, can realize high-efficiency recovery of indium in indium phosphide and high-purity indium chloride, and has high recovery rate of overall process resources and environmental friendliness.
In order to achieve the technical purpose, the invention provides a method for recovering indium phosphide, which comprises the steps of uniformly mixing indium phosphide powder with iron powder, heating for high-temperature solid-phase reaction, cooling to chlorination reaction temperature after the high-temperature solid-phase reaction is finished, introducing hydrogen chloride gas for chlorination to volatilize indium chloride gas, and condensing and recovering the obtained indium chloride gas. The main reaction principle of the indium phosphide recovery process comprises the following steps: inp(s) +3Fe(s) ═ In (s, l) + Fe3P(s)，2In(s,l)+6HCl(g)＝InCl3(g)+3H2(g) In that respect The invention extracts indium element by decomposing indium phosphide, solidifies single-substance gaseous white phosphorus into phosphide, avoids toxic action caused by white phosphorus, and prevents PH from being generated in the subsequent chlorination purification stage3。
As a preferable scheme, the mol ratio of the iron powder to the indium phosphide powder is 3-5: 1; further, the mol ratio of the iron powder to the indium phosphide powder is 3.6-4: 1. the preferred iron powder is a micron-sized iron powder.
In a more preferred embodiment, the particle sizes of the iron powder and the indium phosphide powder are both smaller than 1000 mesh (smaller than 13 μm).
The key of the technical scheme of the invention is that the iron powder and the indium phosphide react at high temperature, the iron powder can play a role of reduction at high temperature, so that indium in the indium phosphide is more thoroughly reduced and decomposed, and can also react with white phosphorus generated by the decomposition of the indium phosphide to generate iron phosphide, a good solidification effect is achieved on phosphorus elements, and white phosphorus and PH are reduced from the source3Is generated. In addition, the iron powder may react with oxygen remaining in the reactor to provide low-oxygen reaction conditions, and thus, the present invention does not require the use of a vacuum reactor. Too little iron powder can not completely cure P, while too much iron powder can cause raw material waste and seriously increase the burden of subsequent treatment.
As a preferable scheme, the temperature of the high-temperature solid phase reaction is 650-800 ℃, and the time is 2-4 hours. Indium phosphide begins to decompose at 650 ℃, and when the temperature reaches 800 ℃, indium phosphide is decomposed in a large amount, in order to ensure that the reaction has sufficient retention time, the decomposition speed of indium phosphide cannot be too fast, and the pressure in a reactor can be increased rapidly due to too fast decomposition, thereby affecting the operation safety.
Preferably, the temperature of the chlorination reaction is 400-600 ℃.
Preferably, the molar ratio of the hydrogen chloride gas to the indium phosphide is 22-50: 1, further, the molar ratio of hydrogen chloride gas to indium phosphide is 38-44: 1. because the indium metal is soft in texture, light oxidation is easy to occur in the air, the indium metal is inconvenient to store and transport, and the indium metal is further purified, so the indium metal is converted into indium chloride by adopting a chlorination fixation method, and the indium metal is convenient to store and transport.
As a preferred embodiment, the temperature of the condensation is not higher than 150 ℃.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) according to the technical scheme provided by the invention, when the indium element in the indium phosphide is recovered, highly toxic and inflammable white phosphorus smoke and phosphine gas are not generated, the influence on the environment is reduced, the cost is low, and the method is suitable for large-scale production.
(2) The technical scheme provided by the invention has simple and convenient flow and easy operation, does not need to adopt a vacuum reaction kettle and temperature change program setting, and the obtained by-product ferric phosphate can be used as a raw material of the lithium iron phosphate battery, thereby further reducing the production cost and improving the economic benefit.
(3) The technical scheme provided by the invention can effectively improve the recovery rate and purity of indium in the indium phosphide waste material, the recovery rate of indium can reach more than 98%, and the purity of indium chloride can reach 99.9%.
Detailed Description
The present invention and the embodiments thereof are described in further detail with reference to the following examples, but the invention is not limited thereto, and all modifications and equivalents of the technical solutions of the present invention can be made without departing from the spirit and scope of the technical solutions of the present invention.
The invention is characterized by the following steps:
A. the indium phosphide with the granularity of less than 1000 meshes (13 mu m) and the iron powder with the granularity of less than 1000 meshes (13 mu m) are uniformly mixed, and the molar ratio of the iron powder to the indium phosphide is not less than 3.
B. And B, placing the mixed powder obtained in the step A into a quartz boat, then placing the quartz boat into an atmosphere furnace, heating to 650-800 ℃, and preserving heat for not less than 2 hours.
C. And C, cooling the mixed powder obtained in the step B to 400-600 ℃, and introducing hydrogen chloride into the atmosphere furnace, wherein the molar ratio of the hydrogen chloride gas to the indium phosphide is not less than 22.
D. And D, condensing and recovering the gaseous indium chloride obtained in the step C.
The granularity of the indium phosphide and the iron powder is not less than 1000 meshes (13 mu m), and the molar ratio of the iron powder to the indium phosphide is not less than 3.
The heating temperature of the mixed powder of the indium phosphide and the iron powder is 650-800 ℃.
The temperature range of introducing the mixed powder of the indium phosphide and the iron powder into hydrogen chloride is 400-600 ℃, and the molar ratio of the introduced hydrogen chloride gas to the indium phosphide is not lower than 22. Several examples are given below for further illustration: example 1
Indium phosphide having a particle size of 1000 mesh (13 μm) was made uniform by round with iron powder having a particle size of 1000 mesh (13 μm) in the same manner, and the molar ratio of iron powder to indium phosphide was 3. The obtained mixed powder is placed in a quartz boat and then placed in an atmosphere furnace to be heated to 650 ℃, and the temperature is kept for 2 hours. And cooling the mixed powder to 400 ℃, introducing gaseous hydrogen chloride into the atmosphere furnace, and condensing and recovering the gaseous indium chloride, wherein the molar ratio of the hydrogen chloride gas to the indium phosphide is 22.
Example 2
Indium phosphide having a particle size of 2000 mesh (6.5 μm) was made uniform by round with iron powder having a particle size of 2000 mesh (6.5 μm) in the same manner, and the molar ratio of iron powder to indium phosphide was 3.5. The obtained mixed powder is placed in a quartz boat and then is placed in an atmosphere furnace to be heated to 700 ℃, and the temperature is kept for 2 hours. And cooling the mixed powder to 500 ℃, introducing gaseous hydrogen chloride into the atmosphere furnace, and condensing and recovering the gaseous indium chloride, wherein the molar ratio of the hydrogen chloride gas to the indium phosphide is 33.
Example 3
Indium phosphide having a particle size of 2000 mesh (6.5 μm) was made uniform by round with iron powder having a particle size of 2000 mesh (6.5 μm) in the same manner, and the molar ratio of iron powder to indium phosphide was 4. The obtained mixed powder is placed in a quartz boat, then is placed in an atmosphere furnace to be heated to 800 ℃, and is kept for 2 hours. And cooling the mixed powder to 600 ℃, introducing gaseous hydrogen chloride into the atmosphere furnace, and condensing and recovering the gaseous indium chloride, wherein the molar ratio of the hydrogen chloride gas to the indium phosphide is 44.
Example 4
Indium phosphide having a particle size of 2000 mesh (6.5 μm) was made uniform by round with iron powder having a particle size of 2000 mesh (6.5 μm) in the same manner, and the molar ratio of iron powder to indium phosphide was 3.8. The obtained mixed powder is placed in a quartz boat and then is placed in an atmosphere furnace to be heated to 700 ℃, and the temperature is kept for 2 hours. And cooling the mixed powder to 600 ℃, introducing gaseous hydrogen chloride into the atmosphere furnace, and condensing and recovering the gaseous indium chloride, wherein the molar ratio of the hydrogen chloride gas to the indium phosphide is 40.
Example 5
Indium phosphide having a particle size of 2000 mesh (6.5 μm) was made uniform by round with iron powder having a particle size of 2000 mesh (6.5 μm) in the same manner, and the molar ratio of iron powder to indium phosphide was 3.6. The obtained mixed powder is placed in a quartz boat, then is placed in an atmosphere furnace to be heated to 800 ℃, and is kept for 2 hours. And cooling the mixed powder to 600 ℃, introducing gaseous hydrogen chloride into the atmosphere furnace, and condensing and recovering the gaseous indium chloride, wherein the molar ratio of the hydrogen chloride gas to the indium phosphide is 38.
Indium recovery and gaseous phosphide comparison in each of the above examples: (examples 3 to 5 the differences between the effects of examples 1 and 2 are large, and the specification needs to add several preferable conditions)
| In(％) | P (%) gaseous volatile PH3 | |
| Example 1 | 80 | 2 |
| Example 2 | 87 | 1.1 |
| Example 3 | 98 | 0.6 |
| Example 4 | 98.6 | 0.8 |
| Example 5 | 98.8 | 0.9 |
Claims (7)
1. A method for recovering indium in indium phosphide is characterized by comprising the following steps: and uniformly mixing the indium phosphide powder and iron powder, heating to perform high-temperature solid-phase reaction, cooling to chlorination reaction temperature after the high-temperature solid-phase reaction is finished, introducing hydrogen chloride gas to perform chlorination to volatilize indium chloride gas, and condensing and recovering the obtained indium chloride gas.
2. The method according to claim 1, wherein the indium recovery method comprises: the mol ratio of the iron powder to the indium phosphide powder is 3-5: 1.
3. the method according to claim 1 or 2, wherein the indium recovery unit further comprises: the particle sizes of the iron powder and the indium phosphide powder are both smaller than 1000 meshes.
4. The method according to claim 1, wherein the indium recovery method comprises: the temperature of the high-temperature solid-phase reaction is 650-800 ℃, and the time is 2-4 hours.
5. The method according to claim 1, wherein the indium recovery method comprises: the temperature of the chlorination reaction is 400-600 ℃.
6. The method according to claim 1, wherein the indium recovery method comprises: the molar ratio of the hydrogen chloride gas to the indium phosphide is 22-50: 1.
7. the method according to claim 1, wherein the indium recovery method comprises: the temperature of the condensation is not higher than 150 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210129275.XA CN114380323A (en) | 2022-02-11 | 2022-02-11 | Method for recovering indium from indium phosphide |
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| CN202210129275.XA CN114380323A (en) | 2022-02-11 | 2022-02-11 | Method for recovering indium from indium phosphide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116177505A (en) * | 2023-03-03 | 2023-05-30 | 安徽工业大学 | Method for efficiently recycling indium and phosphorus in indium phosphide waste material by using molten salt system |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01179712A (en) * | 1988-01-08 | 1989-07-17 | Mitsubishi Metal Corp | Treatment of scrap indium-phosphorus compound semiconductor |
| US6051201A (en) * | 1998-06-25 | 2000-04-18 | James C. Barber And Associates, Inc. | Preparation of phosphatic feedstock from phosphorus-containing waste |
| CN101294073A (en) * | 2008-06-12 | 2008-10-29 | 上海交通大学 | Indium phosphide fluorescence quantum pot synthesizing method |
| JP2011026701A (en) * | 2009-06-23 | 2011-02-10 | Osaka Prefecture Univ | Method for collecting metal |
| US20130272944A1 (en) * | 2010-11-15 | 2013-10-17 | Sgl Carbon Se | Method for recycling organic waste material |
| CN106586988A (en) * | 2016-11-25 | 2017-04-26 | 广东先导稀材股份有限公司 | Method for comprehensive recovery of indium and phosphorus from indium phosphide waste material |
| CN113774491A (en) * | 2021-09-07 | 2021-12-10 | 广东先导微电子科技有限公司 | Method for preparing indium phosphide polycrystal from indium phosphide tailings |
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- 2022-02-11 CN CN202210129275.XA patent/CN114380323A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01179712A (en) * | 1988-01-08 | 1989-07-17 | Mitsubishi Metal Corp | Treatment of scrap indium-phosphorus compound semiconductor |
| US6051201A (en) * | 1998-06-25 | 2000-04-18 | James C. Barber And Associates, Inc. | Preparation of phosphatic feedstock from phosphorus-containing waste |
| CN101294073A (en) * | 2008-06-12 | 2008-10-29 | 上海交通大学 | Indium phosphide fluorescence quantum pot synthesizing method |
| JP2011026701A (en) * | 2009-06-23 | 2011-02-10 | Osaka Prefecture Univ | Method for collecting metal |
| US20130272944A1 (en) * | 2010-11-15 | 2013-10-17 | Sgl Carbon Se | Method for recycling organic waste material |
| CN106586988A (en) * | 2016-11-25 | 2017-04-26 | 广东先导稀材股份有限公司 | Method for comprehensive recovery of indium and phosphorus from indium phosphide waste material |
| CN113774491A (en) * | 2021-09-07 | 2021-12-10 | 广东先导微电子科技有限公司 | Method for preparing indium phosphide polycrystal from indium phosphide tailings |
Non-Patent Citations (3)
| Title |
|---|
| TERAKADO O等: "Pyrometallurgical Separation of Indium Phosphide through the Phosphorous Removal by Iron and the Chlorination Process Utilizing Ammonium Chloride", MATERIALS TRANSACTIONS, vol. 59, no. 6, pages 2 - 2 * |
| 曹笑;郭学益;李栋;田庆华;: "从二次资源中回收铟的研究现状", 金属材料与冶金工程, no. 02 * |
| 董志远, 赵有文, 曾一平, 段满龙, 李晋闽: "高温退火处理的磷化铟中的深能级缺陷", 中国科学E辑, no. 05 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116177505A (en) * | 2023-03-03 | 2023-05-30 | 安徽工业大学 | Method for efficiently recycling indium and phosphorus in indium phosphide waste material by using molten salt system |
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