CN107312931B - Method that is a kind of while recycling noble metal and prepare HIGH-PURITY SILICON - Google Patents

Method that is a kind of while recycling noble metal and prepare HIGH-PURITY SILICON Download PDF

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CN107312931B
CN107312931B CN201710363321.1A CN201710363321A CN107312931B CN 107312931 B CN107312931 B CN 107312931B CN 201710363321 A CN201710363321 A CN 201710363321A CN 107312931 B CN107312931 B CN 107312931B
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silicon
noble metal
base alloy
purity
powder
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CN107312931A (en
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雷云
马文会
伍继君
李绍元
魏奎先
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Kunming University of Science and Technology
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    • 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

Abstract

The present invention relates to a kind of methods for recycling noble metal simultaneously and preparing HIGH-PURITY SILICON, belong to Precious Metals Resources clean utilization and silicon purification technique field.Noble metal materials to be processed, silicon materials and additive are subjected to melting together, obtain slag and silicon-base alloy after heat preservation；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 object phase of wet-leaching silicon grain boundaries, the noble metal becomeing trapped in silicon-base alloy is made to be transferred to leachate；Material will be leached and be filtered processing, respectively obtain solid-state high-purity silicon powder and the leachate containing noble metal；Obtained high-purity silicon powder is recirculated as silicon materials and is used, or is sent to photovoltaic or electronic product enterprise as the raw material for preparing solar energy level silicon or electronic-grade silicon.The present invention has the advantages that non-carbon-emitting, low cost, process are short compared with existing iron method of trapping and copper trapping method.

Description

Method that is a kind of while recycling noble metal and prepare HIGH-PURITY SILICON
Technical field
The present invention relates to a kind of methods for recycling noble metal simultaneously and preparing HIGH-PURITY SILICON, belong to Precious Metals Resources clean utilization With silicon purification technique field.
Background technique
Method of the recycling containing noble metal materials mainly has pyrogenic process and wet process at present.Wet process is simple with recovery process, handles The advantages that at low cost and equipment is simple, but when the failure automobile catalysis of a large amount of complicated Precious Metals Resources such as platinum group metal of processing When agent and petro chemical industry carried catalyst, the problems such as sour consumption is big, the processing time is long and environmental pollution will be faced.
The noble metal that pyrogenic process traps in 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 efficiently single treatment largely can contain Precious Metals Resources, such as the platinum group metal failure increasingly increased Automobile catalyst and petro chemical industry carried catalyst, with the rate of recovery, high, short processing time and low environment pollute excellent 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 mainly with iron With copper as trapping agent, main process is：Spent auto-catalysts, additive, carbon containing reducer, ferriferous oxide or copper are aoxidized Ferriferous oxide or Cu oxide are reduced into metallic iron or metallic copper by object melting together, carbon, and metallic iron or metallic copper will fail vapour Platinum group metal in vehicle catalyst traps in fusant or copper melts.Since the fusing point of iron is higher, when using iron as trapping agent Mainly use plasmamelt process.This method has many advantages, such as that the rate of recovery is high and speed of melting is fast, but energy consumption is high, equipment purchasing It is relatively high with maintenance cost.The fusing point of copper lower than the fusing point of iron more than 400 is spent, and compared with iron method of trapping, copper trapping method has melting The advantages that temperature is low, production equipment is simple, and Ke Xunhuanliyong as the copper of trapping agent.
Currently, the relevant technologies of iron method of trapping are 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.
Summary of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention provides a kind of while recycling noble metal and preparation height The method of pure silicon.Present invention firstly discloses a kind of completely new technologies using silicon as noble metal collector, catch with existing iron Collection method is compared with copper trapping method, has the advantages that non-carbon-emitting, low cost, process are short.The present invention is real by the following technical programs It is existing.
Method that is a kind of while recycling noble metal and prepare HIGH-PURITY SILICON comprising following steps：
（1）Noble metal materials to be processed, silicon materials and additive are subjected to melting together, obtain slag and silicon substrate after heat preservation Alloy；
（2）By step（1）Obtained in silicon-base alloy it is thermally treated, make noble metal in silicon process of setting toward silicon wafer circle it is inclined Analysis and enrichment；
（3）By step（2）In it is heat treated after silicon-base alloy be ground into powder；It is non-with wet-leaching silicon grain boundaries Silicon object phase, makes the noble metal becomeing trapped in silicon-base alloy be transferred to leachate；
（4）By step（3）Middle leaching material is filtered processing, respectively obtains solid-state high-purity silicon powder and the leaching containing noble metal Liquid out；
（5）By step（4）Obtained in high-purity silicon powder as step（1）In silicon materials recirculate and use, or be sent to Photovoltaic or electronic product enterprise are as the raw material for preparing solar energy level silicon or electronic-grade silicon.
The step（1）In noble metal materials to be processed 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 MgO arbitrary proportion mixture, always Additive amount be noble metal materials quality to be processed >=30%；But works as in noble metal materials and contained CaO, SiO2、Al2O3, in MgO Two kinds and it is two or more when, the case where additive can be added without.
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 700 DEG C hereinafter, cooling velocity is >=0.1 DEG C/min.
The step（3）The leaching agent being added in middle wet method leaching process is hydrofluoric acid containing, in hydrochloric acid, nitric acid, sulfuric acid One or more arbitrary proportion mixtures, leaching detailed process is：Leachate and silicon-base alloy powder liquid-solid ratio are >=1:1mL/ G, extraction temperature are >=25 DEG C, and extraction time is >=1 hour.
Above-mentioned steps（1）Main component is CaO, SiO in obtained slag2、Al2O3And MgO, content range are 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, recycling noble metal can be reached simultaneously and purify the dual purpose of silicon；
（2）The present invention is recycled using silicon as trapping agent containing the noble metal in noble metal materials, and silicon materials first catch noble metal Collection enters silicon substrate melt, and during wet-leaching non-silicon object phase, noble metal is transferred to leachate by silicon-base alloy again, and silicon It will not be consumed in leaching process due to not reacted with leachate, the silicon rate of recovery is greater than 90 %；
（3）The HIGH-PURITY SILICON that the present invention obtains, which both can be used as silicon materials re-circulation use, can also be used for photovoltaic or electronics row The former material of industry silicon；
（4）Silicon method of trapping of the invention has the following advantages that compared with existing iron method of trapping：1. smelting temperature is lower； 2. silicon can be used with repetitive cycling；3. the ferroalloy containing noble metal that iron method of trapping obtains need further to remove iron with wet process and Separate noble metal with iron, and the silicon-base alloy containing noble metal that silicon method of trapping of the invention obtains does not need to remove the mistake of silicon Journey, but using noble metal the characteristics of silicon wafer circle is sufficiently precipitated, it can be incited somebody to action by the noble metal of wet-leaching silicon grain boundaries Noble metal is transferred to leachate by silicon-base alloy, achievees the purpose that silicon and precious metal separation, silicon will not be disappeared in acid cleaning process Consumption；4. it needs that ferriferous oxide is reduced into metallic iron with carbon in iron method of trapping, and silicon method of trapping of the invention does not have carbon to restore Process, therefore the present invention is a kind of technology of carbon-free and exhaust gas discharge, has particular advantages at environmental-friendly aspect；5. iron traps Method is due to obtaining the leachate containing noble metal after removing iron with wet process in the follow-up process, it is necessary to strict control trapping agent iron Additive amount, and the silicon method of trapping invented removes silicon process without wet process, without controlling the amount of trapping agent silicon, silicon materials can with slag with Any quality compares melting.Iron method of trapping and the comparison of process flow of silicon method of trapping are as depicted in figs. 1 and 2.
（5）Silicon method of trapping of the invention has the following advantages that compared with existing copper trapping method：What 1. copper trapping method obtained Copper alloy containing noble metal needs further to make copper be oxidized to Cu oxide by oxygen blown method to be enriched with noble metal again, and The silicon-base alloy containing noble metal that silicon method of trapping of the invention obtains does not need oxygen blast except silicon process, but utilizes noble metal in silicon Noble metal directly can be transferred to leaching by silicon-base alloy by pickling silicon-base alloy powder by the characteristics of crystal boundary is sufficiently precipitated Liquid, silicon will not be consumed in acid cleaning process；2. the copper alloy of the concentration of precious metal obtained after oxidation blowing in copper trapping method, It needs further to separate noble metal with copper with wet process or cupric electrolysis, and silicon method of trapping of the invention only passes through pickling energy Separate noble metal with silicon；Although requiring carbon for copper oxygen every time 3. the copper of copper trapping method may be implemented to be recycled Compound is reduced into metallic copper, and silicon method of trapping of the invention is without CARBON REDUCTION PROCESS OF TANTALUM, is a kind of technology of carbon-free and exhaust gas discharge, Environmental-friendly aspect has particular advantages.Copper trapping method and the comparison of process flow of silicon method of trapping are as depicted in figs. 1 and 2.
Detailed description of the invention
Fig. 1 is copper trapping method and iron method of trapping process flow chart in the prior art；
Fig. 2 is silicon method of trapping process flow chart of the present invention.
Specific embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
As shown in Fig. 2, the method for recycling noble metal simultaneously and preparing HIGH-PURITY SILICON comprising following steps：
（1）To fail cleaning catalyst for tail gases of automobiles（Platiniferous, palladium and about 2000 g tons of rhodium total amount）, metallurgical grade silicon and add Add agent to carry out melting together and obtains slag and silicon-base alloy, melting condition：The cleaning catalyst for tail gases of automobiles containing failure and metallurgical grade The mass ratio of silicon is 1:1；Smelting temperature is 1500 DEG C, keeps the temperature 5 hours at 1500 DEG C；Additive is CaO, and additive amount is failure 30 % of cleaning catalyst for tail gases of automobiles quality.
（2）By step（1）Obtained in 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 700 DEG C or less.
（3）By step（2）In it is heat treated after silicon-base alloy be ground into granularity and be lower than 75 microns of powder；By what is obtained Powdered silicon-base alloy leaches noble metal and other non-silicon object 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）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）As leachate, liquid-solid ratio 10:1mL/g, 80 DEG C of extraction temperature, extraction time is 5 hours.
（4）By step（3）Obtained in solid liquid phase be filtered processing, respectively obtain solid-state silicon powder（Purity is greater than 99.98%）With the leachate of platiniferous, palladium and rhodium.
（5）By step（4）Obtained in silicon powder be re-used as step（1）In silicon materials be recycled.
Through step（1）To step（5）Afterwards, the rate of recovery of silicon is 90.5%, less than 2%, i.e., platinum, palladium and the total loss late of rhodium are Platinum, palladium and rhodium greater than 98% enter leachate.
Embodiment 2
As shown in Fig. 2, the method for recycling noble metal simultaneously and preparing HIGH-PURITY SILICON comprising following steps：
（1）To fail cleaning catalyst for tail gases of automobiles（Platiniferous, palladium and about 2000 g tons of rhodium total amount）, metallurgical grade silicon and add Add agent to carry out melting together and obtains slag and silicon-base alloy, melting condition：The cleaning catalyst for tail gases of automobiles containing failure and metallurgical grade The mass ratio of silicon is 2:1；Smelting temperature is 1500 DEG C, keeps the temperature 5 hours at 1500 DEG C；Additive is CaO and SiO2, additive amount Respectively the 45% and 15% of failure cleaning catalyst for tail gases of automobiles quality.
（2）By step（1）Obtained in 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 cold with 0.1 DEG C/min But to 600 DEG C or less.
（3）By step（2）In it is heat treated after silicon-base alloy be ground into granularity lower than 75 microns of powder；The powder that will be obtained Last shape silicon-base alloy leaches noble metal and other non-silicon object phases, leaching condition with leachate：First with hydrofluoric acid（Concentration is 15mol/L）As leachate, liquid-solid ratio 20:1mL/g, extraction temperature are 80 DEG C, and extraction time is 4 hours, then with chloroazotic acid （Volume ratio is hydrochloric acid：Nitric acid=3：1, hydrochloric acid and nitric acid are the pure concentrated acid of analysis, no dilution）As leachate, liquid-solid ratio 8: 1mL/g, 80 DEG C of extraction temperature, extraction time is 4 hours.
（4）By step（3）Obtained in solid liquid phase be filtered processing, respectively obtain solid-state high-purity silicon powder（Purity is greater than 99.995 %）With the leachate of platiniferous, palladium and rhodium.
（5）By step（4）Obtained in 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%, less than 2.2%, i.e., platinum, palladium and the total loss late of rhodium are Platinum, palladium and rhodium greater than 97.8% enter leachate.
Embodiment 3
As shown in Fig. 2, the method for recycling noble metal simultaneously and preparing HIGH-PURITY SILICON comprising following steps：
（1）To fail cleaning catalyst for tail gases of automobiles（Platiniferous, palladium and about 2000 g tons of rhodium total amount）, silico-aluminum（Containing aluminium 5wt%）It carries out melting together with additive and obtains 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, keeps the temperature 8 hours at 1450 DEG C；Additive is CaO, SiO2 And Al2O3, additive amount is respectively 45%, 45% and the 5% of failure cleaning catalyst for tail gases of automobiles quality.
（2）By step（1）Obtained in 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 600 DEG C or less.
（3）By step（2）In it is heat treated after silicon-base alloy be ground into granularity lower than 75 microns of powder；Obtained powder Shape silicon-base alloy leaches noble metal and other non-silicon object 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）As leachate, liquid-solid ratio It is 1:1mL/g, extraction temperature are 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）As leachate, liquid-solid ratio 8:1mL/g, 85 DEG C of extraction temperature, extraction time It is 4 hours.
（4）By step（3）Obtained in solid liquid phase be filtered processing, respectively obtain solid-state high-purity silicon powder（Purity is greater than 99.99 %）With the leachate of platiniferous, palladium and rhodium.
（5）By step（4）Obtained in high-purity silicon powder as step（1）In silicon materials be recycled.
Through step（1）To step（5）Afterwards, the rate of recovery of silicon is 92%, less than 4 %, i.e., platinum, palladium and the total loss late of rhodium are Platinum, palladium and rhodium greater than 96 % enter leachate.
Embodiment 4
As shown in Fig. 2, the method for recycling noble metal simultaneously and preparing HIGH-PURITY SILICON comprising following steps：
（1）By petro chemical industry carried catalyst（Platiniferous 0.35wt%）, Antaciron（Iron content 4wt%）And additive Melting is carried out together obtains slag and silicon-base alloy, melting condition：Petro chemical industry carried catalyst and Antaciron Mass ratio is 2:1；Smelting temperature is 1600 DEG C, keeps the temperature 5 hours at 1600 DEG C；Additive is CaO and SiO2, additive amount difference It is the 70% and 15% of petro chemical industry carried catalyst quality.
（2）By step（1）Obtained in 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 are cooled to 600 DEG C or less with 1 DEG C/min.
（3）By step（2）In it is heat treated after silicon-base alloy be ground into granularity lower than 75 microns of powder；The powder that will be obtained 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 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）As leaching Liquid, liquid-solid ratio 9:1mL/g, 75 DEG C of extraction temperature, extraction time is 5 hours.
（4）By step（3）Obtained in solid liquid phase be filtered processing, respectively obtain solid-state high-purity silicon powder（Purity is greater than 99.99 %）With the leachate of platiniferous.
（5）By step（4）Obtained in high-purity silicon powder as step（1）In silicon materials be recycled.
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., greater than 98 %'s Platinum enters leachate.
Embodiment 5
As shown in Fig. 2, the method for recycling noble metal simultaneously and preparing HIGH-PURITY SILICON comprising following steps：
（1）By petro chemical industry carried catalyst（0.2wt% containing palladium）, calcium-silicon（Calcic 2wt%）And additive Melting is carried out together obtains slag and silicon-base alloy, melting condition：Petro chemical industry carried catalyst and calcium-silicon Mass ratio is 2:1；Smelting temperature is 1600 DEG C, keeps the temperature 1 hour at 1600 DEG C；Additive is CaO, SiO2And MgO, additive amount Respectively 70%, 15% and 5 % of petro chemical industry carried catalyst quality.
（2）By step（1）Obtained in 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 be ground into granularity lower than 75 microns of powder；The powder that will be obtained Last shape silicon-base alloy leaches palladium, leaching condition with leachate：First with the nitration mixture of hydrofluoric acid and 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 8:1ml/g, extraction temperature are 60 DEG C, leaching The time is 5 hours out, then with chloroazotic acid（Volume ratio is hydrochloric acid：Nitric acid=3：1, no dilution）As leachate, liquid-solid ratio 10: 1mL/g, 80 DEG C of extraction temperature, extraction time is 1 hour.
（4）By step（3）Obtained in solid liquid phase be filtered processing, respectively obtain solid-state high-purity silicon powder（Purity is greater than 99.99 %）With the leachate containing palladium.
（5）By step（4）Obtained in 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., greater than 98 %'s Palladium enters leachate.
Embodiment 6
As shown in Fig. 2, the method for recycling noble metal simultaneously and preparing HIGH-PURITY SILICON comprising following steps：
（1）By the waste residue containing noble metal（The residual residue in spent auto-catalysts after noble metal is extracted with pyrogenic process, is contained CaO、SiO2And Al2O3Mass percent be respectively 23%, 32% and 27%, platiniferous, palladium and about 50 g tons of rhodium total amount,）And metallurgy Grade silicon carries out melting together and obtains slag and silicon-base alloy, melting condition：The cleaning catalyst for tail gases of automobiles containing failure and metallurgical grade The mass ratio of silicon is 1:1；Smelting temperature is 1500 DEG C, keeps the temperature 5 hours at 1500 DEG C；It is additive-free.
（2）By step（1）Obtained in 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 be ground into granularity and be lower than 75 microns of powder；By what is obtained Powdered silicon-base alloy leaches noble metal and other non-silicon object phases, leaching condition with leachate：First with chloroazotic acid（Volume ratio is salt Acid：Nitric acid=3：1, no dilution）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 10:1mL/g, extraction temperature are 80 DEG C, and extraction time is 5 hours.
（4）By step（3）Obtained in solid liquid phase be filtered processing, respectively obtain solid-state high-purity silicon powder（Purity is greater than 99.99%）With the leachate of platiniferous, palladium and rhodium.
（5）By step（4）Obtained in high-purity silicon powder be re-used as step（1）In silicon materials be recycled.
Through step（1）To step（5）Afterwards, the rate of recovery of silicon is 95.5%, platinum, palladium and the total loss late of rhodium be less than 10%, Platinum, palladium and rhodium i.e. greater than 90% enter leachate.
In conjunction with attached drawing, the embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned Embodiment within the knowledge of a person skilled in the art can also be before not departing from present inventive concept Put that various changes can be made.

Claims (6)

1. a kind of method for recycling noble metal simultaneously and preparing HIGH-PURITY SILICON, it is characterised in that include the following steps：
（1）Noble metal materials to be processed, silicon materials and additive are subjected to melting together, slag is obtained after heat preservation and silicon substrate is closed Gold；
（2）By step（1）Obtained in silicon-base alloy it is thermally treated, make noble metal in silicon process of setting toward silicon cyrystal boundary segregation and Enrichment；The step（2）Middle heat treatment process includes that 700 DEG C are cooled to after being heated to silicon-base alloy remelting hereinafter, heating 700 DEG C are subsequently cooled to below to silicon-base alloy fusing point hereinafter, cooling velocity is >=0.1 DEG C/min；
（3）By step（2）In it is heat treated after silicon-base alloy be ground into powder；With the non-silicon object of wet-leaching silicon grain boundaries Phase makes the noble metal becomeing trapped in silicon-base alloy be transferred to leachate；
（4）By step（3）Middle leaching material is filtered processing, respectively obtains solid-state high-purity silicon powder and the leaching containing noble metal Liquid；
（5）By step（4）Obtained in high-purity silicon powder as step（1）In silicon materials recirculate and use, or be sent to photovoltaic Or electronic product enterprise is as the raw material for preparing solar energy level silicon or electronic-grade silicon.
2. method that is according to claim 1 while recycling noble metal and prepare HIGH-PURITY SILICON, it is characterised in that：The step （1）In noble metal materials to be processed be primarily referred to as the material containing at least one precious metal element, the mistake including platinum group metal Imitate cleaning catalyst for tail gases of automobiles or petro chemical industry carried catalyst.
3. method that is according to claim 1 while recycling noble metal and prepare 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. method that is according to claim 1 while recycling noble metal and prepare HIGH-PURITY SILICON, it is characterised in that：The step （1）Middle additive is CaO, SiO2、Al2O3, one or more of MgO arbitrary proportion mixture, total addition level is to be processed expensive Metalliferous material quality >=30%；But works as in noble metal materials and contained CaO, SiO2、Al2O3, two kinds in MgO and two or more When, the case where additive can be added without.
5. method that is according to claim 1 while recycling noble metal and prepare HIGH-PURITY SILICON, it is characterised in that：The step （1）Middle smelting temperature is >=1450 DEG C, soaking time >=1 hour.
6. method that is according to claim 1 while recycling noble metal and prepare HIGH-PURITY SILICON, it is characterised in that：The step （3）The leaching agent being added in middle wet method leaching process is one of hydrofluoric acid containing, hydrochloric acid, nitric acid, sulfuric acid or a variety of any ratios Example mixture, leaching detailed process is：Leachate and silicon-base alloy powder liquid-solid ratio are >=1:1mL/g, extraction temperature are >=25 DEG C, extraction time is >=1 hour.
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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
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