CN112981101A - Method for simultaneously recycling cut silicon waste and trapping rare and precious metals in spent catalyst - Google Patents

Method for simultaneously recycling cut silicon waste and trapping rare and precious metals in spent catalyst Download PDF

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CN112981101A
CN112981101A CN202110141888.0A CN202110141888A CN112981101A CN 112981101 A CN112981101 A CN 112981101A CN 202110141888 A CN202110141888 A CN 202110141888A CN 112981101 A CN112981101 A CN 112981101A
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CN112981101B (en
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雷云
雷敏鹏
马文会
何勇
杨清源
杨东方
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Kunming University of Science and Technology
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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    • C01B33/00—Silicon; Compounds thereof
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    • C22B11/00—Obtaining noble metals
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    • C22B11/021—Recovery of noble metals from waste materials
    • C22B11/026—Recovery of noble metals from waste materials from spent catalysts
    • C22B11/028—Recovery of noble metals from waste materials from spent catalysts using solid sorbents, e.g. getters or catchment gauzes
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    • C22B11/048—Recovery of noble metals from waste materials from spent catalysts
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    • C22B59/00—Obtaining rare earth metals
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    • 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
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    • Y02P10/20—Recycling
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to a method for simultaneously recycling cut silicon waste and trapping rare and precious metals in a spent catalyst, belonging to the field of utilization of solid waste resources. Reducing and smelting the silicon waste, the spent catalyst containing rare and noble metals, the slag former and the additive together, and separating slag from metal after smelting to obtain silicon-based alloy containing rare and noble metals and waste slag; grinding the obtained silicon-based alloy containing rare and noble metals to powder smaller than 74 microns, and pickling with aqua regia and filtering to obtain silicon powder and leachate containing rare and noble metals; pickling the obtained silicon powder with a fluorine-containing acid solution and filtering to obtain high-purity silicon and a filtrate containing precious metal; adding fluoride into the obtained leaching solution containing rare and noble metals to form a precipitate, and filtering to obtain rare earth metal fluoride precipitate and a filtrate containing noble metals. The invention can simultaneously treat two different industrial solid wastes and has obvious economic benefit and industrialization prospect.

Description

Method for simultaneously recycling cut silicon waste and trapping rare and precious metals in spent catalyst
Technical Field
The invention relates to a method for simultaneously recycling cut silicon waste and trapping rare and precious metals in a spent catalyst, belonging to the field of utilization of solid waste resources.
Background
With the gradual depletion of traditional non-renewable energy sources such as petroleum and coal and the environmental protection concept of clean production, clean and renewable solar energy resources are widely concerned by various countries and researchers in the world. As a big country of solar energy resource utilization, China has the installed capacity of solar cells in the photovoltaic industry continuously positioned the first world since 2013, the raw material for producing the solar cell important components is high-purity solar-grade silicon (99.9999%), the high-purity solar-grade silicon can be obtained by purifying low-purity metallurgical-grade silicon (99%) through a pyrogenic process or a wet process, and the method is also the main way for preparing the solar-grade silicon at present. The preparation process of the solar cell module is to cut a solar-grade silicon rod or a silicon ingot into silicon wafers and then treat and use the silicon wafers. The existing cutting methods mainly comprise a diamond wire cutting method and a mortar cutting method, and compared with the mortar cutting method, the diamond wire cutting method has larger and larger market share due to higher efficiency and lower silicon loss in the cutting process. When the silicon rod is cut by adopting the diamond wire cutting method, the diameter of the cutting wire is approximately equal to the thickness of the cut silicon wafer, so that approximately 35-40% of crystalline silicon can be cut into micron-sized silicon powder in the cutting process, and the micron-sized silicon powder becomes cut silicon waste. With the rapid development of the photovoltaic industry, more and more silicon powder waste is generated, and 24 ten thousand tons of silicon waste is cut every year in China. Silicon crystals carry a large amount of impurities during the cutting process, such as: carbon and oxygen elements are introduced into the cooling liquid, aluminum elements are introduced into the silicon ingot by cutting the fixed base, and the total amount of the mixed impurities reaches 14% and is difficult to remove. Therefore, how to efficiently recycle the crystalline silicon cutting waste is a problem faced at present.
The platinum group metals are mainly used in the industrial production of catalysts, such as automobile exhaust gas purification catalysts and catalysts for petrochemical industry. Since platinum group metals have special catalytic ability for purifying automobile exhaust, more than 60% of platinum, palladium and rhodium are used in the production of automobile exhaust purification catalysts every year, and the resource reserves of platinum group metals are very limited, and although many organizations are researching new catalysts to replace or reduce the use of platinum group metals, the demand for platinum group metals is further increased with the increase of the number of automobiles and the improvement of environmental standards. In 2020, the quantity of automobiles in China can reach 2.81 hundred million, and 2200 million of invalid automobile exhaust purification catalysts are expected to be generated in China every year after 2025 as automobiles with exhaust purification devices begin to enter the scrapping period in large quantities. Because platinum group metal resources are rare and expensive, the recovery of rare and precious metals from the spent automobile exhaust purification catalyst is significant and receives attention from various governments. In addition, the spent automobile exhaust purification catalyst also contains a small amount of rare metals which are not recovered by an effective method at present. In view of the current situation of platinum group metals and rare metals, a higher demand is put on the technology for recovering the platinum group metals and rare metals in the spent automobile exhaust gas purification catalyst. In addition to automotive exhaust gas purification catalysts, platinum group metals are also used in the manufacture of spent petrochemical catalysts, such as alumina-supported catalysts containing platinum group metals, and how to recover platinum group metals from spent petrochemical catalysts by combined fire-wet processes is one of the current resource recovery problems. Therefore, if a method is available to effectively recycle the platinum group metals and rare metal resources from the spent catalyst, it would be beneficial to the recycling of the rare metal resources and sustainable development of the environment.
The difference between the invention and the patent ZL201710613387.1 is as follows: (1) the invention provides a method for strengthening the trapping process of platinum group metals by directly adding a small amount of Fe, Cu and oxides thereof with affinity with the platinum group metals in the process of trapping the precious metals in a silicon trapping catalyst, wherein the added Fe and Cu can not only strengthen the trapping process of the platinum group metals, improve the trapping rate of the platinum group metals, but also improve the density of a silicon alloy after silicon trapping, so that the silicon alloy can be settled below slag ZL, and are more favorable for discharging silicon-based melt at a furnace bottom furnace door opening in the industrialized process to achieve the purpose of separating slag from gold, but only silicon is used as a trapping agent in patent 201710363321.1, because the density of the silicon is not greatly different from the density of the slag, although the slag and the silicon can also be separated, the silicon-based alloy is generally in the middle part of the slag (surrounded by molten slag), therefore, in the actual industrialized process, the silicon-based alloy melt cannot be discharged through the furnace bottom furnace opening, the slag and the silicon alloy are difficult to separate in the industrial application process; (2) the silicon material in patent ZL201710613387.1 only comprises silicon and silicon-based alloy, while the silicon material in the present invention is mainly silicon waste with very low price, including cut silicon waste generated in the cutting process of polysilicon, monocrystalline silicon, etc., leftover materials of silicon ingot, ineffective solar cell silicon wafers, etc., wherein the cost of the preferred cut silicon waste is about 1/4 of silicon, and the patent proposes that C, O and Al impurities in the silicon waste can be removed while the silicon waste traps rare precious metals in ineffective automobile catalysts, and the effect of trapping rare precious metals by using the silicon waste is the same as the effect of trapping rare precious metals by using pure silicon; (3) patent ZL201710613387.1 is only a method for enriching rare and precious metals, valuable metal enrichment is not further recycled, and the invention adopts a wet method technology to obtain high-purity silicon and separate and recycle rare earth in rare and precious metal leachate. The difference between the present invention and ZL201710363321.1 is: (1) the invention provides a method for strengthening the trapping process of platinum group metals by directly adding a small amount of Fe, Cu and oxides thereof with affinity with the platinum group metals in the process of trapping the precious metals in a silicon trapping catalyst, wherein the added Fe and Cu can not only strengthen the trapping process of the platinum group metals, improve the trapping rate of the platinum group metals, but also improve the density of a silicon alloy after silicon trapping, so that the silicon alloy can be settled below slag ZL, and are more favorable for discharging silicon-based melt at a furnace bottom furnace door opening in the industrialized process to achieve the purpose of separating slag from gold, but only silicon is used as a trapping agent in patent 201710363321.1, because the density of the silicon is not greatly different from the density of the slag, although the slag and the silicon can also be separated, the silicon-based alloy is generally in the middle part of the slag (surrounded by molten slag), therefore, in the actual industrialized process, the silicon-based alloy melt cannot be discharged through the furnace bottom furnace opening, the slag and the silicon alloy are difficult to separate in the industrial application process; (2) the silicon material in patent ZL201710363321.1 is silicon and silicon-based alloy, while the silicon material in the invention is mainly silicon waste with very low price, including cut silicon waste generated in the cutting process of polycrystalline silicon, monocrystalline silicon and the like, leftover materials of silicon ingot, ineffective solar cell silicon wafers and the like, wherein the cost of the preferred cut silicon waste is about 1/4 of silicon, and the patent proposes that C, O and Al impurities in the silicon waste can be removed while the silicon waste traps rare and noble metals in ineffective automobile catalysts, and the effect of trapping rare and noble metals by using the silicon waste is the same as the effect of trapping rare and noble metals by using pure silicon; (3) patent ZL201710363321.1 recovers only the platinum group metals, while the invention can recover the platinum group metals, rare earth and rare metals in the catalyst at the same time. The difference between the invention and the patent CN201811268803.X is that: (1) patent CN201811268803.X uses carbon-containing material, hydrogen, CO and other reducing agent mixed iron oxide or copper oxide, invalid catalyst to reduce at low temperature, and then uses simple substance silicon or silicon-based alloy to perform high temperature smelting and trapping of rare and precious metals, but the invention does not use carbon-containing material, hydrogen, CO and other reducing agent to reduce iron oxide or copper oxide, and has C emission, but uses silicon waste to reduce iron oxide or copper oxide, or directly adds metallic iron or metallic copper to improve platinum group metal trapping rate and silicon alloy density, the invention has no C emission; (2) in patent CN201811268803.X, elemental silicon or silicon-based alloy is used for high-temperature smelting and trapping of rare and precious metals, the trapping agent adopted by the invention is silicon waste, especially when silicon cutting waste is adopted, the price of the silicon cutting waste is only 1/4 of the elemental silicon, and the patent proposes that C, O and Al impurities in the silicon waste can be removed while the silicon waste traps the rare and precious metals in the dead automobile catalyst, and the effect of trapping the rare and precious metals by using the silicon waste is the same as that of trapping the rare and precious metals by using pure silicon.
Disclosure of Invention
In view of the problems of the prior art, the invention provides a method for simultaneously recovering and utilizing silicon cutting waste materials and trapping rare and precious metals in a spent catalyst. The method can simultaneously treat two different industrial solid wastes, can prepare the silicon wastes into high-purity silicon (99.9%), can also recycle rare and precious metal resources in the spent catalyst, and has obvious economic benefit and industrialization prospect. The invention is realized by the following technical scheme.
A method for simultaneously recycling cut silicon waste and trapping rare and precious metals in a spent catalyst comprises the following steps:
step 1, reducing and smelting silicon waste, a spent catalyst containing rare noble metals, a slag former and an additive together, wherein the slag former is CaO and SiO2、MgO、Al2O3The smelting temperature of one or a mixture of more of the raw materials is higher than 1773K, the smelting time is 3-10 hours, and after the smelting is finished, slag and metal are separated to obtain silicon-based alloy containing rare and noble metals and waste slag;
step 2, grinding the silicon-based alloy containing rare and noble metals obtained in the step 1 to powder smaller than 74 microns, and pickling with aqua regia and filtering to obtain silicon powder and leachate containing rare and noble metals;
step 3, pickling the silicon powder obtained in the step 2 with a fluorine-containing acid solution, and filtering to obtain high-purity silicon and a filtrate containing precious metals;
and 4, adding fluoride into the leachate containing the rare and noble metals obtained in the step 2 to form a precipitate, and filtering to obtain a rare earth metal fluoride precipitate and a filtrate containing the noble metals.
The silicon waste in the step 1 is a reducing agent, the silicon waste is industrial solid waste taking silicon as a matrix, and the industrial solid waste comprises cut silicon waste generated in the cutting process of polycrystalline silicon, monocrystalline silicon and the like, leftover materials of silicon ingots, invalid solar cell silicon wafers and the like, and the cut silicon waste with low purity and low price is preferably selected.
The dead catalyst containing rare noble metals in the step 1 comprises a dead automobile exhaust purification catalyst and a dead catalyst taking alumina or other oxides as carriers in the petrochemical industry.
The additive in the step 1 is a metal with affinity for platinum group metals and oxides thereof, including iron, copper, iron alloy, copper oxide, nickel alloy or nickel oxide, and the additive may or may not be added, and the main difference is that the direct yield of the platinum group metals can be improved by adding the additive.
The fluoride in the step 4 is all that can form F in aqueous solution-Fluoride of (2), including HF or NH4F。
The additive in the step 1 can be not added
The invention has the beneficial effects that:
(1) according to the invention, the silicon waste is used as the rare and noble metal trapping agent to extract rare and noble metals in the spent catalyst, so that during the smelting and trapping process, the silicon waste has an obvious removing effect on C, O, Al and other impurities in the silicon waste, and the purpose of recovering the silicon waste can be achieved during the smelting and trapping process;
(2) the invention not only can prepare the silicon waste into high-purity silicon to realize the recycling of the silicon waste, but also can trap rare noble metals in the failed catalyst by a pyrogenic process;
(3) compared with the existing recovery treatment of the spent catalyst by a copper capture method and an iron capture method, the method has the advantages that the method can effectively capture the platinum group metal and the rare metal in the spent catalyst at the same time, has no carbon emission and less silicon loss, and does not need to consider the slag-silicon ratio and the dosage of a capture agent;
(4) the invention is a technology without waste gas generation, carbon emission, low cost, environmental protection and high efficiency;
(5) the invention provides a method for separating rare earth metal and noble metal in a solution containing rare noble metal by adding fluoride;
(6) according to the invention, a small amount of Fe and Cu which have affinity with platinum group metals and oxides thereof are directly added in the process of collecting the precious metals in the catalyst by silicon to reinforce the collection process of the platinum group metals, and the density of the silicon alloy is improved, so that the separation of the silicon alloy and slag in the industrial process is facilitated; when the additives are Fe and Cu oxides, conventional C, H is not used2CO, etc. as reductionThe agent reduces the oxides of Fe and Cu, but directly uses silicon waste as a reducing agent to reduce the oxides of Fe and Cu, and no C is discharged in the reduction process.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
Example 1
As shown in FIG. 1, the method for simultaneously recycling cut silicon waste and trapping rare noble metals in a spent catalyst comprises the following steps:
step 1, taking a failed automobile exhaust purification catalyst (cordierite is used as a carrier, the contents of Pt, Pd, Ph, Zr, Ce, Nd and La are 522ppmw, 546ppmw, 143ppmw, 6.5 mass%, 3.8 mass%, 0.55 mass% and 0.64 mass% respectively), cut silicon waste (Si content 85 wt%, wherein the contents of main impurities C, O and Al are 1.52mass%, 5.97mass% and 0.91mass% respectively), an additive (metallic Fe accounting for 10% of the cut silicon waste mass) and a slag forming agent (CaO, SiO, mass ratio)2、Al2O3And MgO, the addition amounts of which respectively account for 19.6%, 17.3%, 8.5% and 1% of the mass of the failed automobile exhaust purification catalyst, are reduced and smelted under the argon atmosphere, and the proportion of the total slag amount to the silicon carbide cutting silicon waste material is 1: 1; the smelting temperature is 1823K, the smelting time is 3 hours, the silicon-based alloy containing rare and precious metals and waste slag are obtained after slag-metal separation, and the direct yield of Pt, Pd, Ph, Zr, Ce, Nd and La in the spent automobile exhaust purification catalyst is respectively 98.6%, 99.4% and 97.1%, 88.2%, 79.5%, 77.5% and 67.2%;
and 2, grinding the silicon-based alloy containing rare and noble metals obtained in the step 1 to powder smaller than 75 microns, and carrying out acid washing by using aqua regia, wherein the solid-to-liquid ratio is 1: 10g/ml, 3 percent of aqua regia by volume: 1 HCl (analytical grade) and HNO3(analytically pure), the pickling temperature is 348K, the pickling time is 5 hours, and silicon powder and leachate containing rare and noble metals are obtained after filtration;
and 3, pickling the silicon powder obtained in the step 2 by using HF (hydrogen fluoride) together with HCl, wherein the solid-to-liquid ratio is 1: 10g/ml, HF (analytically pure) and HCl (analytically pure) volume ratio 1: 1, pickling at a temperature of 348K for 4 hours, and filtering to obtain high-purity silicon powder (99.965%, wherein the contents of C, O, Pt, Pd, Rh, Zr, Ce, Nd, La, Ca, Al, Mg and Fe are respectively 0.01mass%, 0.8 ppmw, 0.7 ppmw, 1.1 ppmw, 4.3 ppmw, 1.2 ppmw, 0.8 ppmw, 0.02 ppmw, 3.2 ppmw, 87 ppmw, 27 ppmw and 23 ppmw) and a filtrate containing precious metals;
step 4, adding NH into the leaching solution containing rare and precious metals obtained in the step 24The rare earth elements in the acid solution are precipitated by F acid (analytically pure) in the form of cerium fluoride, neodymium fluoride and lanthanum fluoride mixture, and the rare earth fluoride mixture with the purity of 97.36% (the contents of main impurities of Ca, Al, Cl, Mg and Fe are respectively 1mass%, 0.35 mass%, 0.72 mass%, 0.29 mass% and 0.28 mass%) and the filtrate containing the noble metal are obtained after filtration, washing and drying.
Example 2
As shown in fig. 1, the method for simultaneously recycling cut silicon waste and trapping rare noble metals in a spent catalyst comprises the following steps:
step 1, cutting silicon waste (Si content 86.9 wt.%, wherein the contents of main impurities C, O and Al are respectively 0.83mass%, 3.85mass% and 0.87 mass%), and additives (Cu) by taking cordierite as a carrier and the contents of Pt, Pd, Ph, Zr, Ce, Nd and La are respectively 522ppmw, 546ppmw, 143ppmw, 6.5 mass%, 3.8 mass%, 0.55 mass% and 0.64 mass%), and using the waste (Cu content 86.9 wt.%), wherein the contents of main impurities C, O and Al are respectively 0.83mass%, 3.85mass% and 0.87 mass%), and mixing the waste with the waste2O, accounting for 10 percent of the mass of the cutting silicon waste material) and slag forming agents (CaO, SiO)2、Al2O3And the addition amounts respectively account for 19.1%, 18.3% and 10.5% of the mass of the failed automobile exhaust purification catalyst) and are subjected to reduction smelting in an argon atmosphere, wherein the proportion of the total slag amount to the cutting silicon waste is 1: 1, the smelting temperature is 1873K, the smelting time is 3 hours, silicon-based alloy containing rare and precious metals and waste slag are obtained after slag-metal separation, and the direct yield of Pt, Pd, Ph, Zr, Ce, Nd and La in the spent automobile exhaust purification catalyst is respectively 98.9%, 99.1% and 98.7%, 88.5%, 82.2%, 80.2% and 68.9%;
step 2, grinding the silicon-based alloy containing rare noble metals obtained in the step 1 to be less than75-micron powder, acid-washed by aqua regia, and the solid-to-liquid ratio is 1: 10g/ml, 3 percent of aqua regia by volume: 1: 1 HCl (analytical grade), HNO3(analytical purity), H2O, the pickling temperature is 348K, the pickling time is 5 hours, and silicon powder and leachate containing rare and noble metals are obtained after filtration;
and 3, pickling the silicon powder obtained in the step 2 by using HF (hydrogen fluoride) together with HCl, wherein the solid-to-liquid ratio is 1: 10g/ml, HF (analytically pure) and HCl (analytically pure) volume ratio 1: 1, pickling at a temperature of 348K for 3 hours, and filtering to obtain high-purity silicon powder (99.965%, wherein the contents of C, O, Pt, Pd, Rh, Zr, Ce, Nd, La, Ca, Al, Mg and Cu are respectively 0.01mass%, 0.6 ppmw, 1.1 ppmw, 0.5 ppmw, 3.9ppmw, 1.5 ppmw, 1.1 ppmw, 0.05 ppmw, 4.5 ppmw, 101 ppmw, 21 ppmw and 15 ppmw) and a filtrate containing precious metals;
and 4, adding HF acid (analytically pure) into the leaching solution containing the rare and precious metals obtained in the step 2 to separate out the rare earth elements in the acid solution in the form of cerium fluoride, neodymium fluoride and lanthanum fluoride mixture precipitates, and filtering, washing and drying to obtain a rare earth fluoride mixture with the purity of 97.68% (the contents of main impurities of Ca, Al, Cl, Mg and Cu are respectively 0.87mass%, 0.23 mass%, 0.45 mass%, 0.32 mass% and 0.45 mass%) and a precious metal-containing filtrate.
Example 3
As shown in fig. 1, the method for simultaneously recycling cut silicon waste and trapping rare noble metals in a spent catalyst comprises the following steps:
step 1, carrying out reduction smelting on a spent petrochemical industry carrier catalyst (alumina is used as a carrier, and the Ce content and the Pt content are respectively 4.8 mass percent and 2300 ppmw), cut silicon waste (Si content is 86.9 wt.%, wherein the main impurities C, O and the Al content are respectively 0.83mass percent, 3.85mass percent and 0.87mass percent), an additive (metallic copper accounting for 8 percent of the mass of the cut silicon waste), and a slag former (CaO and MgO, the addition amounts respectively account for 79.2 percent and 9 percent of the mass of the catalyst) in an argon atmosphere, wherein the proportion of the total slag amount to the cut silicon waste is 1: 0.4, the smelting temperature is 1923K, the smelting time is 3 hours, then the mixture is cooled at the cooling rate of 2K/min, silicon alloy containing platinum and cerium and waste slag are obtained after slag-metal separation, and the direct yield of Pt and Ce in the catalyst is 99.6 percent and 87.4 percent respectively.
And 2, grinding the silicon alloy containing the platinum and the cerium obtained in the step 1 to powder smaller than 75 micrometers, and carrying out acid washing by using aqua regia, wherein the volume ratio of the aqua regia is 3: 1 HCl (analytical grade) and HNO3(analytical purity), solid-to-liquid ratio 1: 10g/ml, acid washing temperature of 348K and acid washing time of 6h, and filtering to obtain silicon powder and leachate containing rare and noble metals;
step 3, matching the silicon powder obtained in the step 2 with HF (hydrogen fluoride) with H2C2O4Acid washing is carried out, wherein the solid-to-liquid ratio is 1: 10g/ml, HF (analytically pure) and H2C2O4Volume ratio (analytically pure) 2: 1, pickling at a temperature of 348K for 2 hours, and filtering to obtain high-purity silicon powder (99.95 percent, and the contents of main impurities C, O, Ca, Mg, Al, Pt, Ce and Cu are respectively 0.02mass percent, 0.01mass percent, 21 ppmw, 107 ppmw, 183 ppmw, 0.8 ppmw, 3.5 ppmw and 4.7 ppmw) and a filtrate containing precious metals;
and 4, adding HF acid (analytically pure) into the leaching solution containing the rare and noble metals obtained in the step 2 to separate out cerium in the acid solution in the form of cerium fluoride, and filtering, washing and drying to obtain cerium fluoride (the contents of main impurities of Ca, Al, Cl, Mg and Cu are respectively 0.75 mass%, 0.33 mass%, 0.56 mass%, 0.34 mass% and 0.51 mass%) with the purity of 97.51% and a filtrate containing the noble metals.
Example 4
Step 1, cutting silicon waste (Si content 86.9 wt.%, wherein the contents of main impurities C, O and Al are respectively 0.83mass%, 3.85mass% and 0.87 mass%) and slagging agent (CaO and SiO) by taking cordierite as a carrier and the contents of Pt, Pd, Ph, Zr, Ce, Nd and La are respectively 522ppmw, 546ppmw, 143ppmw, 6.5 mass%, 3.8 mass%, 0.55 mass% and 0.64 mass%) and waste automobile exhaust purification catalyst (CaO and SiO and 0.87 mass%)2The addition amounts of the silicon-containing slag and the cutting silicon waste respectively account for 16.8 percent and 20 percent of the mass of the failed automobile exhaust purification catalyst) and are reduced and smelted together in the argon atmosphere, and the proportion of the total slag amount to the cutting silicon waste is 1: 0.6, the smelting temperature is 1823K, the smelting time is 8 hours, and the silicon-based alloy containing rare noble metals is obtained after slag-metal separationAnd waste residues, wherein the direct yield of Pt, Pd, Ph, Zr, Ce, Nd and La in the spent automobile exhaust purification catalyst is 95.4%, 96.1% and 92.7%, 79.2%, 71.4%, 68.5% and 64.2% respectively;
step 2, grinding the silicon-based alloy containing rare and noble metals obtained in the step 1 to powder smaller than 75 microns, and carrying out acid washing by using aqua regia, wherein the volume ratio of the aqua regia is 3: 1 HCl (analytical grade) and HNO3(analytical purity), solid-to-liquid ratio 1: 10g/ml, the pickling temperature is 348K, the pickling time is 5 hours, and silicon powder and leachate containing rare and noble metals are obtained after filtration;
and 3, pickling the silicon powder obtained in the step 2 by using HF (hydrogen fluoride) together with HCl, wherein the solid-to-liquid ratio is 1: 10g/ml, HF (analytically pure) and HCl (analytically pure) volume ratio 1: 1, pickling at a temperature of 348K for 4 hours, and filtering to obtain high-purity silicon powder (99.955%, wherein the contents of C, O, Pt, Pd, Rh, Zr, Ce, Nd, La, Ca, Al and Mg are respectively 0.02mass%, 0.01mass%, 1.2 ppmw, 0.9 ppmw, 0.5 ppmw, 3.2 ppmw, 0.9 ppmw, 0.7 ppmw, 0.05 ppmw, 2ppmw, 98 ppmw and 35 ppmw) and a filtrate containing precious metals;
and 4, adding HF acid (analytically pure) into the leaching solution containing the rare and precious metals obtained in the step 2 to separate out the rare earth elements in the acid solution in the form of cerium fluoride, neodymium fluoride and lanthanum fluoride mixture precipitates, and filtering, washing and drying to obtain a rare earth fluoride mixture with the purity of 97.46% (the contents of main impurities of Ca, Al, Cl and Mg are respectively 1.1mass%, 0.32 mass%, 0.8 mass% and 0.32 mass%) and a filtrate containing the precious metals.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.

Claims (6)

1. A method for simultaneously recycling cut silicon waste and trapping rare and precious metals in a spent catalyst is characterized by comprising the following steps:
step 1, silicon waste, a spent catalyst containing rare noble metals, a slagging agent and an additive are mixed togetherReducing and smelting, wherein the slag former is CaO and SiO2、MgO、Al2O3The smelting temperature of one or a mixture of more of the raw materials is higher than 1773K, the smelting time is 3-10 hours, and after the smelting is finished, slag and metal are separated to obtain silicon-based alloy containing rare and noble metals and waste slag;
step 2, grinding the silicon-based alloy containing rare and noble metals obtained in the step 1 to powder smaller than 74 microns, and pickling with aqua regia and filtering to obtain silicon powder and leachate containing rare and noble metals;
step 3, pickling the silicon powder obtained in the step 2 with a fluorine-containing acid solution, and filtering to obtain high-purity silicon and a filtrate containing precious metals;
and 4, adding fluoride into the leachate containing the rare and noble metals obtained in the step 2 to form a precipitate, and filtering to obtain a rare earth metal fluoride precipitate and a filtrate containing the noble metals.
2. The method for simultaneously recycling cut silicon scrap and trapping rare noble metals in spent catalyst according to claim 1, characterized in that: the silicon waste in the step 1 is a reducing agent, is an industrial solid waste taking silicon as a substrate, and comprises cutting silicon waste, silicon ingot leftover materials and invalid solar cell silicon wafers, wherein the cutting silicon waste is generated in the cutting process of polycrystalline silicon and monocrystalline silicon.
3. The method for simultaneously recycling cut silicon scrap and trapping rare noble metals in spent catalyst according to claim 1, characterized in that: the dead catalyst containing rare noble metals in the step 1 comprises a dead automobile exhaust purification catalyst and a dead catalyst taking alumina or other oxides as carriers in the petrochemical industry.
4. The method for simultaneously recycling cut silicon scrap and trapping rare noble metals in spent catalyst according to claim 1, characterized in that: the additive in the step 1 is a metal with affinity of platinum group metals and oxides thereof, including iron, copper, iron alloy, copper oxide, nickel alloy or nickel oxide.
5. The method for simultaneously recycling cut silicon scrap and trapping rare noble metals in spent catalyst according to claim 1, characterized in that: the fluoride in the step 4 is all that can form F in aqueous solution-Fluoride of (2), including HF or NH4F。
6. The method for simultaneously recycling cut silicon scrap and trapping rare noble metals in spent catalyst according to claim 1, characterized in that: the additives in step 1 can be omitted.
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