CN116177505A - Method for efficiently recycling indium and phosphorus in indium phosphide waste material by using molten salt system - Google Patents
Method for efficiently recycling indium and phosphorus in indium phosphide waste material by using molten salt system Download PDFInfo
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- CN116177505A CN116177505A CN202310197897.0A CN202310197897A CN116177505A CN 116177505 A CN116177505 A CN 116177505A CN 202310197897 A CN202310197897 A CN 202310197897A CN 116177505 A CN116177505 A CN 116177505A
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 112
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 112
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002699 waste material Substances 0.000 title claims abstract description 68
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 67
- 239000011574 phosphorus Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 57
- 150000003839 salts Chemical class 0.000 title claims abstract description 52
- 238000004064 recycling Methods 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 22
- 230000005496 eutectics Effects 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005580 one pot reaction Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 230000001360 synchronised effect Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000012429 reaction media Substances 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 238000004876 x-ray fluorescence Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 1
- 229910013697 LiCl—NaCl Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005486 microgravity Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C01B25/02—Preparation of phosphorus
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of nonferrous metal metallurgy, and particularly relates to a method for efficiently recycling indium and phosphorus in indium phosphide waste by a molten salt system. The technical scheme of the invention has the characteristics of short flow, high efficiency, low equipment requirement, low cost and the like, and can realize the high-efficiency short-flow comprehensive recovery of the indium phosphide waste; the molten salt system does not participate in chemical reaction, only plays a role of providing a reaction medium, and the inorganic salt recovered after the reaction is finished can be recycled after simple grinding and drying treatment, so that the whole reaction process does not theoretically consume any chemical reagent, the production cost is low, and the economic benefit is good; the production process does not produce waste gas, waste water and waste residue, and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of nonferrous metal metallurgy, and particularly relates to a method for efficiently recycling indium and phosphorus in indium phosphide waste materials by a molten salt system.
Background
Indium has excellent physicochemical properties and is widely used in the fields of semiconductors, electrical components, photoelectricity, communication and the like. With the progress of technology and the development of society, the demand for indium in the field of high and new technology industry is rapidly increasing year by year. However, indium is a rare earth metal and the average abundance of crust is only 50-200ppb. Indium is not an independent deposit in nature and is mainly associated with zinc sulfide ores, so that the indium is often obtained as a byproduct of zinc smelting, but the content of indium in the zinc sulfide ores is only 1-100ppm. Therefore, the natural resources of indium are very limited, the increasing demands of industry for indium are difficult to meet, and recycling indium from secondary resources is an important supplement to limited indium primary resources.
Indium phosphide (InP) is an important III-V compound semiconductor material, has the excellent characteristics of wider forbidden band width, direct transition type energy band structure, strong radiation resistance, high electron mobility and the like, and is widely applied to high and new technical fields such as optical fiber communication, solar cells, integrated circuits, high-speed high-frequency devices and the like. However, indium phosphide has strong brittleness and low hardness, and the rejection rate in the process of producing an InP device is about 70%. On the other hand, with the rapid development of the semiconductor industry, indium phosphide semiconductor devices will also undergo numerous refresh iterations, producing a large amount of indium phosphide waste. Therefore, the indium phosphide waste is an important indium secondary resource, and the efficient comprehensive recovery of the indium phosphide waste is of great significance to the sustainable development of related industries.
At present, the research on recycling of indium phosphide waste is relatively limited. And (3) searching:
chinese patent publication No. CN106586988B discloses a method for comprehensively recovering indium and phosphorus from indium phosphide waste, in which indium phosphide waste powder is placed in a vacuum tube furnace, and indium phosphide is decomposed into indium and phosphorus vapor under high temperature and vacuum conditions, and the indium and phosphorus vapor are further separately recovered. Although the method can realize the short-process comprehensive recovery of the indium phosphide waste, the production process is realized under the conditions of high temperature and vacuum, so that the energy consumption is high, the vacuum smelting equipment with higher investment cost is needed, and the production cost is higher.
The chinese patent publication No. CN106319224B discloses a method for recovering indium from indium phosphide waste, which uses concentrated hydrochloric acid and sodium chlorate as leaching agents to fully dissolve the indium phosphide waste, and further adds zinc powder into the leaching solution to obtain sponge indium by replacement. Although the technology can effectively recover the metal indium from the indium phosphide waste, the chloride ion leaching system under the high acidity condition has serious corrosion to equipment, and the volatile hydrogen chloride gas pollutes the production environment; in addition, the thermodynamic driving force of replacing indium by zinc powder is limited, the purity of the sponge indium product can be reduced by adding excessive zinc powder, the zinc powder belongs to a tubular reagent which is easy to explosion, and the production safety risk is high.
The Chinese patent publication No. CN114380323A discloses a method for recovering indium from indium phosphide, which comprises mixing indium phosphide powder with iron powder uniformly, performing solid-phase reaction at high temperature, further introducing hydrogen chloride gas to selectively chlorinate indium to generate volatile indium chloride, and condensing in gas phase to recover InCl 3 . The indium chloride recovered by the method has higher purity, but the whole recovery process flow is long, the operation is complex, the requirement on equipment is high, and the indium is recovered in the form of indium chloride and can be obtained into a metal indium product through further treatment.
In summary, the existing indium phosphide waste recovery process still has a large optimization and promotion space, and further development and operation of an indium phosphide waste comprehensive recovery process technology which is simple in operation, short in flow, high in efficiency, low in cost and environment-friendly are necessary, so that sustainable development of related industries is supported.
Disclosure of Invention
The invention aims to solve the problems of long process flow, high equipment requirement, low efficiency, high production cost and the like of the conventional comprehensive recovery process of indium phosphide waste, and provides a method for efficiently recovering indium and phosphorus in the indium phosphide waste by using a molten salt system. The process technology has the characteristics of short flow, high efficiency, low equipment requirement, low cost and the like, and can realize the high-efficiency short-flow comprehensive recovery of the indium phosphide waste.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
a method for efficiently recovering indium and phosphorus in indium phosphide waste by a molten salt system is characterized in that under the normal pressure condition, the indium phosphide waste is thermally decomposed in the molten salt system, and the synchronous recovery of metal indium and elemental phosphorus is realized through one-step reaction.
Further, the specific operation comprises the following steps:
1) Mixing indium phosphide waste powder and an inorganic salt system uniformly in proportion;
2) Placing the mixture in a tube furnace, heating to a preset temperature and reacting for a period of time at constant temperature, wherein the whole process is carried out under the protection of flowing inert atmosphere, the generated liquid metal indium exists in molten salt, and elemental phosphorus enters a condensation area along with protective gas, so that the elemental phosphorus is recovered;
3) Cooling along with the furnace after the reaction is finished, separating the solidified inorganic salt from the metal indium, and washing and drying the metal indium to obtain a metal indium product; the separated inorganic salt can be recycled.
Further, in the step 1), the indium phosphide waste material is ball-milled in advance until the particle size is less than or equal to 300 mu m.
Further, in step 1), the inorganic salt system is MCl x -NCl y A binary eutectic salt, wherein M and N are any two of Li, na, K, ca, and x and y have a value of 1 or 2.
Further, in the step 1), the mass ratio of the inorganic salt system to the indium phosphide waste material is controlled to be 5-50:1.
Further, in the step 2), the predetermined temperature is MCl x -NCl y The temperature rising rate is 5-30 ℃/min at 50-100 ℃ above the eutectic point of the binary eutectic salt; after the temperature is raised to the preset temperature, the constant-temperature reaction time is 1-10h.
Further, in the step 2), the inert shielding gas is one of argon, nitrogen and helium, and the gas flow rate is 1-5L/min.
Further, in the step 2), the temperature of the recovered elemental phosphorus in the condensation zone is controlled between 50 and 90 ℃.
Further, in the step 3), the recovered metal indium is washed 4-8 times by deionized water.
Further, in the step 3), the washed metal indium is dried for 24-72 hours at the temperature of 60-100 ℃ to obtain a metal indium product.
The beneficial effects of the invention are as follows:
1. according to the method for efficiently recycling indium and phosphorus in the indium phosphide waste material in the molten salt system, disclosed by the invention, the indium phosphide waste material is subjected to thermal decomposition in the molten salt system, the synchronous recycling of metal indium and elemental phosphorus can be realized through one-step reaction, the production flow is short, the efficiency is high, and the efficient short-flow comprehensive recycling of the indium phosphide waste material can be realized.
2. According to the method for efficiently recovering indium and phosphorus in the indium phosphide waste material by using the molten salt system, disclosed by the invention, the vacuum-like anaerobic environment can be provided for the reaction process by using the molten salt medium, so that the process of recovering metal indium and elemental phosphorus by thermally decomposing the indium phosphide waste material can be realized under normal pressure, the expected effect can be achieved by adopting a common tubular furnace commonly used in the metallurgical industry, the vacuum metallurgical equipment required in the traditional method is not required, the equipment requirement is low, and the energy consumption and the equipment investment cost required by the reaction can be greatly reduced; in addition, the molten salt medium can provide a micro-gravity field environment for the reaction process, so that indium phosphide waste powder is fully and uniformly dispersed in a molten salt system, the reaction rate and the conversion rate are improved, and the recovery rate of metal indium and elemental phosphorus is high.
3. According to the method for efficiently recycling indium and phosphorus in the indium phosphide waste material by using the molten salt system, the molten salt system does not participate in chemical reaction, but only plays a role of providing a reaction medium, and the inorganic salt recycled after the reaction is finished can be recycled after simple grinding and drying treatment, so that the whole reaction process does not theoretically consume any chemical reagent, the production cost is low, and the economic benefit is good; the production process does not produce waste gas, waste water and waste residue, and is environment-friendly.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Related embodiments of the invention are as follows:
the invention provides a method for efficiently recycling indium and phosphorus in indium phosphide waste in a molten salt system, which is characterized in that under the normal pressure condition, the indium phosphide waste is thermally decomposed in the molten salt system, and the synchronous recycling of metal indium and elemental phosphorus can be realized through one-step reaction. The technical scheme of the invention has the characteristics of short flow, high efficiency, low equipment requirement, low cost and the like, and can realize the high-efficiency short-flow comprehensive recovery of the indium phosphide waste. The production process specifically comprises the following steps:
1) Mixing indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance with an inorganic salt system in proportion uniformly, wherein the inorganic salt system comprises MCl x -NCl y (M, n= Li, na, K, ca; x, y=1 or 2) binary eutectic salts, controlling the mass ratio of inorganic salt system to indium phosphide waste material between 5:1 and 50:1.
2) Placing the mixture into a tube furnace, and heating to MCl at a rate of 5-30deg.C/min x -NCl y The temperature of the binary mixed system is 50-100 ℃ above the eutectic point, the reaction is carried out for 1-10 hours at constant temperature, the whole process is carried out under the protection condition of flowing inert atmosphere, inert protective gas is one of argon, nitrogen and helium, the gas flow rate is 1-5L/min, the generated liquid metal indium exists in molten salt, and the elemental phosphorus enters a condensing zone with the temperature of 50-90 ℃ along with the protective gas, so that the elemental phosphorus is recovered.
3) Cooling along with the furnace after the reaction is finished, separating the solidified inorganic salt from the metal indium, washing the metal indium by deionized water for 4-8 times, and drying at 60-100 ℃ for 24-72h to obtain a metal indium product.
The invention is further described below in connection with specific embodiments.
Example 1
The embodiment provides a method for efficiently recycling indium and phosphorus in indium phosphide waste by a molten salt system, which specifically comprises the following steps:
1) And uniformly mixing indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance with LiCl-NaCl binary eutectic salt, and controlling the mass ratio of an inorganic salt system to the indium phosphide waste to be 5:1.
2) The mixture is placed in a tube furnace, the temperature is raised to 620 ℃ at the speed of 30 ℃/min, the reaction is carried out for 1h at a constant temperature, the whole process is carried out under the protection of flowing argon atmosphere, the gas flow rate is 1L/min, the generated liquid metal indium exists in molten salt, and the elemental phosphorus enters a condensing zone with the temperature of 50 ℃ along with the protection gas, so that the elemental phosphorus is recovered.
3) And cooling the reaction product in a furnace after the reaction is finished, separating the solidified inorganic salt from the metal indium, washing the metal indium with deionized water for 4 times, and drying the metal indium at 60 ℃ for 72 hours to obtain a metal indium product.
By adopting the method of the embodiment, the recovery rate and purity of the metal indium and the elemental phosphorus are analyzed by combining aqua regia dissolution with an inductively coupled plasma mass spectrometer (ICP-MS) and an X-ray fluorescence spectrometer (XRF), and the result is that the recovery rate of the metal indium and the elemental phosphorus are respectively 98.5 percent and 97.8 percent, and the purity of the metal indium and the elemental phosphorus are respectively 99.95 percent and 99.23 percent.
Example 2
The embodiment provides a method for efficiently recycling indium and phosphorus in indium phosphide waste by a molten salt system, which specifically comprises the following steps:
1) And uniformly mixing indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance with LiCl-KCl binary eutectic salt, and controlling the mass ratio of an inorganic salt system to the indium phosphide waste to be 50:1.
2) The mixture is placed in a tube furnace, the temperature is raised to 450 ℃ at the speed of 5 ℃/min, the reaction is carried out for 10 hours at a constant temperature, the whole process is carried out under the protection of flowing nitrogen atmosphere, the gas flow rate is 5L/min, the generated liquid metal indium exists in molten salt, and the elemental phosphorus enters a condensing zone with the temperature of 90 ℃ along with the protection gas, so that the elemental phosphorus is recovered.
3) And cooling the reaction product in a furnace after the reaction is finished, separating the solidified inorganic salt from the metal indium, washing the metal indium by deionized water for 8 times, and drying the metal indium at 100 ℃ for 24 hours to obtain a metal indium product.
By adopting the method of the embodiment, the recovery rate and purity of the metal indium and the elemental phosphorus are analyzed by combining aqua regia dissolution with an inductively coupled plasma mass spectrometer (ICP-MS) and an X-ray fluorescence spectrometer (XRF), and the result is that the recovery rate of the metal indium and the elemental phosphorus are 97.6 percent and 97.2 percent respectively, and the purity of the metal indium and the elemental phosphorus are 99.93 percent and 99.18 percent respectively.
Example 3
The embodiment provides a method for efficiently recycling indium and phosphorus in indium phosphide waste by a molten salt system, which specifically comprises the following steps:
1) Mixing the indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance with LiCl-CaCl 2 The binary eutectic salt is uniformly mixed, and the mass ratio of the inorganic salt system to the indium phosphide waste material is controlled to be 15:1.
2) The mixture is placed in a tube furnace, the temperature is raised to 550 ℃ at the speed of 10 ℃/min, the reaction is carried out for 3 hours at a constant temperature, the whole process is carried out under the protection of flowing helium atmosphere, the gas flow rate is 2L/min, the generated liquid metal indium exists in molten salt, and the elemental phosphorus enters a condensing zone with the temperature of 60 ℃ along with the protection gas, so that the elemental phosphorus is recovered.
3) And cooling the reaction product in a furnace after the reaction is finished, separating the solidified inorganic salt from the metal indium, washing the metal indium with deionized water for 5 times, and drying the metal indium at 70 ℃ for 60 hours to obtain a metal indium product.
By adopting the method of the embodiment, the recovery rate and purity of the metal indium and the elemental phosphorus are analyzed by combining aqua regia dissolution with an inductively coupled plasma mass spectrometer (ICP-MS) and an X-ray fluorescence spectrometer (XRF), and the result is that the recovery rate of the metal indium and the elemental phosphorus are respectively 98.8 percent and 98.2 percent, and the purity of the metal indium and the elemental phosphorus are respectively 99.97 percent and 99.36 percent.
Example 4
The embodiment provides a method for efficiently recycling indium and phosphorus in indium phosphide waste by a molten salt system, which specifically comprises the following steps:
1) And uniformly mixing indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance with NaCl-KCl binary eutectic salt, and controlling the mass ratio of an inorganic salt system to the indium phosphide waste to be 30:1.
2) The mixture is placed in a tube furnace, the temperature is raised to 700 ℃ at a speed of 15 ℃/min, the reaction is carried out for 6 hours at a constant temperature, the whole process is carried out under the protection of flowing helium atmosphere, the gas flow rate is 3L/min, the generated liquid metal indium exists in molten salt, and the elemental phosphorus enters a condensing zone with the temperature of 70 ℃ along with the protection gas, so that the elemental phosphorus is recovered.
3) And cooling the reaction product in a furnace after the reaction is finished, separating the solidified inorganic salt from the metal indium, washing the metal indium by deionized water for 6 times, and drying the metal indium at 80 ℃ for 48 hours to obtain a metal indium product.
By adopting the method of the embodiment, the recovery rate and purity of the metal indium and the elemental phosphorus are analyzed by combining aqua regia dissolution with an inductively coupled plasma mass spectrometer (ICP-MS) and an X-ray fluorescence spectrometer (XRF), and the result is that the recovery rate of the metal indium and the elemental phosphorus are 97.6 percent and 96.8 percent respectively, and the purity of the metal indium and the elemental phosphorus are 99.94 percent and 99.46 percent respectively.
Example 5
The embodiment provides a method for efficiently recycling indium and phosphorus in indium phosphide waste by a molten salt system, which specifically comprises the following steps:
1) Mixing indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance with NaCl-CaCl 2 The binary eutectic salt is uniformly mixed, and the mass ratio of the inorganic salt system to the indium phosphide waste material is controlled to be 40:1.
2) The mixture is placed in a tube furnace, the temperature is raised to 550 ℃ at the speed of 20 ℃/min, the reaction is carried out for 8 hours at a constant temperature, the whole process is carried out under the protection of flowing argon atmosphere, the gas flow rate is 4L/min, the generated liquid metal indium exists in molten salt, and the elemental phosphorus enters a condensing zone with the temperature of 80 ℃ along with the protection gas, so that the elemental phosphorus is recovered.
3) And cooling the reaction product in a furnace after the reaction is finished, separating the solidified inorganic salt from the metal indium, washing the metal indium with deionized water for 7 times, and drying the metal indium at 90 ℃ for 36 hours to obtain a metal indium product.
By adopting the method of the embodiment, the recovery rate and the purity of the metal indium and the elemental phosphorus are analyzed by combining aqua regia dissolution with an inductively coupled plasma mass spectrometer (ICP-MS) and an X-ray fluorescence spectrometer (XRF), and the result is that the recovery rate of the metal indium and the elemental phosphorus are respectively 99.2 percent and 98.7 percent, and the purity of the metal indium and the elemental phosphorus are respectively 99.98 percent and 99.38 percent.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. A method for efficiently recycling indium and phosphorus in indium phosphide waste material by using a molten salt system is characterized in that the indium phosphide waste material is subjected to thermal decomposition in the molten salt system under the normal pressure condition, and the synchronous recycling of metal indium and elemental phosphorus is realized through one-step reaction.
2. The method for efficiently recovering indium and phosphorus in indium phosphide waste material by using a molten salt system as claimed in claim 1, wherein the specific operation comprises the following steps:
1) Mixing indium phosphide waste powder and an inorganic salt system uniformly in proportion;
2) Placing the mixture in a tube furnace, heating to a preset temperature and reacting for a period of time at constant temperature, wherein the whole process is carried out under the protection of flowing inert atmosphere, the generated liquid metal indium exists in molten salt, and elemental phosphorus enters a condensation area along with protective gas, so that the elemental phosphorus is recovered;
3) Cooling along with the furnace after the reaction is finished, separating the solidified inorganic salt from the metal indium, and washing and drying the metal indium to obtain a metal indium product; the separated inorganic salt can be recycled.
3. The method for efficiently recycling indium and phosphorus in indium phosphide waste material by using a molten salt system as claimed in claim 2, wherein the method comprises the following steps: in the step 1), the indium phosphide waste is ball-milled in advance until the particle size is less than or equal to 300 mu m.
4. The method for efficiently recycling indium and phosphorus in indium phosphide waste material by using a molten salt system as claimed in claim 2, wherein the method comprises the following steps: in the step 1), the inorganic salt system is MCl x -NCl y A binary eutectic salt, wherein M and N are any two of Li, na, K, ca, and x and y have a value of 1 or 2.
5. The method for efficiently recycling indium and phosphorus in indium phosphide waste material by using a molten salt system according to claim 4, wherein the method comprises the following steps: in the step 1), the mass ratio of the inorganic salt system to the indium phosphide waste material is controlled to be 5-50:1.
6. The method for efficiently recycling indium and phosphorus in indium phosphide waste material by using a molten salt system according to claim 4, wherein the method comprises the following steps: in step 2), the predetermined temperature is MCl x -NCl y The temperature rising rate is 5-30 ℃/min at 50-100 ℃ above the eutectic point of the binary eutectic salt; after the temperature is raised to the preset temperature, the constant-temperature reaction time is 1-10h.
7. The method for efficiently recycling indium and phosphorus in indium phosphide waste material by using a molten salt system as claimed in claim 2, wherein the method comprises the following steps: in the step 2), the inert shielding gas is one of argon, nitrogen and helium, and the gas flow rate is 1-5L/min.
8. The method for efficiently recycling indium and phosphorus in indium phosphide waste material by using a molten salt system as claimed in claim 2, wherein the method comprises the following steps: in the step 2), the temperature of the recovered elemental phosphorus in the condensing zone is controlled between 50 and 90 ℃.
9. The method for efficiently recycling indium and phosphorus in indium phosphide waste material by using a molten salt system as claimed in claim 2, wherein the method comprises the following steps: in the step 3), the recovered metal indium is washed for 4 to 8 times by adopting deionized water.
10. The method for efficiently recycling indium and phosphorus in indium phosphide waste material by using a molten salt system as claimed in claim 2, wherein the method comprises the following steps: in the step 3), the washed metal indium is dried for 24-72 hours at the temperature of 60-100 ℃ to obtain a metal indium product.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6024331A (en) * | 1983-07-20 | 1985-02-07 | Nippon Mining Co Ltd | Treatment of scrap of iii-v group compound semiconductor |
| WO2006080742A1 (en) * | 2004-10-26 | 2006-08-03 | 9Digit Company Limited | Method for recovering high purity indium |
| CN101186976A (en) * | 2006-09-28 | 2008-05-28 | 同和金属矿业有限公司 | Method for withdrawing indium from indium-containing material |
| JP2011032567A (en) * | 2009-08-06 | 2011-02-17 | Doshisha | Method of phosphorizing material surface by using molten salt electrochemical process |
| CN106795580A (en) * | 2016-01-27 | 2017-05-31 | 王娜 | A kind of method that fused salt chemistry method reclaims hard alloy scraps |
| CN108754544A (en) * | 2018-05-29 | 2018-11-06 | 昆明理工大学 | A method of using melten salt electriochemistry method thick indium is recycled from useless ITO powder |
| CN112408345A (en) * | 2020-11-24 | 2021-02-26 | 中国电子科技集团公司第十三研究所 | Method for purifying non-metallic material |
| CN114380323A (en) * | 2022-02-11 | 2022-04-22 | 株洲科能新材料股份有限公司 | Method for recovering indium from indium phosphide |
| CN115341245A (en) * | 2022-06-22 | 2022-11-15 | 安徽工业大学 | Method for synchronously extracting metal and tellurium from solid semiconductor telluride through molten salt electrolysis |
-
2023
- 2023-03-03 CN CN202310197897.0A patent/CN116177505B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6024331A (en) * | 1983-07-20 | 1985-02-07 | Nippon Mining Co Ltd | Treatment of scrap of iii-v group compound semiconductor |
| WO2006080742A1 (en) * | 2004-10-26 | 2006-08-03 | 9Digit Company Limited | Method for recovering high purity indium |
| CN101186976A (en) * | 2006-09-28 | 2008-05-28 | 同和金属矿业有限公司 | Method for withdrawing indium from indium-containing material |
| JP2011032567A (en) * | 2009-08-06 | 2011-02-17 | Doshisha | Method of phosphorizing material surface by using molten salt electrochemical process |
| CN106795580A (en) * | 2016-01-27 | 2017-05-31 | 王娜 | A kind of method that fused salt chemistry method reclaims hard alloy scraps |
| CN108754544A (en) * | 2018-05-29 | 2018-11-06 | 昆明理工大学 | A method of using melten salt electriochemistry method thick indium is recycled from useless ITO powder |
| CN112408345A (en) * | 2020-11-24 | 2021-02-26 | 中国电子科技集团公司第十三研究所 | Method for purifying non-metallic material |
| CN114380323A (en) * | 2022-02-11 | 2022-04-22 | 株洲科能新材料股份有限公司 | Method for recovering indium from indium phosphide |
| CN115341245A (en) * | 2022-06-22 | 2022-11-15 | 安徽工业大学 | Method for synchronously extracting metal and tellurium from solid semiconductor telluride through molten salt electrolysis |
Non-Patent Citations (2)
| Title |
|---|
| DONALDR.SADOWAY, 李运姣: "稀土金属的熔盐电解", 稀土, no. 05, 25 October 1992 (1992-10-25), pages 1 - 2 * |
| GUPTA, A等: "Diffusion-Limited Kinetics of Isovalent Cation Exchange in III-V Nanocrystals Dispersed in Molten Salt Reaction Media", 《NANO LETTERS》, vol. 22, no. 16, 24 August 2022 (2022-08-24), pages 6545 - 6552 * |
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