CN116281912A - Comprehensive recycling method for indium phosphide waste - Google Patents
Comprehensive recycling method for indium phosphide waste Download PDFInfo
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- CN116281912A CN116281912A CN202310197861.2A CN202310197861A CN116281912A CN 116281912 A CN116281912 A CN 116281912A CN 202310197861 A CN202310197861 A CN 202310197861A CN 116281912 A CN116281912 A CN 116281912A
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- indium
- indium phosphide
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- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002699 waste material Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000004064 recycling Methods 0.000 title description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 110
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 110
- 238000002386 leaching Methods 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 238000011084 recovery Methods 0.000 claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 15
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 15
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- 238000000605 extraction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims abstract description 4
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052782 aluminium Inorganic materials 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 238000010907 mechanical stirring Methods 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 11
- 238000006073 displacement reaction Methods 0.000 claims description 9
- 229910001449 indium ion Inorganic materials 0.000 claims description 9
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 8
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 8
- 239000011268 mixed slurry Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 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
- 238000011161 development Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004891 communication 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
- 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
- 229920000742 Cotton Polymers 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 210000004024 hepatic stellate cell Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 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
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/36—Aluminium phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of nonferrous metal metallurgy, and particularly relates to a comprehensive recovery method of indium phosphide waste, which is characterized in that the indium phosphide waste is treated by an atmospheric pressure oxidation acid leaching process, so that phosphorus generates stable weak acid phosphoric acid, and the efficient leaching of the indium phosphide waste is realized; treating the leaching solution by adopting a metal replacement process, and recovering the metal indium; further, the tail liquid of indium extraction is treated by ammonia water neutralization and evaporation crystallization processes, and aluminum phosphate and ammonium sulfate are respectively recovered, so that the comprehensive recovery of valuable elements in the system is realized. The technical scheme of the invention has the characteristics of simple operation, low equipment requirement, high efficiency, low energy consumption, low cost and the like, and can realize the efficient comprehensive recovery of the indium phosphide waste.
Description
Technical Field
The invention belongs to the technical field of nonferrous metal metallurgy, and particularly relates to a comprehensive recycling method of indium phosphide waste.
Background
Indium has excellent physicochemical properties such as good light transmittance, conductivity, fatigue resistance, ductility, corrosion resistance, and the like, and thus has been widely used in the fields of high and new technology industries such as solar cells, ITO thin films, semiconductors, fluorescent materials, and the like. Indium phosphide (InP) is a III-V compound semiconductor material and has the characteristics of larger forbidden bandwidth, high electron mobility and the like. With the rapid development of technologies such as 5G communication, navigation satellite and millimeter wave communication, the industry demand for indium phosphide is increasing.
However, indium is a dilute metal, and has no independent deposit, and is currently mainly obtained as a byproduct of the heavy metal smelting process such as zinc, lead and the like. Thus, recovery of indium from secondary sources would be of great importance to the sustainable development of the indium industry. The indium phosphide has the characteristics of low hardness and strong brittleness, so that the rejection rate is higher in the process of producing the InP device, and the proportion of production waste 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 material becomes an important secondary resource of indium, and the comprehensive recovery of the indium phosphide waste material is an important supplement to the limited primary resource of indium.
At present, the research on recycling of indium phosphide waste is relatively limited. And (3) searching:
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.
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. 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 the indium industry is supported.
Disclosure of Invention
The invention aims to solve the problems of long process flow, low efficiency, high equipment requirement, high production cost and the like of the conventional indium phosphide waste comprehensive recovery process, and provides a method for comprehensively recovering the indium phosphide waste. The process technology has the characteristics of simple operation, low equipment requirement, high efficiency, low energy consumption, low cost and the like, and can realize the efficient 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:
an indium phosphide waste comprehensive recovery method is characterized in that indium phosphide waste is treated through an atmospheric pressure oxidation acid leaching process, phosphorus is oxidized from-3 valence to +5 valence, stable weak acid phosphoric acid is generated, and efficient leaching of the indium phosphide waste is realized; treating the leaching solution by adopting a metal replacement process, and recovering the metal indium; further, the tail liquid of indium extraction is treated by ammonia water neutralization and evaporation crystallization processes, and aluminum phosphate and ammonium sulfate are respectively recovered, so that the comprehensive recovery of valuable elements in the system is realized.
Further, the specific operation comprises the following steps:
1) Adding indium phosphide waste powder into sulfuric acid solution containing hydrogen peroxide, heating the system to a preset temperature, oxidizing phosphorus from-3 price to +5 price under the condition of mechanical stirring to generate stable weak acid phosphoric acid, and forming indium sulfate which is easy to dissolve in water by indium so as to realize efficient leaching of the indium phosphide waste;
2) Filtering after the reaction is finished to realize solid-liquid separation to obtain leaching liquid;
3) Inserting an aluminum plate into the leaching solution to enable metal aluminum and indium ions to undergo a displacement reaction, and separating out metal indium;
4) Filtering the replaced liquid, recovering the sponge indium suspended in the solution, and recovering the sponge indium attached to the surface of the aluminum plate after the replacement reaction is finished; repeatedly washing and drying the recovered sponge indium by adopting deionized water to obtain metal indium;
5) Adding ammonia water into the tail liquid of indium extraction under the condition of mechanical stirring, and separating out aluminum phosphate;
6) Filtering the mixed slurry to realize solid-liquid separation and obtain filter residues and filtrate; repeatedly washing and drying filter residues by adopting deionized water to obtain aluminum phosphate powder; evaporating and crystallizing the filtrate to recover ammonium sulfate crystals.
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, H 2 O 2 And InP molar ratio is controlled to be 4-10:1, sulfuric acid concentration is controlled to be 0-1.5, pH value of leaching end point solution is controlled to be 0-700r/min, mechanical stirring speed is controlled to be 300-700r/min, and reaction temperature is controlled to beThe reaction time is 1-10h at 25-95 ℃.
Further, in the step 2), the solid-liquid separation temperature is consistent with the temperature of the oxidation acid leaching process in the step 1).
Further, in step 3), al and In are controlled 3+ The molar ratio is 2-10:1, the reaction temperature is 55-95 ℃, and the reaction time is 2-12h.
Further, in the step 4), the filtering temperature is consistent with the temperature of the replacement reaction process in the step 3), the reclaimed sponge indium is washed for 4-8 times by adopting deionized water, and the sponge indium is dried for 24-72 hours at the temperature of 60-100 ℃ to obtain the metal indium.
Further, in the step 5), the addition amount of ammonia water controls the pH value of the reaction end point solution to be between 4 and 6, the mechanical stirring speed is 300 to 700r/min, the reaction temperature is 25 to 95 ℃, and the reaction time is 1 to 5 hours.
Further, the solid-liquid separation temperature in the step 6) is consistent with the reaction temperature in the step 5), deionized water is adopted to wash filter residues for 4-8 times, and the filter residues are dried for 24-72 hours at the temperature of 60-100 ℃ to obtain aluminum phosphate powder; evaporating and crystallizing the filtrate to obtain ammonium sulfate crystals.
The beneficial effects of the invention are as follows:
1. according to the comprehensive recovery method of the indium phosphide waste, the mild sulfuric acid and the hydrogen peroxide are used as the leaching agent, so that the efficient leaching of the indium phosphide waste is realized, meanwhile, the corrosion to equipment is small, the sulfuric acid is not easy to volatilize, and the operation is easy; in the oxidation leaching process, phosphorus is oxidized from-3 valence to +5 valence with the highest valence to generate stable phosphoric acid, no toxic phosphine gas is generated in the leaching process, only a small amount of oxygen escapes, and the production process is environment-friendly.
2. According to the comprehensive recovery method of the indium phosphide waste material, most of sulfuric acid In a system is converted into weakly acidic phosphoric acid after the leaching process is finished, leaching liquid is further treated by adopting an aluminum plate replacement process, the aluminum plate is subjected to a replacement reaction with indium ions In the solution preferentially to generate metallic indium, and Al and In 3+ The thermodynamic driving force of the reaction is large, and the replacement reaction efficiency is high; in the replacement reaction process, a small amount of aluminum can react with phosphoric acid, so that a small amount of bubbles on the surface of the aluminum plate can escape, thereby being beneficial to the replacement of generated seaThe cotton indium is automatically separated from the surface of the aluminum plate, so that the fresh unreacted aluminum surface is directly contacted with the solution, the continuous reaction is facilitated, and the recovery rate of the indium is high; and the excessive aluminum plate can not pollute the replaced sponge indium, and the purity of the metal indium product is high.
3. According to the comprehensive recovery method of the indium phosphide waste material, ammonia water is added into the tail liquid for indium extraction to neutralize and recover the aluminum phosphate, so that the method is an adsorption material with excellent properties, and has wide application in the field of environmental protection; finally evaporating and crystallizing to recover ammonium sulfate crystals, which can be used as nitrogenous fertilizer in the agricultural field; the whole production process can realize the efficient and comprehensive recovery of valuable elements in the system, and has low production cost and good economic benefit.
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.
The invention provides a comprehensive recovery method of indium phosphide waste, which is characterized in that the indium phosphide waste is treated by an atmospheric pressure oxidation acid leaching process, so that phosphorus generates stable weak acid phosphoric acid, and the efficient leaching of the indium phosphide waste is realized; treating the leaching solution by adopting a metal replacement process, and recovering the metal indium; further, the tail liquid of indium extraction is treated by ammonia water neutralization and evaporation crystallization processes, and aluminum phosphate and ammonium sulfate are respectively recovered, so that the comprehensive recovery of valuable elements in the system is realized. The technical scheme of the invention has the characteristics of simple operation, low equipment requirement, high efficiency, low energy consumption, low cost and the like, and can realize the efficient comprehensive recovery of the indium phosphide waste.
The production process specifically comprises the following steps:
1) Adding indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance into sulfuric acid solution containing hydrogen peroxide, and adding the hydrogen peroxide into the solutionControl H 2 O 2 The molar ratio of the InP to the sulfuric acid is between 4:1 and 10:1, and the sulfuric acid concentration controls the pH value of the leaching end point solution to be between 0 and 1.5; reacting for 1-10h under the mechanical stirring condition of 25-95 ℃ and the rotating speed of 300-700r/min, oxidizing phosphorus from-3 valence to +5 valence to generate stable weak acid phosphoric acid, and forming indium sulfate which is easy to dissolve in water by indium, thereby realizing the efficient leaching of the indium phosphide waste.
2) Filtering at 25-95deg.C (same as the temperature of the oxidation acid leaching process) after the reaction, and separating solid from liquid to obtain the leaching solution.
3) Inserting an aluminum plate into the leaching solution at 55-95deg.C for reacting for 2-12h, and controlling the dosage of Al/In 3+ The molar ratio is between 2:1 and 10:1, so that the metallic aluminum and the indium ions undergo a displacement reaction to separate out metallic indium.
4) Filtering the replaced liquid at 55-95 ℃ which is consistent with the temperature of the replacement reaction process, recovering the suspended sponge indium in the solution, and recovering the sponge indium attached to the surface of the aluminum plate after the replacement reaction is finished; and washing the recovered sponge indium with deionized water for 4-8 times, and further drying at 60-100 ℃ for 24-72 hours to obtain the metal indium.
5) Adding ammonia water into the tail liquid of indium extraction under the mechanical stirring condition of the temperature of 25-95 ℃ and the rotating speed of 300-700r/min for reaction for 1-5h, controlling the pH value of the reaction end point solution to be 4-6 by the addition of the ammonia water, and separating out aluminum phosphate.
6) Filtering the mixed slurry at 25-95 ℃ which is consistent with the reaction process temperature of the neutralized precipitated aluminum phosphate, and realizing solid-liquid separation to obtain filter residues and filtrate; washing the filter residue with deionized water for 4-8 times, and further drying at 60-100deg.C for 24-72 hr to obtain aluminum phosphate powder; evaporating and crystallizing the filtrate to obtain ammonium sulfate crystals.
The invention is further described below in connection with specific embodiments.
Example 1
The method for comprehensively recycling the indium phosphide waste material in the embodiment specifically comprises the following steps:
1) Adding indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance into sulfuric acid solution containing hydrogen peroxideHydrogen peroxide adding amount control H 2 O 2 The molar ratio of the InP to the sulfuric acid is 4:1, and the pH value of the leaching end point solution is controlled to be 0; reacting for 10 hours at 25 ℃ under the mechanical stirring condition with the rotating speed of 300r/min, oxidizing phosphorus from-3 price to +5 price, generating stable weak acid phosphoric acid, and forming indium sulfate which is easy to dissolve in water by indium, thereby realizing the efficient leaching of the indium phosphide waste.
2) Filtering at 25 ℃ after the reaction is finished to realize solid-liquid separation, thus obtaining leaching liquid.
3) Inserting an aluminum plate into the leaching solution at 55 ℃ for reaction for 12 hours, and controlling the dosage of the aluminum plate to Al/In 3+ The molar ratio is 2:1, so that the metallic aluminum and the indium ions undergo a displacement reaction to separate out metallic indium.
4) Filtering the replaced liquid at 55 ℃, recovering the sponge indium suspended in the solution, and recovering the sponge indium attached to the surface of the aluminum plate after the replacement reaction is finished; and washing the recovered sponge indium with deionized water for 4 times, and further drying at 60 ℃ for 72 hours to obtain the metal indium.
5) Adding ammonia water into the tail liquid of indium extraction at 25 ℃ under the mechanical stirring condition with the rotating speed of 300r/min for reaction for 5 hours, controlling the pH value of the reaction end point solution to be 4 by the addition amount of the ammonia water, and separating out aluminum phosphate.
6) Filtering the mixed slurry at 25 ℃ to realize solid-liquid separation, thereby obtaining filter residues and filtrate; washing the filter residue with deionized water for 4 times, and further drying at 60 ℃ for 72 hours to obtain aluminum phosphate powder; evaporating and crystallizing the filtrate to obtain ammonium sulfate crystals.
By the method of this example, the recovery rate and purity of the metal indium were analyzed by aqua regia dissolution in combination with inductively coupled plasma mass spectrometry (ICP-MS), and as a result, the recovery rate of the metal indium was 96.8%, and the purity of the metal indium was 99.5%.
Example 2
The method for comprehensively recycling the indium phosphide waste material in the embodiment specifically comprises the following steps:
1) Adding indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance into sulfuric acid solution containing hydrogen peroxide, and controlling the addition amount of the hydrogen peroxide to H 2 O 2 The molar ratio of the InP to the sulfuric acid is 10:1, and the pH value of the leaching end point solution is controlled to be 1.5; the reaction is carried out for 1h under the mechanical stirring condition of 95 ℃ and the rotating speed of 700r/min, so that phosphorus is oxidized from-3 price to +5 price, stable weak acid phosphoric acid is generated, indium forms indium sulfate which is easy to dissolve in water, and the efficient leaching of the indium phosphide waste is realized.
2) Filtering at 95 ℃ after the reaction is finished to realize solid-liquid separation, thus obtaining leaching liquid.
3) Inserting an aluminum plate into the leaching solution at 95 ℃ for reaction for 2 hours, and controlling the dosage of the aluminum plate to Al/In 3+ The molar ratio is 10:1, so that metallic aluminum and indium ions undergo a displacement reaction to separate out metallic indium.
4) Filtering the displaced liquid at the temperature of 95 ℃, recovering the sponge indium suspended in the solution, and simultaneously recovering the sponge indium attached to the surface of the aluminum plate after the displacement reaction is finished; and washing the recovered sponge indium by deionized water for 8 times, and further drying at 100 ℃ for 24 hours to obtain the metal indium.
5) Adding ammonia water into the tail liquid of indium extraction under the mechanical stirring condition of the temperature of 95 ℃ and the rotating speed of 700r/min for reaction for 1h, controlling the pH value of the reaction end point solution to be 6 by the addition amount of the ammonia water, and separating out aluminum phosphate.
6) Filtering the mixed slurry at the temperature of 95 ℃ to realize solid-liquid separation, so as to obtain filter residues and filtrate; washing the filter residue by deionized water for 8 times, and further drying at 100 ℃ for 24 hours to obtain aluminum phosphate powder; evaporating and crystallizing the filtrate to obtain ammonium sulfate crystals.
By the method of this example, the recovery rate and purity of the metal indium were analyzed by aqua regia dissolution in combination with inductively coupled plasma mass spectrometry (ICP-MS), and as a result, the recovery rate of the metal indium was 97.1% and the purity of the metal indium was 99.8%.
Example 3
The method for comprehensively recycling the indium phosphide waste material in the embodiment specifically comprises the following steps:
1) Adding indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance into sulfuric acid solution containing hydrogen peroxide, and controlling the addition amount of the hydrogen peroxide to H 2 O 2 The molar ratio of the InP to the sulfuric acid is 5.5:1, and the sulfuric acid concentration is controlledThe pH value of the leaching end point solution is 0.3; the reaction is carried out for 8 hours under the mechanical stirring condition of 45 ℃ and the rotating speed of 400r/min, so that phosphorus is oxidized from-3 price to +5 price, stable weak acid phosphoric acid is generated, indium forms indium sulfate which is easy to dissolve in water, and the efficient leaching of the indium phosphide waste is realized.
2) Filtering at 45 ℃ after the reaction is finished to realize solid-liquid separation, thus obtaining leaching liquid.
3) Inserting an aluminum plate into the leaching solution at 65 ℃ for reaction for 10 hours, and controlling the dosage of the aluminum plate to Al/In 3+ The molar ratio is 4:1, so that the metallic aluminum and the indium ions undergo a displacement reaction to separate out metallic indium.
4) Filtering the replaced liquid at 65 ℃, recovering the sponge indium suspended in the solution, and recovering the sponge indium attached to the surface of the aluminum plate after the replacement reaction is finished; and washing the recovered sponge indium by deionized water for 5 times, and further drying at 70 ℃ for 60 hours to obtain the metal indium.
5) Adding ammonia water into the tail liquid of indium extraction at 45 ℃ under the mechanical stirring condition with the rotating speed of 400r/min for reaction for 4 hours, controlling the pH value of the reaction end point solution to be 4.5 by the addition amount of the ammonia water, and separating out aluminum phosphate.
6) Filtering the mixed slurry at 45 ℃ to realize solid-liquid separation, so as to obtain filter residues and filtrate; washing the filter residue with deionized water for 5 times, and further drying at 70 ℃ for 60 hours to obtain aluminum phosphate powder; evaporating and crystallizing the filtrate to obtain ammonium sulfate crystals.
By the method of this example, the recovery rate and purity of the metal indium were analyzed by aqua regia dissolution in combination with inductively coupled plasma mass spectrometry (ICP-MS), and as a result, the recovery rate of the metal indium was 96.2% and the purity of the metal indium was 99.6%.
Example 4
The method for comprehensively recycling the indium phosphide waste material in the embodiment specifically comprises the following steps:
1) Adding indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance into sulfuric acid solution containing hydrogen peroxide, and controlling the addition amount of the hydrogen peroxide to H 2 O 2 The molar ratio of the/InP is 7:1, and the concentration of sulfuric acid controls the pH value of the leaching end point solution to be 0.8; at 60℃,The phosphorus is oxidized from-3 price to +5 price under the condition of mechanical stirring with the rotating speed of 500r/min for 6 hours, so that stable weak acid phosphoric acid is generated, and indium forms indium sulfate which is easy to dissolve in water, thereby realizing the efficient leaching of the indium phosphide waste.
2) Filtering at 60 ℃ after the reaction is finished to realize solid-liquid separation, thus obtaining leaching liquid.
3) Inserting an aluminum plate into the leaching solution at the temperature of 75 ℃ for reaction for 8 hours, and controlling the dosage of the aluminum plate to Al/In 3+ The molar ratio is 6:1, so that the metallic aluminum and the indium ions undergo a displacement reaction to separate out metallic indium.
4) Filtering the replaced liquid at the temperature of 75 ℃, recovering the sponge indium suspended in the solution, and simultaneously recovering the sponge indium attached to the surface of the aluminum plate after the replacement reaction is finished; and washing the recovered sponge indium by deionized water for 6 times, and further drying at 80 ℃ for 48 hours to obtain the metal indium.
5) Adding ammonia water into the tail liquid of indium extraction at 60 ℃ under the condition of mechanical stirring with the rotating speed of 500r/min for 3h, controlling the pH value of the reaction end point solution to be 5 by the addition of the ammonia water, and separating out aluminum phosphate.
6) Filtering the mixed slurry at 60 ℃ to realize solid-liquid separation, and obtaining filter residues and filtrate; washing the filter residue by deionized water for 6 times, and further drying at 80 ℃ for 48 hours to obtain aluminum phosphate powder; evaporating and crystallizing the filtrate to obtain ammonium sulfate crystals.
By the method of this example, the recovery rate and purity of the metal indium were analyzed by aqua regia dissolution in combination with inductively coupled plasma mass spectrometry (ICP-MS), and as a result, the recovery rate of the metal indium was 97.5%, and the purity of the metal indium was 99.8%.
Example 5
The method for comprehensively recycling the indium phosphide waste material in the embodiment specifically comprises the following steps:
1) Adding indium phosphide waste powder which is ball-milled to be less than 300 mu m in advance into sulfuric acid solution containing hydrogen peroxide, and controlling the addition amount of the hydrogen peroxide to H 2 O 2 The molar ratio of the InP to the sulfuric acid is 8.5:1, and the pH value of the leaching end point solution is controlled to be 1.2; reacting at 80 ℃ under the mechanical stirring condition with the rotating speed of 600r/min for 3And h, oxidizing phosphorus from-3 to +5 to generate stable weak acidic phosphoric acid, and forming indium sulfate which is easy to dissolve in water by indium to realize efficient leaching of indium phosphide waste.
2) Filtering at 80 ℃ after the reaction is finished to realize solid-liquid separation, thus obtaining leaching liquid.
3) Inserting an aluminum plate into the leaching solution at the temperature of 85 ℃ for reaction for 5 hours, and controlling the dosage of the aluminum plate to Al/In 3+ The molar ratio is 4:1, so that the metallic aluminum and the indium ions undergo a displacement reaction to separate out metallic indium.
4) Filtering the replaced liquid at the temperature of 85 ℃, recovering the sponge indium suspended in the solution, and simultaneously recovering the sponge indium attached to the surface of the aluminum plate after the replacement reaction is finished; and washing the recovered sponge indium by deionized water for 7 times, and further drying at 90 ℃ for 36 hours to obtain the metal indium.
5) Adding ammonia water into the tail liquid of indium extraction at 80 ℃ under the mechanical stirring condition with the rotating speed of 600r/min for 2h, controlling the pH value of the reaction end point solution to be 5.5 by the addition of the ammonia water, and separating out aluminum phosphate.
6) Filtering the mixed slurry at the temperature of 80 ℃ to realize solid-liquid separation, thereby obtaining filter residues and filtrate; washing the filter residue with deionized water for 7 times, and further drying at 90 ℃ for 36 hours to obtain aluminum phosphate powder; evaporating and crystallizing the filtrate to obtain ammonium sulfate crystals.
By the method of this example, the recovery rate and purity of metallic indium were analyzed by aqua regia dissolution in combination with inductively coupled plasma mass spectrometry (ICP-MS), and as a result, the recovery rate of metallic indium was 98.1% and the purity of metallic indium was 99.6%.
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 (8)
1. A comprehensive recovery method of indium phosphide waste is characterized by comprising the following steps: the indium phosphide waste is treated by an atmospheric pressure oxidation acid leaching process, so that phosphorus is oxidized to +5 from-3 to generate stable weak acid phosphoric acid, and the efficient leaching of the indium phosphide waste is realized; treating the leaching solution by adopting a metal replacement process, and recovering the metal indium; further, the tail liquid of indium extraction is treated by ammonia water neutralization and evaporation crystallization processes, and aluminum phosphate and ammonium sulfate are respectively recovered, so that the comprehensive recovery of valuable elements in the system is realized.
2. The method for comprehensively recovering the indium phosphide waste as recited in claim 1, wherein the specific operation comprises the following steps:
1) Adding indium phosphide waste powder into sulfuric acid solution containing hydrogen peroxide, heating the system to a preset temperature, oxidizing phosphorus from-3 price to +5 price under the condition of mechanical stirring to generate stable weak acid phosphoric acid, and forming indium sulfate which is easy to dissolve in water by indium so as to realize efficient leaching of the indium phosphide waste;
2) Filtering after the reaction is finished to realize solid-liquid separation to obtain leaching liquid;
3) Inserting an aluminum plate into the leaching solution to enable metal aluminum and indium ions to undergo a displacement reaction, and separating out metal indium;
4) Filtering the replaced liquid, recovering the sponge indium suspended in the solution, and recovering the sponge indium attached to the surface of the aluminum plate after the replacement reaction is finished; repeatedly washing and drying the recovered sponge indium by adopting deionized water to obtain metal indium;
5) Adding ammonia water into the tail liquid of indium extraction under the condition of mechanical stirring, and separating out aluminum phosphate;
6) Filtering the mixed slurry to realize solid-liquid separation and obtain filter residues and filtrate; repeatedly washing and drying filter residues by adopting deionized water to obtain aluminum phosphate powder; evaporating and crystallizing the filtrate to recover ammonium sulfate crystals.
3. A method for the comprehensive recovery of indium phosphide waste as set forth in claim 2,the method is characterized in that: 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, H 2 O 2 And InP molar ratio is controlled to be 4-10:1, sulfuric acid concentration is controlled to be 0-1.5, pH value of leaching end point solution is controlled to be 300-700r/min, reaction temperature is 25-95 ℃, and reaction time is 1-10h.
4. A method for the integrated recovery of indium phosphide waste as recited in claim 3, wherein: in the step 2), the solid-liquid separation temperature is consistent with the temperature of the oxidation acid leaching process in the step 1).
5. The method for comprehensively recovering indium phosphide waste as set forth in claim 2, wherein: in step 3), al and In are controlled 3+ The molar ratio is 2-10:1, the reaction temperature is 55-95 ℃, and the reaction time is 2-12h.
6. The method for comprehensively recovering indium phosphide waste as set forth in claim 5, wherein: in the step 4), the filtering temperature is consistent with the temperature of the replacement reaction process in the step 3), the reclaimed sponge indium is washed for 4-8 times by adopting deionized water, and the reclaimed sponge indium is dried for 24-72 hours at the temperature of 60-100 ℃ to obtain the metal indium.
7. The method for comprehensively recovering indium phosphide waste as set forth in claim 2, wherein: in the step 5), the addition amount of ammonia water controls the pH value of the reaction end point solution to be between 4 and 6, the mechanical stirring speed is 300 to 700r/min, the reaction temperature is 25 to 95 ℃ and the reaction time is 1 to 5 hours.
8. The method for comprehensively recovering indium phosphide waste as set forth in claim 7, wherein: the solid-liquid separation temperature in the step 6) is consistent with the reaction temperature in the step 5), deionized water is adopted to wash filter residues for 4-8 times, and the filter residues are dried for 24-72 hours at the temperature of 60-100 ℃ to obtain aluminum phosphate powder; evaporating and crystallizing the filtrate to obtain ammonium sulfate crystals.
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