CN107312931A - It is a kind of at the same reclaim noble metal and prepare HIGH-PURITY SILICON method - Google Patents
It is a kind of at the same reclaim noble metal and prepare HIGH-PURITY SILICON method Download PDFInfo
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- CN107312931A CN107312931A CN201710363321.1A CN201710363321A CN107312931A CN 107312931 A CN107312931 A CN 107312931A CN 201710363321 A CN201710363321 A CN 201710363321A CN 107312931 A CN107312931 A CN 107312931A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000010703 silicon Substances 0.000 title claims abstract description 100
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 83
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 65
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 54
- 239000000956 alloy Substances 0.000 claims abstract description 54
- 238000002386 leaching Methods 0.000 claims abstract description 25
- 239000002893 slag Substances 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 16
- 239000002210 silicon-based material Substances 0.000 claims abstract description 15
- 239000007769 metal material Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000010970 precious metal Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000009413 insulation Methods 0.000 claims abstract description 3
- 238000005204 segregation Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 44
- 239000010949 copper Substances 0.000 abstract description 23
- 229910052742 iron Inorganic materials 0.000 abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052802 copper Inorganic materials 0.000 abstract description 21
- 238000001926 trapping method Methods 0.000 abstract description 10
- 238000000746 purification Methods 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 52
- 229910052763 palladium Inorganic materials 0.000 description 26
- 229910052703 rhodium Inorganic materials 0.000 description 20
- 239000010948 rhodium Substances 0.000 description 20
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 20
- 229910052697 platinum Inorganic materials 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000006396 nitration reaction Methods 0.000 description 5
- 230000001698 pyrogenic effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/037—Purification
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/026—Recovery of noble metals from waste materials from spent catalysts
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
-
- 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
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a kind of while the method for reclaiming noble metal and preparing HIGH-PURITY SILICON, belongs to Precious Metals Resources clean utilization and silicon purification technique field.Slag and silicon-base alloy are obtained after pending noble metal materials, silicon materials and additive are carried out into melting, insulation together；Obtained silicon-base alloy is thermally treated, make noble metal in silicon process of setting toward silicon cyrystal boundary segregation and enrichment；Silicon-base alloy after will be heat treated is ground into powder；With the non-silicon thing phase of wet-leaching silicon grain boundaries, make to become trapped in the noble metal in silicon-base alloy and be transferred to leachate；Material will be leached and carry out filtration treatment, solid-state high-purity silicon powder and the leachate containing noble metal is respectively obtained；Obtained high-purity silicon powder is recirculated as silicon materials and used, or is sent to photovoltaic or electronic product enterprise as the raw material for preparing solar energy level silicon or electronic-grade silicon.It is of the invention compared with existing iron method of trapping and copper trapping method, have the advantages that non-carbon-emitting, low cost, flow are short.
Description
Technical field
The present invention relates to a kind of while the method for reclaiming noble metal and preparing HIGH-PURITY SILICON, belongs to Precious Metals Resources clean utilization
With silicon purification technique field.
Background technology
Reclaiming the method containing noble metal materials at present mainly has pyrogenic process and wet method.Wet method has that recovery process is simple, processing
The advantages of cost is low and equipment is simple, but when the failure automobile for handling substantial amounts of complicated Precious Metals Resources such as platinum group metal is catalyzed
When agent and petro chemical industry carried catalyst, the problems such as big sour consumption, processing time length and environmental pollution will be faced.
Noble metal in pyrogenic process trapping complicated resource is a kind of main stream approach both domestic and external.Although the energy consumption of pyrogenic process method of trapping
Height, but this method can efficiently single treatment it is substantial amounts of contain Precious Metals Resources, the platinum group metal failure for example increasingly risen
Automobile catalyst and petro chemical industry carried catalyst, it is short and low environment pollution excellent with rate of recovery height, processing time
Point.By taking platinum group metal in pyrogenic process trapping spent auto-catalysts as an example, the intellectual property applied both at home and abroad at present is main with iron
With copper as trapping agent, main process is：By the oxidation of spent auto-catalysts, additive, carbon containing reducer, ferriferous oxide or copper
Ferriferous oxide or Cu oxide are reduced into metallic iron or metallic copper by thing melting together, carbon, and metallic iron or metallic copper will fail vapour
Platinum group metal in car catalyst is trapped in fusant or copper melts.Because the fusing point of iron is higher, during using iron as trapping agent
Mainly use plasmamelt process.This method has the advantages that the rate of recovery is high and speed of melting is fast, but high energy consumption, equipment purchasing
It is higher with maintenance cost.The fusing point of copper much lower than the fusing point of iron 400 is spent, and compared with iron method of trapping, copper trapping method has melting
Temperature is low, production equipment is simple, and as trapping agent copper reusable edible the advantages of.
At present, the correlation technique of iron method of trapping is mainly by American-European noble metal company monopolizing, and the related skill of copper trapping method
Art is by the noble metal company monopolizing of Japan.
The content of the invention
The problem of existing for above-mentioned prior art and deficiency, the present invention provide a kind of recovery noble metal simultaneously and prepared high
The method of pure silicon.Present invention firstly discloses a kind of brand-new technology using silicon as noble metal collector, caught with existing iron
Collection method is compared with copper trapping method, has the advantages that non-carbon-emitting, low cost, flow are short.The present invention is real by the following technical programs
It is existing.
It is a kind of at the same reclaim noble metal and prepare HIGH-PURITY SILICON method, it comprises the following steps：
（1）Pending noble metal materials, silicon materials and additive are carried out together to obtain slag after melting, insulation and silicon substrate is closed
Gold；
（2）By step（1）In obtained silicon-base alloy it is thermally treated, make noble metal in silicon process of setting toward silicon cyrystal boundary segregation and
Enrichment；
（3）By step（2）In it is heat treated after silicon-base alloy be ground into powder；With the non-silicon thing of wet-leaching silicon grain boundaries
Phase, makes to become trapped in the noble metal in silicon-base alloy and is transferred to leachate；
（4）By step（3）Middle leaching material carries out filtration treatment, respectively obtains solid-state high-purity silicon powder and the leaching containing noble metal
Liquid；
（5）By step（4）In obtained high-purity silicon powder as step（1）In silicon materials recirculate and use, or be sent to photovoltaic
Or electronic product enterprise is used as the raw material for preparing solar energy level silicon or electronic-grade silicon.
The step（1）In pending noble metal materials be primarily referred to as the material containing at least one precious metal element, wrap
Include the failure cleaning catalyst for tail gases of automobiles or petro chemical industry carried catalyst of platinum group metal.
The step（1）Middle silicon materials include elemental silicon or the silicon-base alloy based on silicon.
The step（1）Middle additive is CaO, SiO2、Al2O3, one or more of arbitrary proportion mixtures in MgO, always
Addition for pending noble metal materials quality >=30%；But work as and contain CaO, SiO in noble metal materials2、Al2O3, in MgO
Two kinds and it is two or more when, can have the situation for being added without additive.
The step（1）Middle smelting temperature is >=1450 DEG C, soaking time >=1 hour.
The step（2）Middle heat treatment process includes cooling down or being cooled under silicon-base alloy fusing point after silicon-base alloy remelting
Less than 700 DEG C, cooling velocity is >=0.1 DEG C/min.
The step（3）The leaching agent added in middle wet method leaching process is in hydrofluoric acid containing, hydrochloric acid, nitric acid, sulfuric acid
One or more arbitrary proportion mixtures, leaching detailed process is：Leachate is >=1 with silicon-base alloy powder liquid-solid ratio:1mL/
G, extraction temperature is >=25 DEG C, and extraction time is >=1 hour.
Above-mentioned steps（1）Main component is CaO, SiO in obtained slag2、Al2O3And MgO, its content range is respectively
CaO：25 ~ 50wt%, SiO2：20 ~ 45wt%, Al2O3：15 ~ 50wt%, MgO：5~15wt%.
The beneficial effects of the invention are as follows：
（1）Using the method for the invention, the dual purpose for reclaiming noble metal and purification silicon can be reached simultaneously；
（2）The present invention using silicon as trapping agent reclaim containing the noble metal in noble metal materials, silicon materials first by noble metal trap into
Enter silicon substrate melt, during wet-leaching non-silicon thing phase, noble metal is transferred to leachate by silicon-base alloy again, and silicon due to
It will not be consumed in leaching process with leachate reaction, the silicon rate of recovery is more than 90 %；
（3）The HIGH-PURITY SILICON that the present invention is obtained both can recirculate to use as silicon materials can also be used for photovoltaic or used in electronic industry
The former material of silicon；
（4）The silicon method of trapping of the present invention is compared with existing iron method of trapping, with advantages below：1. smelting temperature is lower；2. silicon
It can be used with repetitive cycling；3. the ferroalloy containing noble metal that iron method of trapping is obtained needs further to remove iron with wet method and make expensive
Metal is separated with iron, and the silicon-base alloy containing noble metal that the silicon method of trapping of the present invention is obtained need not remove the process of silicon, and
It is to utilize noble metal the characteristics of silicon wafer circle is fully separated out, just can be by noble metal by the noble metal of wet-leaching silicon grain boundaries
Leachate is transferred to by silicon-base alloy, the purpose of silicon and precious metal separation is reached, silicon will not be consumed in acid cleaning process；4. iron
Need that ferriferous oxide is reduced into metallic iron with carbon in method of trapping, and the silicon method of trapping of the present invention does not have the process that carbon is reduced, because
This present invention is the technology that a kind of carbon-free and waste gas is discharged, and has particular advantages at environment-friendly aspect；5. iron method of trapping due to
It will be removed in subsequent process with wet method and the leachate containing noble metal obtained after iron, it is necessary to the addition of strict control trapping agent iron
Amount, and the silicon method of trapping invented removes silicon process without wet method, the amount without controlling trapping agent silicon, silicon materials can be with slag with any
Quality compares melting.The comparison of process flow of iron method of trapping and silicon method of trapping is as depicted in figs. 1 and 2.
（5）The silicon method of trapping of the present invention is compared with existing copper trapping method, with advantages below：1. copper trapping method is obtained
Copper alloy needs containing noble metal further make copper be oxidized to Cu oxide by oxygen blown method makes noble metal be enriched with again, and
The silicon-base alloy containing noble metal that the silicon method of trapping of the present invention is obtained does not need oxygen blast to remove silicon process, but utilizes noble metal in silicon
The characteristics of crystal boundary is fully separated out, just directly leaching can be transferred to by pickling silicon-base alloy powder by noble metal by silicon-base alloy
Liquid, silicon will not be consumed in acid cleaning process；2. the copper alloy of the concentration of precious metal obtained in copper trapping method after oxidized blowing,
Need further to make noble metal be separated with copper with wet method or cupric electrolysis, and the present invention silicon method of trapping only by pickling with regard to energy
Noble metal is set to be separated with silicon；Although 3. the copper of copper trapping method can realize recycling, carbon is required for by copper oxygen every time
Compound is reduced into metallic copper, and the silicon method of trapping of the present invention is without CARBON REDUCTION PROCESS OF TANTALUM, is the technology that a kind of carbon-free and waste gas is discharged,
Environment-friendly aspect has particular advantages.The comparison of process flow of copper trapping method and silicon method of trapping is as depicted in figs. 1 and 2.
Brief description of the drawings
Fig. 1 is copper trapping method and iron method of trapping process chart in the prior art；
Fig. 2 is silicon method of trapping process chart of the present invention.
Embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
As shown in Fig. 2 this reclaims noble metal and the method for preparing HIGH-PURITY SILICON simultaneously, it comprises the following steps：
（1）To be failed cleaning catalyst for tail gases of automobiles（Platiniferous, palladium and the g ton of rhodium total amount about 2000）, metallurgical grade silicon and additive
Melting is carried out together obtains slag and silicon-base alloy, melting condition：The cleaning catalyst for tail gases of automobiles containing failure and metallurgical grade silicon
Mass ratio is 1:1；Smelting temperature is 1500 DEG C, and 5 hours are incubated at 1500 DEG C；Additive is CaO, and addition is failure automobile
30 % of tai-gas clean-up catalyst quality.
（2）By step（1）In obtained silicon-base alloy separated with slag, the summation of platiniferous, palladium and rhodium is less than 40 in slag
G ton；Silicon-base alloy is heat-treated, heat treatment condition is：It is heated to 1300 DEG C（Below fusing point）And it is cold with 2 DEG C/min
But to less than 700 DEG C.
（3）By step（2）In it is heat treated after silicon-base alloy grind to form granularity and be less than 75 microns of powder；By what is obtained
Powdered silicon-base alloy leaches noble metal and other non-silicon thing phases, leaching condition with leachate：First with hydrofluoric acid and hydrochloric acid
Nitration mixture（Volume ratio is 1:1, the concentration of hydrofluoric acid and hydrochloric acid is 12mol/L before mixing）It is used as leachate, liquid-solid ratio 10:1mL/
G, 80 DEG C of extraction temperature, extraction time is 5 hours；Then with chloroazotic acid（Volume ratio is hydrochloric acid：Nitric acid=3：1, hydrochloric acid is equal with nitric acid
To analyze pure concentrated acid, no dilution）It is used as leachate, liquid-solid ratio 10:1mL/g, 80 DEG C of extraction temperature, extraction time is 5 hours.
（4）By step（3）In obtained solid liquid phase carry out filtration treatment, respectively obtain solid-state silica flour（Purity is more than
99.98%）With the leachate of platiniferous, palladium and rhodium.
（5）By step（4）In obtained silica flour again as step（1）In silicon materials recycle.
Through step（1）To step（5）Afterwards, the rate of recovery of silicon is 90.5%, and less than 2%, i.e., platinum, palladium and the total loss late of rhodium are
Platinum, palladium and rhodium more than 98% enter leachate.
Embodiment 2
As shown in Fig. 2 this reclaims noble metal and the method for preparing HIGH-PURITY SILICON simultaneously, it comprises the following steps：
（1）To be failed cleaning catalyst for tail gases of automobiles（Platiniferous, palladium and the g ton of rhodium total amount about 2000）, metallurgical grade silicon and additive
Melting is carried out together obtains slag and silicon-base alloy, melting condition：The cleaning catalyst for tail gases of automobiles containing failure and metallurgical grade silicon
Mass ratio is 2:1；Smelting temperature is 1500 DEG C, and 5 hours are incubated at 1500 DEG C；Additive is CaO and SiO2, addition difference
For the 45% and 15% of failure cleaning catalyst for tail gases of automobiles quality.
（2）By step（1）In obtained silicon-base alloy separated with slag, the summation of platiniferous, palladium and rhodium is less than 45 in slag
G ton；Silicon-base alloy is heat-treated, heat treatment condition is：1450 DEG C of refuses are heated to, and it is cold with 0.1 DEG C/min
But to less than 600 DEG C.
（3）By step（2）In it is heat treated after silicon-base alloy grind to form granularity less than 75 microns of powder；By obtained powder
Last shape silicon-base alloy leaches noble metal and other non-silicon thing phases, leaching condition with leachate：First with hydrofluoric acid（Concentration is
15mol/L）As leachate, liquid-solid ratio is 20:1mL/g, extraction temperature is 80 DEG C, and extraction time is 4 hours, then with chloroazotic acid
（Volume ratio is hydrochloric acid：Nitric acid=3：1, hydrochloric acid is the pure concentrated acid of analysis, no dilution with nitric acid）It is used as leachate, liquid-solid ratio 8:
1mL/g, 80 DEG C of extraction temperature, extraction time is 4 hours.
（4）By step（3）In obtained solid liquid phase carry out filtration treatment, respectively obtain solid-state high-purity silicon powder（Purity is more than
99.995 %）With the leachate of platiniferous, palladium and rhodium.
（5）By step（4）In obtained high-purity silicon powder as the raw material for preparing solar energy level silicon or electronic-grade silicon.
Through step（1）To step（5）Afterwards, the rate of recovery of silicon is 90%, and less than 2.2%, i.e., platinum, palladium and the total loss late of rhodium are
Platinum, palladium and rhodium more than 97.8% enter leachate.
Embodiment 3
As shown in Fig. 2 this reclaims noble metal and the method for preparing HIGH-PURITY SILICON simultaneously, it comprises the following steps：
（1）To be failed cleaning catalyst for tail gases of automobiles（Platiniferous, palladium and the g ton of rhodium total amount about 2000）, silico-aluminum（Containing aluminium
5wt%）Carry out melting together with additive and obtain slag and silicon-base alloy, melting condition：The cleaning catalyst for tail gases of automobiles containing failure
Mass ratio with silico-aluminum is 3:1；Smelting temperature is 1450 DEG C, and 8 hours are incubated at 1450 DEG C；Additive is CaO, SiO2
And Al2O3, addition is respectively 45%, 45% and the 5% of failure cleaning catalyst for tail gases of automobiles quality.
（2）By step（1）In obtained silicon-base alloy separated with slag, the summation of platiniferous, palladium and rhodium is less than 50 in slag
G ton；Silicon-base alloy is heat-treated, heat treatment condition is：1450 DEG C of refuses are heated to, and with 3 DEG C/min of coolings
To less than 600 DEG C.
（3）By step（2）In it is heat treated after silicon-base alloy grind to form granularity less than 75 microns of powder；Obtained powder
Shape silicon-base alloy leaches noble metal and other non-silicon thing phases, leaching condition with leachate：First with hydrochloric acid, sulfuric acid and hydrofluoric acid
Nitration mixture（Volume ratio is 3:1:1, the concentration of hydrochloric acid, sulfuric acid and hydrofluoric acid is 20mol/L before mixing）It is used as leachate, liquid-solid ratio
For 1:1mL/g, extraction temperature is 25 DEG C, and extraction time is 40 hours, then with chloroazotic acid（Volume ratio is hydrochloric acid：Nitric acid=3：1, salt
Acid is the pure concentrated acid of analysis, no dilution with nitric acid）It is used as leachate, liquid-solid ratio 8:1mL/g, 85 DEG C of extraction temperature, extraction time
For 4 hours.
（4）By step（3）In obtained solid liquid phase carry out filtration treatment, respectively obtain solid-state high-purity silicon powder（Purity is more than
99.99 %）With the leachate of platiniferous, palladium and rhodium.
（5）By step（4）In obtained high-purity silicon powder as step（1）In silicon materials recycle.
Through step（1）To step（5）Afterwards, the rate of recovery of silicon is 92%, and less than 4 %, i.e., platinum, palladium and the total loss late of rhodium are
Platinum, palladium and rhodium more than 96 % enter leachate.
Embodiment 4
As shown in Fig. 2 this reclaims noble metal and the method for preparing HIGH-PURITY SILICON simultaneously, it comprises the following steps：
（1）By petro chemical industry carried catalyst（Platiniferous 0.35wt%）, Antaciron（Iron content 4wt%）With additive together
Carry out melting and obtain slag and silicon-base alloy, melting condition：The quality of petro chemical industry carried catalyst and Antaciron
Than for 2:1；Smelting temperature is 1600 DEG C, and 5 hours are incubated at 1600 DEG C；Additive is CaO and SiO2, addition is respectively stone
The 70% and 15% of the industrial carried catalyst quality of oiling.
（2）By step（1）In obtained silicon-base alloy separated with slag, platinum containing amount is less than 50 g tons in slag；By silicon substrate
Alloy is heat-treated, and heat treatment condition is：1450 DEG C of refuses are heated to, and less than 600 DEG C are cooled to 1 DEG C/min.
（3）By step（2）In it is heat treated after silicon-base alloy grind to form granularity less than 75 microns of powder；By obtained powder
Last shape silicon-base alloy leaches platinum, leaching condition with leachate：First with the nitration mixture of hydrochloric acid, hydrofluoric acid and sulfuric acid（Volume ratio is 3:
1:1, the concentration of hydrochloric acid, hydrofluoric acid and sulfuric acid is 16mol/L before mixing）As leachate, liquid-solid ratio is 10:1mL/g, is leached
Temperature is 80 DEG C, and extraction time is 5 hours, then with chloroazotic acid（Volume ratio is hydrochloric acid：Nitric acid=3：1, no dilution）It is used as leaching
Liquid, liquid-solid ratio 9:1mL/g, 75 DEG C of extraction temperature, extraction time is 5 hours.
（4）By step（3）In obtained solid liquid phase carry out filtration treatment, respectively obtain solid-state high-purity silicon powder（Purity is more than
99.99 %）With the leachate of platiniferous.
（5）By step（4）In obtained high-purity silicon powder as step（1）In silicon materials recycle.
Through step（1）To step（5）Afterwards, the rate of recovery of silicon is 95%, and the loss late of platinum is less than 2%, i.e., more than 98 %'s
Platinum enters leachate.
Embodiment 5
As shown in Fig. 2 this reclaims noble metal and the method for preparing HIGH-PURITY SILICON simultaneously, it comprises the following steps：
（1）By petro chemical industry carried catalyst（0.2wt% containing palladium）, calcium-silicon（Calcic 2wt%）With additive together
Carry out melting and obtain slag and silicon-base alloy, melting condition：The quality of petro chemical industry carried catalyst and calcium-silicon
Than for 2:1；Smelting temperature is 1600 DEG C, and 1 hour is incubated at 1600 DEG C；Additive is CaO, SiO2And MgO, addition difference
For 70%, 15% and 5 % of petro chemical industry carried catalyst quality.
（2）By step（1）In obtained silicon-base alloy separated with slag, amount containing palladium is less than 30 g tons in slag；By silicon substrate
Alloy is heat-treated, and heat treatment condition is：Be heated to 1450 DEG C of refuses, and with 1.5 DEG C/min be cooled to 700 DEG C with
Under.
（3）By step（2）In it is heat treated after silicon-base alloy grind to form granularity less than 75 microns of powder；By obtained powder
Last shape silicon-base alloy leaches palladium, leaching condition with leachate：First with hydrofluoric acid and the nitration mixture of sulfuric acid（Volume ratio is 3:1, mixing
The concentration of preceding hydrofluoric acid and sulfuric acid is 16mol/L）As leachate, liquid-solid ratio is 8:1ml/g, extraction temperature is 60 DEG C, leaching
Go out the time for 5 hours, then with chloroazotic acid（Volume ratio is hydrochloric acid：Nitric acid=3：1, no dilution）It is used as leachate, liquid-solid ratio 10:
1mL/g, 80 DEG C of extraction temperature, extraction time is 1 hour.
（4）By step（3）In obtained solid liquid phase carry out filtration treatment, respectively obtain solid-state high-purity silicon powder（Purity is more than
99.99 %）With the leachate containing palladium.
（5）By step（4）In obtained high-purity silicon powder as the raw material for preparing solar energy level silicon or electronic-grade silicon.
Through step（1）To step（5）Afterwards, the rate of recovery of silicon is 95%, and the loss late of palladium is less than 2 %, i.e., more than 98 %'s
Palladium enters leachate.
Embodiment 6
As shown in Fig. 2 this reclaims noble metal and the method for preparing HIGH-PURITY SILICON simultaneously, it comprises the following steps：
（1）By the waste residue containing noble metal（Extract the residual residue in spent auto-catalysts after noble metal with pyrogenic process, containing CaO,
SiO2And Al2O3Mass percent be respectively 23%, 32% and 27%, platiniferous, palladium and the g ton of rhodium total amount about 50,）And metallurgical grade silicon
Melting is carried out together obtains slag and silicon-base alloy, melting condition：The cleaning catalyst for tail gases of automobiles containing failure and metallurgical grade silicon
Mass ratio is 1:1；Smelting temperature is 1500 DEG C, and 5 hours are incubated at 1500 DEG C；It is additive-free.
（2）By step（1）In obtained silicon-base alloy separated with slag, the summation of platiniferous, palladium and rhodium is less than 5 in slag
G ton；Silicon-base alloy is heat-treated, heat treatment condition is：It is heated to 1450 DEG C and is cooled to 500 DEG C with 1.5 DEG C/min
Below.
（3）By step（2）In it is heat treated after silicon-base alloy grind to form granularity and be less than 75 microns of powder；By what is obtained
Powdered silicon-base alloy leaches noble metal and other non-silicon thing phases, leaching condition with leachate：First with chloroazotic acid（Volume ratio is salt
Acid：Nitric acid=3：1, no dilution）It is used as leachate, liquid-solid ratio 10:1mL/g, 85 DEG C of extraction temperature, extraction time is 5 hours, so
Afterwards with the nitration mixture of hydrofluoric acid, hydrochloric acid and sulfuric acid（Volume ratio is 1:1:1, the concentration of hydrofluoric acid, hydrochloric acid and sulfuric acid is before mixing
12mol/L）As leachate, solid-to-liquid ratio is 10:1mL/g, extraction temperature is 80 DEG C, and extraction time is 5 hours.
（4）By step（3）In obtained solid liquid phase carry out filtration treatment, respectively obtain solid-state high-purity silicon powder（Purity is more than
99.99%）With the leachate of platiniferous, palladium and rhodium.
（5）By step（4）In obtained high-purity silicon powder again as step（1）In silicon materials recycle.
Through step（1）To step（5）Afterwards, the rate of recovery of silicon be 95.5%, platinum, palladium and the total loss late of rhodium be less than 10%,
Platinum, palladium and the rhodium for being more than 90% enter leachate.
Above in association with accompanying drawing to the present invention embodiment be explained in detail, but the present invention be not limited to it is above-mentioned
Embodiment, can also be before present inventive concept not be departed from the knowledge that those of ordinary skill in the art possess
Put that various changes can be made.
Claims (7)
1. it is a kind of while the method for reclaiming noble metal and preparing HIGH-PURITY SILICON, it is characterised in that to comprise the following steps：
（1）Pending noble metal materials, silicon materials and additive are carried out together to obtain slag after melting, insulation and silicon substrate is closed
Gold；
（2）By step（1）In obtained silicon-base alloy it is thermally treated, make noble metal in silicon process of setting toward silicon cyrystal boundary segregation and
Enrichment；
（3）By step（2）In it is heat treated after silicon-base alloy be ground into powder；With the non-silicon thing of wet-leaching silicon grain boundaries
Phase, makes to become trapped in the noble metal in silicon-base alloy and is transferred to leachate；
（4）By step（3）Middle leaching material carries out filtration treatment, respectively obtains solid-state high-purity silicon powder and the leaching containing noble metal
Liquid；
（5）By step（4）In obtained high-purity silicon powder as step（1）In silicon materials recirculate and use, or be sent to photovoltaic
Or electronic product enterprise is used as the raw material for preparing solar energy level silicon or electronic-grade silicon.
2. it is according to claim 1 while the method for reclaiming noble metal and preparing HIGH-PURITY SILICON, it is characterised in that：The step
（1）In pending noble metal materials be primarily referred to as the material containing at least one precious metal element, include the mistake of platinum group metal
Imitate cleaning catalyst for tail gases of automobiles or petro chemical industry carried catalyst.
3. it is according to claim 1 while the method for reclaiming noble metal and preparing HIGH-PURITY SILICON, it is characterised in that：The step
（1）Middle silicon materials include elemental silicon or the silicon-base alloy based on silicon.
4. it is according to claim 1 while the method for reclaiming noble metal and preparing HIGH-PURITY SILICON, it is characterised in that：The step
（1）Middle additive is CaO, SiO2、Al2O3, one or more of arbitrary proportion mixtures in MgO, total addition level is pending expensive
Metalliferous material quality >=30%；But work as and contain CaO, SiO in noble metal materials2、Al2O3, two kinds in MgO and two or more
When, there can be the situation for being added without additive.
5. it is according to claim 1 while the method for reclaiming noble metal and preparing HIGH-PURITY SILICON, it is characterised in that：The step
（1）Middle smelting temperature is >=1450 DEG C, soaking time >=1 hour.
6. it is according to claim 1 while the method for reclaiming noble metal and preparing HIGH-PURITY SILICON, it is characterised in that：The step
（2）Middle heat treatment process includes less than 700 DEG C, cooling speed are cooled down or be cooled under silicon-base alloy fusing point after silicon-base alloy remelting
Spend for >=0.1 DEG C/min.
7. it is according to claim 1 while the method for reclaiming noble metal and preparing HIGH-PURITY SILICON, it is characterised in that：The step
（3）The leaching agent added in middle wet method leaching process is any ratio of one or more in hydrofluoric acid containing, hydrochloric acid, nitric acid, sulfuric acid
Example mixture, leaching detailed process is：Leachate is >=1 with silicon-base alloy powder liquid-solid ratio:1mL/g, extraction temperature is >=25
DEG C, extraction time is >=1 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107557582A (en) * | 2017-07-25 | 2018-01-09 | 昆明理工大学 | A kind of selective extraction and the method for being enriched with valuable metal in more metals resources |
| CN112981101A (en) * | 2021-02-02 | 2021-06-18 | 昆明理工大学 | Method for simultaneously recycling cut silicon waste and trapping rare and precious metals in spent catalyst |
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| JP2006274433A (en) * | 2005-03-30 | 2006-10-12 | Nikko Kinzoku Kk | Method for recovering noble metal from waste brick |
| CN101575674A (en) * | 2001-06-28 | 2009-11-11 | 贵研铂业股份有限公司 | Method for recovering platinum metal from melting trapped material |
| CN105400962A (en) * | 2015-11-18 | 2016-03-16 | 金川集团股份有限公司 | Method for recycling platinum group metal from waste catalysts |
| CN106115717A (en) * | 2016-08-23 | 2016-11-16 | 昆明理工大学 | A kind of remove the method for impurity in metallurgical grade silicon |
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| CN101575674A (en) * | 2001-06-28 | 2009-11-11 | 贵研铂业股份有限公司 | Method for recovering platinum metal from melting trapped material |
| JP2006274433A (en) * | 2005-03-30 | 2006-10-12 | Nikko Kinzoku Kk | Method for recovering noble metal from waste brick |
| CN105400962A (en) * | 2015-11-18 | 2016-03-16 | 金川集团股份有限公司 | Method for recycling platinum group metal from waste catalysts |
| CN106115717A (en) * | 2016-08-23 | 2016-11-16 | 昆明理工大学 | A kind of remove the method for impurity in metallurgical grade silicon |
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| CN107557582A (en) * | 2017-07-25 | 2018-01-09 | 昆明理工大学 | A kind of selective extraction and the method for being enriched with valuable metal in more metals resources |
| CN107557582B (en) * | 2017-07-25 | 2018-11-09 | 昆明理工大学 | A kind of method of selective extraction and valuable metal in the more metals resources of enrichment |
| CN112981101A (en) * | 2021-02-02 | 2021-06-18 | 昆明理工大学 | Method for simultaneously recycling cut silicon waste and trapping rare and precious metals in spent catalyst |
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