CN110484746B - Noble metal leaching agent and method for recovering noble metal from waste catalyst - Google Patents
Noble metal leaching agent and method for recovering noble metal from waste catalyst Download PDFInfo
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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
- 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
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Abstract
The invention discloses a noble metal leaching agent and a method for recovering noble metals from waste catalysts. The precious metal leaching agent consists of ionic liquid, trichloroisocyanuric acid or dichloroisocyanuric acid and a solvent, wherein the mass ratio of the ionic liquid to the trichloroisocyanuric acid or dichloroisocyanuric acid is 30: 1-5: 1, and the volume ratio of the solvent to the ionic liquid is 10: 1-1: 1; the anion of the ionic liquid is selected from at least one of chloride ion, bromide ion, iodide ion, thiocyanate ion and dinitrile amine ion, and the cation is selected from at least one of pyrrolidine, quaternary ammonium salt and quaternary phosphonium salt. The invention provides a method for recovering noble metals from a waste catalyst by using the noble metal leaching agent. The noble metal leaching agent is economic, environment-friendly and efficient, can effectively carry out innocent treatment on the waste catalyst and recover noble metals of the waste catalyst, realizes the recycling of waste resources, reduces the environmental pollution and improves the social and economic benefits at the same time.
Description
Technical Field
The invention relates to a precious metal leaching agent and a method for recovering precious metals in a waste catalyst based on the precious metal leaching agent.
Background
The noble metal mainly refers to 8 metal elements such as gold, silver and platinum group metals (ruthenium, rhodium, palladium, osmium, iridium, platinum). Noble metals are widely used in modern industries due to their high melting point, high boiling point, low vapor pressure, oxidation and corrosion resistance characteristics. With the development of industries such as petroleum, chemical industry, environmental protection and the like, the dosage of the noble metal catalyst is increased year by year. The catalyst loses activity due to problems of poisoning, easy structure of a carrier, carbon accumulation and the like in the using process, and needs to be replaced periodically, according to statistics, the amount of the waste catalyst generated in the world every year is about 50-70 ten thousand tons, and the content of the noble metal in the replaced catalyst is higher than that of corresponding ore, so that the noble metal in the recovered waste catalyst has high economic value and meets the requirement of sustainable development.
In metal catalysts, the recovery of metals from spent catalysts is different from the direct dissolution of metals due to the strong interaction of the metals with the support.
Literature [ Journal of American Chemistry Society,1978, 100:170]It is reported that the supported on TiO2The above group VIII noble metals Pt, Pd, Ru, Rh, Os and Ir are reacted at 500 deg.C2After reduction in the atmosphere, at room temperature to H2The chemical adsorption force with CO is greatly reduced and tends to be zero, and the same material is subjected to H treatment at 200 DEG C2Reduced pair H2And the adsorption capacity of CO has no effect. This phenomenon is known as "Metal-Support Interaction" (SMSI) by the reference.
There has been a great deal of research into the mechanism of strong metal-support interactions, attempting to explain this phenomenon from different perspectives, but no theory has been proposed of the general applicability to different supported catalyst systems. The inter-metal bonding, special morphology structure, interface charge migration and material transport are the most common explanations about the metal-carrier strong interaction mechanism, but no matter which explanation is adopted, the possible changes of the noble metal in the catalyst in the bonding form, the particle structure, the outer layer electronic structure and the like can be explained from different angles, and the method is different from the simple noble metal.
Literature [ Journal of the American Chemistry Society,1978, 100:170]An explanation for the strong metal-support interaction is presented, which suggests Pt/TiO2The surface has TiPt after high-temperature reduction3Two functions possibly exist between the noble metal and the titanium ion or titanium atom, one is d orbital occupied by the noble metal ion and Ti4+And the other part is an intermetallic compound formed by the contribution of an atom having an internal pairing d electron to an empty d orbital atom.
Literature [ Journal of the American Chemistry Society,1979, 101:2870]By using a molecular orbital method, a model of strong interaction of the metal and the carrier is calculated and given, and H is shown2Reduction makes Pt atoms and Ti atoms in close contact to cause intermetallic bonding and intermetallic compound TiPt3And (4) forming. The expanded Brewer inter-ionic bonding interaction theory suggests that intermetallic phases and compounds with stoichiometric ratios are formed between the left half transition metal element (or lack-d electron element) containing a vacant or half-full d-orbitals and the right half transition metal element (or rich-d electron element) containing an anti-bonding d-band, and also supports the view of intermetallic bonding.
In addition to intermetallic bonding, metals in catalysts may also give rise to particular morphological structures, which are also considered to be one of the mechanisms by which strong metal-support interactions may occur. Literature [ Journal of Catalyst, 1979, 56:390]Pt/TiO is observed by a transmission electron microscope2Pt particles in the system generate a two-dimensional raft structure, and the morphology of the Pt particles can be reversibly changed by changing the conditions of high-temperature reduction and oxidation treatment. Literature [ Journal of American Chemistry Society, 2012, 134:8968]Discovery of Pt8/CeO2Catalyst in the Water gas conversion reaction, Pt8The morphology of the particles varies with the adsorbate species, and the DFT calculation also demonstrates the existence of such variation.
Metal-oxide interfacial charge transport, which is an important aspect of metal-carrier interactions, will cause changes in the electron density at the surface of the metal. Literature [ The Journal of Chemical Physics,1983, 87:1327]Firstly, the titanium oxide TiO loaded with Pt is treated2TiO and Ti2O3TEM and XPS studies of (II) indicate that the metal-support interaction is TiO2Conduction band electron tunneling in bulk phase through TiO2The surface is the result of Pt particle migration. Article (Chinese character)Document [ Journal of catalysis, 1983, 82:299]Research on Pt/TiO by EXAFS2And bulk Pt at high temperature H2The d electron filling rate after reduction under the condition shows that the strong metal-carrier interaction is not the result of mass carrier migration, but the more fine electronic structure change. The driving force of the reaction is that the system has a tendency to reduce its surface energy. Literature [ The Journal of Chemical Physics,1984, 88:5172]Research on Pt/TiO treated by high-temperature vacuum by using Auger electron spectroscopy and temperature programming static secondary mass spectrometry2Catalyst, mobile TiO believed to be produced during reductionxThe cladding of the metal is H2And the decrease in CO adsorption activity, and it is considered that electron transfer between the metal and the carrier is also another important cause of the decrease in the adsorption capacity of the catalyst, that is, the strong metal-carrier interaction is a result of both interface substance transport and charge transfer.
Current means of recovering precious metals from spent catalysts include: 1. fire method: such as pyrogenic chlorination and high temperature volatilization, high temperature smelting and metal capture, and incineration. The method is simple and convenient, but has large energy consumption and low metal recovery rate, and the generated waste gas and waste residue bring secondary environmental pollution, thereby limiting the application of the method. 2. And (2) wet method: such as a method of dissolving a carrier, a method of dissolving an active ingredient. The method has the advantages of low cost, high leaching agent recovery rate, small air pollution and the like, and therefore, the method gradually becomes a development trend.
The method for dissolving active components is to add reagent to directly dissolve the noble metals in the waste catalyst and then extract the noble metals from the solution.
Document [ Washe management, 2012,32(6): 1209-]A thiourea leach process was reported using 24g/L thiourea and 0.6% Fe3+After 2h reaction at room temperature, about 90% of gold and 50% of silver were leached out. However, although gold recovery is above 90%, this process is too expensive due to too high consumption of thiourea.
Literature [ Chemical Engineering Journal,2015,259:457-]Selective leaching of gold with iodine-hydrogen peroxide was reported using 3% iodine, at a solid-to-liquid ratio of 15%,1% of H2O2And 100% gold recovery rate is obtained. In this process, an oxidant is required to increase the gold recovery while reducing the iodine consumption. However, the oxidizing agent may cause precipitation of iodine on the gold surface, resulting in a decrease in gold recovery.
The literature [ Hydrometallurgy,2014,13(3):305-350] reports leaching of gold with thiosulfate solutions. The results show that 98% of the gold is leached out after 10h of reaction with a solution of 0.12M thiosulfate and 0.2M ammonia. The main obstacle to the thiosulfate leaching process is the low profitability of commercial applications.
The literature [ Minerals Engineering,2009,22(4): 409-411 ] reports the recovery of gold using chloride as a reactant. The results show that increasing the extraction temperature and reaction time is beneficial to the extraction of gold, and the optimal recovery rate is 98.23% when 3600s are reacted at 873K. However, chloride is difficult to apply because it is highly corrosive and requires oxidizing conditions.
In conclusion, it is very meaningful to formulate a more economical, environmentally friendly and efficient leaching agent to recover the precious metals in the spent catalyst. Therefore, a precious metal recovery system using ionic liquid as a complexing agent and trichloroisocyanuric acid or dichloroisocyanuric acid as an oxidant is provided.
Disclosure of Invention
The invention aims to provide an economic, environment-friendly and efficient precious metal leaching agent.
The second purpose of the invention is to provide a method for recovering precious metals from waste catalysts based on the precious metal leaching agent, which has the advantages of simple process flow, less waste and side emission, capability of effectively carrying out harmless treatment on the waste catalysts and recovering the precious metals, realization of cyclic utilization of waste resources, reduction of environmental pollution and improvement of social and economic benefits.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a precious metal leaching agent which comprises ionic liquid, trichloroisocyanuric acid or dichloroisocyanuric acid and a solvent, wherein the mass ratio of the ionic liquid to the trichloroisocyanuric acid or the dichloroisocyanuric acid is 30: 1-5: 1, and the volume ratio of the solvent to the ionic liquid is 10: 1-1: 1;
the anion of the ionic liquid is selected from at least one of chloride ion, bromide ion, iodide ion, thiocyanate ion and dinitrile amine ion, and the cation is selected from at least one of pyrrolidine, quaternary ammonium salt and quaternary phosphonium salt;
the solvent is water, ethanol, isopropanol, acetone or acetonitrile.
When the leaching agent is prepared, all the components are uniformly mixed.
Preferably, the cation of the ionic liquid is at least one of N-hexylpyridine, N-butylpyridine, N-octylpyridine, N-butyl-N-methylpyrrolidine, tributyl-monomethyl ammonium and tetrabutyl phosphonium.
Preferably, the anion of the ionic liquid is chloride, bromide, iodide or dinitrile amine.
Further preferably, the ionic liquid is tributyl monomethyl ammonium chloride or tetrabutyl phosphonium chloride, N-butylpyridinium dicyanamide salt, N-octylpyridinium chloride salt, N-butyl-N-methylpyrrole bromide salt, N-hexylpyridinium iodide salt.
Preferably, the mass ratio of the ionic liquid to the trichloroisocyanuric acid or the dichloroisocyanuric acid is 20: 1-10: 1.
Preferably, the solvent is acetone or acetonitrile.
The invention further provides a method for recovering noble metals from waste catalysts, wherein the catalysts are supported catalysts, carriers of the supported catalysts are activated carbon, carbon nano tubes, graphene, aluminum oxide, silicon dioxide, titanium dioxide or molecular sieves, and active components of the supported catalysts are noble metals; the method comprises the following steps:
step (1), preparing a precious metal leaching agent;
step (2), leaching precious metals: mixing the noble metal leaching agent obtained in the step (1) with a waste catalyst, controlling the weight ratio of the noble metal leaching agent to the catalyst to be 20: 1-2: 1, stirring for 0.5-10 h at 15-100 ℃, and stirring at the speed of 400-1000 r/min to obtain a mixture;
step (3), solid-liquid separation: carrying out solid-liquid separation on the mixture obtained in the step (2), wherein the obtained liquid phase is an ionic liquid containing a gold complex, and the solid phase is a solid catalyst;
step (4), Soxhlet extraction: separating the ionic liquid adsorbed on the surface of the catalyst carrier from the solid catalyst obtained in the step (3) by adopting a Soxhlet extraction method, wherein the solvent used in the Soxhlet extraction is the same as the solvent in the noble metal leaching agent, the volume of the Soxhlet extraction is 10-30 times of the volume of the noble metal leaching agent, the extraction temperature is 30-180 ℃, the extraction time is 12-72 hours, and after the extraction is finished, the obtained solid phase is the catalyst carrier and can be continuously used for preparing the catalyst;
and (5) reducing: mixing the liquid phase obtained in the step (3) with the liquid phase obtained in the step (4), adding a reducing agent at 10-80 ℃, stirring for reaction, carrying out solid-liquid separation after full reaction, and removing the solvent by using a rotary evaporation method to obtain regenerated ionic liquid; the obtained solid phase is metal, and is washed by deionized water firstly, and then the base metal impurities are washed by nitric acid, so that the pure noble metal is obtained. The regenerated ionic liquid can be reused for preparing precious metal leaching, and the ionic liquid can be recycled.
In the invention, the carrier of the waste catalyst can be active carbon, carbon nano tube, graphene, aluminum oxide, silicon dioxide, titanium dioxide or molecular sieve and the like. The active carbon can be columnar carbon or spherical carbon, the particle size is 10-100 meshes, the ash content is less than or equal to 6.0 wt%, and the specific surface area is 500-1500 m2The pore volume is 0.25-2.5 mL/g. The carbon nano tube can be processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, the ash content is less than or equal to 6.0 wt%, and the specific surface area is 250-1200 m2The pore volume is 0.2-1.5 mL/g. The graphene can be processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, the ash content is less than or equal to 6.0 wt%, and the specific surface area is 500-1200 m2The pore volume is 0.2-2.5 mL/g. The aluminum oxide can be gamma-Al203And can be processed into columnar or spherical shape with particle size of 10-100 meshes and specific surface area of 250-800 m2The pore volume is 0.2-1.2 mL/g. The above-mentionedThe silicon dioxide can be processed into columnar or spherical shape, the particle size is l 0-100 meshes, and the specific surface area is 250-800 m2(iv)/g, pore volume 0.2-2.0 mL/g. The titanium dioxide can be processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 250-800 m2The pore volume is 0.1-1.2 mL/g. The molecular sieve can be ZSM-5, B molecular sieve, gamma molecular sieve, 5A molecular sieve, 10X molecular sieve or 13X molecular sieve, and can be processed into column or sphere with particle size of 10-100 meshes and specific surface area of 500-1500 m2The pore volume is 0.1-1.2 mL/g. The noble metal in the catalyst can be gold, silver and/or platinum group metal (ruthenium, rhodium, palladium, osmium, iridium and platinum). The invention has no special requirement on the content of the noble metal in the waste catalyst, and generally speaking, the noble metal loading of the supported catalyst is between 0.1 and 10 percent.
Preferably, in the step (2), the temperature is 20-40 ℃, the stirring time is 4-6 hours, and the stirring speed is 600-800 r/min.
Preferably, the solid-liquid separation in the step (3) and the step (5) is performed by a water circulation type filter.
Preferably, in the step (4), the volume of the solvent used in the Soxhlet extraction is 15-25 times of the volume of the leaching agent in the step (1), the extraction temperature is 80-120 ℃, and the extraction time is 24-48 h.
Preferably, the reducing agent is hydrazine hydrate, formic acid or borazane. The mass ratio of the added reducing agent to the noble metal in the waste catalyst is 50: 1-5: 1, and more preferably 30: 1-10: 1.
Preferably, in the step (5), the reduction temperature is 20-30 ℃, the stirring time is 0.5-5 h (more preferably 0.5-1 h), and the stirring speed is 400-1000 r/min (more preferably 600-800 r/min).
Preferably, in step (5), the concentration of nitric acid is 5 to 15 wt%.
Compared with the prior art, the invention has the following advantages:
1. the precious metal leaching agent is environment-friendly, low in use cost and high in precious metal leaching efficiency;
2. the method for recovering the noble metal from the waste catalyst has high recovery rate of the noble metal. In the process of leaching the noble metal in the waste catalyst by the method, the ionic liquid is adsorbed on the surface of the carrier, and generates strong coordination and complexation with the noble metal, so that the interaction between the noble metal and the carrier is weakened, the noble metal enters an ionic liquid phase from the surface of the carrier, and the aim of improving the recovery rate is fulfilled.
3. The recovery method provided by the invention has the advantages of simple process and mild conditions, and the recovery process only needs simple dissolving, evaporating and filtering operations, and does not need complex processes such as incineration, ion exchange, liquid phase digestion and the like.
4. The recovery method is environment-friendly, the main extraction component of the used leaching agent is ionic liquid, the property is stable, the volatility is extremely low, the leaching agent is non-toxic and harmless, the leaching agent is recycled in the whole recovery process, and the influence on the environment is extremely small; the incineration process of the traditional recovery method is avoided, and no waste gas is discharged; and a liquid phase digestion process is not needed, so that the use of strong acid and strong oxidant is avoided, and the discharge of waste liquid is greatly reduced.
5. The recovery method has high resource utilization rate, the recovered carrier can be reused to prepare the catalyst, and the ionic liquid and the solvent used in the recovery process can be recycled after simple separation. Compared with the traditional recovery method, the method has less resource waste and accords with the green chemical development direction.
Detailed Description
The invention is illustrated by the following specific examples. It should be noted that the examples are only intended to illustrate the invention further, but should not be construed as limiting the scope of the invention, which is in no way limited thereto. Those skilled in the art may make insubstantial modifications and adaptations to the invention described above.
Example 1
The method is described by the document [ functional material, 2012, 43: 222-225]The method prepares the Au @ AC catalyst with the loading capacity (relative to the mass of the carrier) of 3wt percent, wherein the carrier is columnar activated carbon, the particle size is 50 meshes, the ash content is 3.0wt percent, and the specific surface area is 1200m2The catalyst is used for catalyzing the reaction of oxidizing the ethylene glycol to become a waste catalyst。
Mixing 3g of ionic liquid tributyl-methyl ammonium chloride, 0.3g of trichloroisocyanuric acid and 5mL of acetone, adding 1g of the Au @ AC waste catalyst, stirring at the speed of 600r/min at the temperature of 20 ℃ for 5 hours, and then carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the gold complex, and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetone as solvent at 120 ℃ for 36 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.8ml of 80% hydrazine hydrate at 25 ℃, and stirring at the speed of 600r/min for 1 h. After solid-liquid separation, the solid phase is metal, washed by deionized water, and then washed by 0.5mL of 10% nitric acid to remove base metal impurities, so that 0.0297g of Au is obtained, and the recovery rate reaches 99%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 2
The synthesis of the protein by literature [ petroleum refining and chemical, 2009, 40 (2): 31-35]The method prepares Au @ SiO with the loading (relative to the mass of the carrier) of 1 weight percent2The catalyst has columnar SiO as carrier2The particle diameter is 50 meshes, the specific surface area is 300m2The catalyst is used for catalyzing and oxidizing cyclohexane to become a waste catalyst after being used for catalyzing and oxidizing the cyclohexane, and the pore volume is 0.7 mL/g.
2g of ionic liquid tributyl-methyl ammonium chloride, 0.3g of trichloroisocyanuric acid and 5mL of acetonitrile are mixed, and 3g of the Au @ SiO2 is added2Stirring the waste catalyst at the temperature of 30 ℃ at the speed of 500r/min for 6 hours, and then carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the palladium complex and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetonitrile as solvent at 100 ℃ for 48 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.8ml of 80% hydrazine hydrate at 25 ℃, and stirring at the speed of 600r/min for 2 h. After solid-liquid separation, the solid phase is metal, washed by deionized water, and then washed by 0.3mL of 10% nitric acid to remove base metal impurities, so that Au is 0.0291g, and the recovery rate reaches 97%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 3
The synthesis of the compounds by literature [ catalytic article, 2007, 28 (5):240-245]the method prepares the Au @ ZSM-5 catalyst with the load capacity (relative to the mass of the carrier) of 5wt percent, wherein the carrier is a columnar ZSM-5 molecular sieve, the particle size is 50 meshes, and the specific surface area is 300m2The catalyst is used for catalyzing and oxidizing beta-ionone to form a waste catalyst after reaction.
5g of ionic liquid tributyl-methyl ammonium chloride, 0.2g of trichloroisocyanuric acid and 5mL of ethanol are mixed, 1g of the Au @ ZSM-5 waste catalyst is added, and after stirring is carried out at the temperature of 40 ℃ at the speed of 600r/min for 4 hours, solid-liquid separation is carried out, wherein the liquid phase is the ionic liquid containing the palladium complex, and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 200mL of ethanol as solvent at 110 ℃ for 48 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 1ml of 85% formic acid at 25 deg.C, and stirring at 800r/min for 1 h. After solid-liquid separation, the solid phase is metal, washed by deionized water, and then washed by 0.7mL of 10% nitric acid to remove base metal impurities, so that 0.048g of Au is obtained, and the recovery rate reaches 96%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 4
The synthesis of the protein by the literature [ college chemical bulletin, 2013, 27 (5): 811-817]The method prepares the Pd @ AC catalyst with the loading capacity (relative to the mass of the carrier) of 3wt percent, wherein the carrier is columnar active carbon, the particle size is 50 meshes, the ash content is 3.0wt percent, and the specific surface area is 1200m2The catalyst is used for catalyzing the hydrogenation reaction of chloronitrobenzene to become a waste catalyst.
Mixing 3g of ionic liquid tributyl-methyl ammonium chloride, 0.4g of trichloroisocyanuric acid and 5mL of acetone, adding 1g of Pd @ AC, stirring at the temperature of 15 ℃ at the speed of 600r/min for 5 hours, and carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the gold complex, and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetone as solvent at 120 ℃ for 36 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.8ml of 80% hydrazine hydrate at 25 ℃, and stirring at the speed of 600r/min for 1 h. After solid-liquid separation, the solid phase is metal, washed by deionized water, and then washed by 0.5mL of 10% nitric acid to remove base metal impurities, so that Pd is 0.0288g, and the recovery rate reaches 96%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 5
By literature [ silicate report, 2016, 35 (5): 1427-1437]The method prepares Pd @ SiO with the selective loading (relative to the mass of the carrier) of 1wt percent2The catalyst has spherical SiO as carrier2The particle diameter is 50 meshes, the specific surface area is 300m2The catalyst is used for catalyzing hydrogen and oxygen to directly synthesize hydrogen peroxide, and becomes a waste catalyst after the reaction.
Mixing 4g of ionic liquid tetrabutyl phosphonium chloride, 0.3g of trichloroisocyanuric acid and 5mL of acetonitrile, and adding 2g of Pd @ SiO2Stirring the waste catalyst at the temperature of 30 ℃ at the speed of 800r/min for 6 hours, and then carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the palladium complex and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetonitrile as solvent at 100 ℃ for 48 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.5ml of 80% hydrazine hydrate at 25 ℃, and stirring at the speed of 600r/min for 2 h. After solid-liquid separation, the solid phase is metal, washed by deionized water, and then washed by 0.3mL of 10% nitric acid to remove base metal impurities, so that Pd is 0.0199g, and the recovery rate reaches 99%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 6
The method is characterized by comprising the following steps of (1): 94-100]The method prepares the Pd @ ZSM-5 catalyst with the loading capacity (relative to the mass of the carrier) of 5wt percent, wherein the carrier is columnar ZSM-5, the particle size is 50 meshes, and the specific surface area is 300m2The catalyst is used for catalyzing the combustion reaction of low-concentration methane to become a waste catalyst.
Mixing 2g of ionic liquid tetrabutyl phosphonium chloride, 0.2g of trichloroisocyanuric acid and 5mL of ethanol, adding 1g of the Pd @ ZSM-5 waste catalyst, stirring at the temperature of 40 ℃ at the speed of 600r/min for 4 hours, and then carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the palladium complex, and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL ethanol as solvent at 110 ℃ for 48 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 1ml of 85% formic acid at 25 deg.C, and stirring at 800r/min for 1 h. After solid-liquid separation, the solid phase is metal, washed by deionized water, and then washed by 0.7mL of 10% nitric acid to remove base metal impurities, so that Pd is 0.0475g, and the recovery rate reaches 95%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 7
The method is described by literature [ noble metal, 2012, 33 (1): 84-88]The Ru @ AC catalyst with the loading capacity (relative to the mass of the carrier) of 3 wt% is prepared by the method, the carrier of the Ru @ AC catalyst is columnar active carbon, the particle size is 50 meshes, the ash content is 3.0 wt%, and the specific surface area is 1200m2The catalyst is used for catalyzing the hydrogenation reaction of the aliphatic aldehyde to become a waste catalyst.
Mixing 3g of ionic liquid tetrabutyl phosphonium chloride, 0.3g of trichloroisocyanuric acid and 5mL of acetone, adding 1g of the Ru @ AC waste catalyst, stirring at the temperature of 20 ℃ at the speed of 600r/min for 3 hours, and carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the gold complex, and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetone as solvent at 120 ℃ for 36 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.8ml of 80% hydrazine hydrate at 25 ℃, and stirring at the speed of 600r/min for 1 h. After solid-liquid separation, the solid phase is metal, washed by deionized water, and then washed by 0.5mL of 10% nitric acid to remove base metal impurities, so that Ru is 0.0289g, and the recovery rate reaches 96%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 8
By literature [ chemical reaction engineering and process, 2017, 33 (2): 151-156]The method prepares Ru @ TiO with the loading (relative to the mass of the carrier) of 1 weight percent2Catalyst with spherical TiO as carrier2The particle diameter is 20 meshes, the specific surface area is 700m2The catalyst is used for catalyzing the organic acid oxidation reaction to become a waste catalyst.
Mixing 2g of ionic liquid tetrabutyl phosphonium chloride, 0.3g of trichloroisocyanuric acid and 5mL of acetonitrile, and adding2g of the above Ru @ TiO2Stirring the waste catalyst at the temperature of 30 ℃ at the speed of 800r/min for 6 hours, and then carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the palladium complex and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetonitrile as solvent at 100 ℃ for 48 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.5ml of 80% hydrazine hydrate at 25 ℃, and stirring at the speed of 600r/min for 2 h. After solid-liquid separation, the solid phase is metal, and is washed by deionized water, and then 0.3mL of 10% nitric acid is used for washing out base metal impurities, so that Ru is 0.0193g, and the recovery rate reaches 96%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 9
Through the literature [ Journal of catalysis,2013,301(5):175-]The method prepares the Ru @ MCM-49 catalyst with the load (relative to the mass of the carrier) of 5wt percent, wherein the carrier is columnar MCM-49, the particle size is 50 meshes, and the specific surface area is 800m2The catalyst is used for catalyzing the hydrogenation reaction of levulinic acid to become a waste catalyst.
Mixing 3g of ionic liquid N-butylpyridine dicyandiamide salt, 0.2g of trichloroisocyanuric acid and 5mL of ethanol, adding 1g of Ru @ MCM-49 waste catalyst, stirring at 40 ℃ at a speed of 500r/min for 4 hours, and carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the palladium complex, and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL ethanol as solvent at 110 ℃ for 48 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 1ml of 85% formic acid at 25 deg.C, and stirring at 800r/min for 1 h. The solid phase is metal, washed by deionized water and then by 0.7mL of 10% nitric acid to remove base metal impurities, so that Ru is 0.0481g, and the recovery rate reaches 96%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 10
Through literature [ low temperature and special gas, 2016,34(3): 28-32)]The method prepares the Pt @ AC catalyst with the loading capacity (relative to the mass of the carrier) of 3wt percent, wherein the carrier is columnar active carbon, the grain diameter is 50 meshes, the ash content is 3.0wt percent, and the specific surface area is 1200m2The catalyst is used for catalyzing CO oxidation reaction to become a waste catalyst.
Mixing 3g of ionic liquid N-octyl pyridine chloride salt, 0.4g of trichloroisocyanuric acid and 5mL of acetone, adding 1g of Pt @ AC, stirring at the temperature of 20 ℃ at the speed of 600r/min for 5 hours, and carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the gold complex, and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetone as solvent at 120 ℃ for 36 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.8ml of 80% hydrazine hydrate at 25 ℃, and stirring at the speed of 600r/min for 1 h. The solid phase is metal, washed by deionized water and then by 0.5mL of 10% nitric acid to remove base metal impurities, so that Pt is 0.0290g, and the recovery rate reaches 97%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 11
Through the literature [ Zhejiang metallurgy, 2011,2: 18-20)]The method prepares the Rh @ AC catalyst with the loading amount (relative to the mass of the carrier) of 1 wt%, wherein the carrier is columnar activated carbon, the particle size is 50 meshes, the ash content is 3.0 wt%, and the specific surface area is 1200m2The catalyst is used for catalyzing aromatic ring hydrogenation reaction to become a waste catalyst.
4g of ionic liquid N-butyl-N-methylpyrrole bromide, 0.3g of trichloroisocyanuric acid and 5mL of acetonitrile are mixed, 3g of Rh @ AC waste catalyst is added, and after stirring is carried out at the temperature of 30 ℃ at the speed of 800r/min for 6 hours, solid-liquid separation is carried out, wherein the liquid phase is the ionic liquid containing the palladium complex, and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetonitrile as solvent at 100 ℃ for 48 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.8ml of 80% hydrazine hydrate at 25 ℃, and stirring at the speed of 600r/min for 2 h. The solid phase is metal, washed by deionized water and then by 0.5mL of 10% nitric acid to remove base metal impurities, and the obtained Rh is 0.0289g, and the recovery rate reaches 96%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 12
Through the literature [ university of inner Mongolia, 2013, 44(6):578-583]The method prepares the Ag @ AC catalyst with the load capacity (relative to the mass of the carrier) of 5wt percent, wherein the carrier is columnar active carbon, the particle size is 50 meshes, the ash content is 3.0wt percent, and the specific surface area is 1200m2The catalyst is used for catalyzing and oxidizing cyclohexene to form a waste catalyst after reaction.
Mixing 5g of ionic liquid N-hexyl pyridine iodide, 0.4g of trichloroisocyanuric acid and 5mL of ethanol, adding 1g of the Ag @ AC molecular sieve waste catalyst, stirring at 40 ℃ at the speed of 500r/min for 4 hours, and then carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the palladium complex, and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 200mL of ethanol as solvent at 110 ℃ for 48 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 1ml of 85% formic acid at 25 deg.C, and stirring at 800r/min for 1 h. The solid phase is metal, washed by deionized water and then by 0.8mL of 10% nitric acid to remove base metal impurities, so that the Ag is 0.0485g, and the recovery rate reaches 97%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Example 13
The synthesis of the protein by literature [ petroleum refining and chemical, 2009, 40 (2): 31-35]The method prepares Au @ SiO with the loading (relative to the mass of the carrier) of 3 weight percent2The catalyst has columnar SiO as carrier2The particle diameter is 50 meshes, the specific surface area is 300m2The catalyst is used for catalyzing and oxidizing cyclohexane to become a waste catalyst after being used for catalyzing and oxidizing the cyclohexane, and the pore volume is 0.7 mL/g.
Mixing 3g of ionic liquid tributyl-monomethyl ammonium chloride, 0.3g of trichloroisocyanuric acid and 5mL of acetone, adding 1g of the Au @ SiO2 waste catalyst, stirring at the speed of 600r/min at the temperature of 20 ℃ for 5 hours, and carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the gold complex, and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetone as solvent at 120 ℃ for 36 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.8ml of 80% hydrazine hydrate at 25 ℃, and stirring at the speed of 600r/min for 1 h. After solid-liquid separation, the solid phase is metal, washing with deionized water, and then washing with 0.8mL of 10% nitric acid to remove base metal impurities to obtain 0.0297g of Au, wherein the recovery rate reaches 99%; the solvent in the liquid phase was removed by rotary evaporation to obtain regenerated ionic liquid, 0.3g of trichloroisocyanuric acid and 5mL of acetone were added to prepare a leaching agent, 1g of the same Au @ SiO2 spent catalyst was added, and the above recovery procedure was repeated to obtain 0.0291g of Au, with a recovery rate of 97%.
Example 14
The synthesis of the protein by literature [ petroleum refining and chemical, 2009, 40 (2): 31-35]The method prepares Au @ SiO with the loading (relative to the mass of the carrier) of 3 weight percent2The catalyst has columnar SiO as carrier2The particle diameter is 50 meshes, the specific surface area is 300m2The catalyst is used for catalyzing and oxidizing cyclohexane to become a waste catalyst after being used for catalyzing and oxidizing the cyclohexane, and the pore volume is 0.7 mL/g.
Mixing 3g of ionic liquid tributyl-monomethyl ammonium chloride, 0.3g of trichloroisocyanuric acid and 5mL of acetone, adding 1g of the Au @ SiO2 waste catalyst, stirring at the speed of 600r/min at the temperature of 20 ℃ for 5 hours, and carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the gold complex, and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetone as solvent at 120 ℃ for 36 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.8ml of 80% hydrazine hydrate at 25 ℃, and stirring at the speed of 600r/min for 1 h. After solid-liquid separation, the solid phase is metal, washing with deionized water, and then washing with 0.8mL of 10% nitric acid to remove base metal impurities to obtain 0.0297g of Au, wherein the recovery rate reaches 99%; removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid, adding 0.3g of trichloroisocyanuric acid and 5mL of acetone to prepare a leaching agent, adding 1g of the same Au @ SiO2 waste catalyst, and repeating the recovery step to obtain 0.0291g of Au, wherein the recovery rate is 97%. After the ionic liquid is recycled for 2 times, 0.0285g of Au is obtained, and the recovery rate reaches 95%. After the ionic liquid was recycled for 3 times, 0.0279g of Au was obtained, and the recovery rate was 93%. After the ionic liquid is recycled for 4 times, 0.0273g of Au is obtained, and the recovery rate reaches 91%. After the ionic liquid is recycled for 5 times, 0.0269g of Au is obtained, and the recovery rate reaches 90%.
Comparative example 1
By literature [ petroleum refining and chemical engineering, 20)09，40(2)：31-35]The method prepares Au @ SiO with the loading (relative to the mass of the carrier) of 3 weight percent2The catalyst has columnar SiO as carrier2The particle diameter is 50 meshes, the specific surface area is 300m2The catalyst is used for catalyzing and oxidizing cyclohexane to become a waste catalyst after being used for catalyzing and oxidizing the cyclohexane, and the pore volume is 0.7 mL/g.
Mixing 3g of ionic liquid tributyl-methyl ammonium chloride, 0.3g of hydrogen peroxide and 5mL of acetone, adding 1g of the Au @ AC waste catalyst, stirring at the temperature of 20 ℃ at the speed of 600r/min for 5 hours, carrying out solid-liquid separation, wherein the liquid phase does not detect the gold and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetone as solvent at 120 ℃ for 36 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.8ml of hydrazine hydrate with the concentration of 80% at 25 ℃, and stirring at the speed of 600r/min for 1h to obtain 0g of Au, wherein the recovery rate reaches 0%.
Comparative example 2
The synthesis of the protein by literature [ petroleum refining and chemical, 2009, 40 (2): 31-35]The method prepares Au @ SiO with the loading (relative to the mass of the carrier) of 3 weight percent2The catalyst has columnar SiO as carrier2The particle diameter is 50 meshes, the specific surface area is 300m2The catalyst is used for catalyzing and oxidizing cyclohexane to become a waste catalyst after being used for catalyzing and oxidizing the cyclohexane, and the pore volume is 0.7 mL/g.
Mixing 3g of ionic liquid 1-butyl-3-methylimidazole chloride salt, 0.3g of trichloroisocyanuric acid and 5mL of acetone, adding 1g of the Au @ SiO2 waste catalyst, stirring at the temperature of 20 ℃ at the speed of 600r/min for 5 hours, and carrying out solid-liquid separation, wherein the liquid phase is the ionic liquid containing the gold complex and the solid phase is the catalyst. The catalyst is subjected to Soxhlet extraction with 150mL acetone as solvent at 120 ℃ for 36 h. Mixing the liquid phase obtained by solid-liquid separation with the liquid phase obtained by Soxhlet extraction, adding 0.3ml of 80% hydrazine hydrate at 25 ℃, and stirring at the speed of 600r/min for 1 h. After solid-liquid separation, the solid phase was metal, washed with deionized water, and then washed with 0.5mL of 10% nitric acid to remove base metal impurities, yielding 0.0135g of Au, with a recovery rate of 45%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Comparative example 3
After 3g of ionic liquid tributyl-monomethyl ammonium chloride, 0.3g of trichloroisocyanuric acid and 5mL of acetone are mixed, 0.03gAu is added, after stirring at the speed of 600r/min for 5h at the temperature of 20 ℃, 0.8mL of 80% hydrazine hydrate is added at the temperature of 25 ℃, and stirring is carried out at the speed of 600r/min for 1 h. After solid-liquid separation, 0.0298g of Au was obtained, and the recovery rate was 99%. And removing the solvent from the liquid phase by using a rotary evaporation method to obtain regenerated ionic liquid.
Claims (10)
1. A precious metal leaching agent is characterized in that: the precious metal leaching agent consists of ionic liquid, trichloroisocyanuric acid or dichloroisocyanuric acid and a solvent, wherein the mass ratio of the ionic liquid to the trichloroisocyanuric acid or dichloroisocyanuric acid is 30: 1-5: 1, and the volume ratio of the solvent to the ionic liquid is 10: 1-1: 1;
the anion of the ionic liquid is selected from at least one of chloride ion, bromide ion, iodide ion, thiocyanate ion and dinitrile amine ion, and the cation is selected from at least one of pyrrolidine, quaternary ammonium salt and quaternary phosphonium salt;
the solvent is water, ethanol, isopropanol, acetone or acetonitrile.
2. The precious metal leachant of claim 1, wherein: the cation of the ionic liquid is at least one of N-hexylpyridine, N-butylpyridine, N-octylpyridine, N-butyl-N-methylpyrrolidine, tributyl-monomethyl ammonium and tetrabutyl phosphonium.
3. The precious metal leachant of claim 1, wherein: the anion of the ionic liquid is chloride ion, bromide ion, iodide ion or dinitrile amine radical ion.
4. The precious metal leachant of claim 1, wherein: the ionic liquid is tributyl monomethyl ammonium chloride or tetrabutyl phosphonium chloride, N-butylpyridine dicyandiamide salt, N-octyl pyridine chloride salt, N-butyl-N-methylpyrrole bromide salt and N-hexyl pyridine iodide salt.
5. The precious metal leachant of any of claims 1 to 4, wherein: the mass ratio of the ionic liquid to the trichloroisocyanuric acid or the dichloroisocyanuric acid is 20: 1-10: 1.
6. A method for recovering noble metals from waste catalysts is disclosed, wherein the catalysts are supported catalysts, carriers of the supported catalysts are activated carbon, carbon nano tubes, graphene, aluminum oxide, silicon dioxide, titanium dioxide or molecular sieves, and active components of the supported catalysts are noble metals; the method is characterized in that: the method comprises the following steps:
step (1) of preparing the noble metal leaching agent according to claim 1;
step (2), leaching precious metals: mixing the noble metal leaching agent obtained in the step (1) with a waste catalyst, controlling the weight ratio of the noble metal leaching agent to the catalyst to be 20: 1-2: 1, stirring for 0.5-10 h at 15-100 ℃, and stirring at the speed of 400-1000 r/min to obtain a mixture;
step (3), solid-liquid separation: carrying out solid-liquid separation on the mixture obtained in the step (2), wherein the obtained liquid phase is an ionic liquid containing a gold complex, and the solid phase is a solid catalyst;
step (4), Soxhlet extraction: separating the ionic liquid adsorbed on the surface of the catalyst carrier from the solid catalyst obtained in the step (3) by adopting a Soxhlet extraction method, wherein the solvent used in the Soxhlet extraction is the same as the solvent in the noble metal leaching agent, the volume of the Soxhlet extraction is 10-30 times of the volume of the noble metal leaching agent, the extraction temperature is 30-180 ℃, the extraction time is 12-72 hours, and after the extraction is finished, the obtained solid phase is the catalyst carrier;
and (5) reducing: mixing the liquid phase obtained in the step (3) with the liquid phase obtained in the step (4), adding a reducing agent at 10-80 ℃, stirring for reaction, carrying out solid-liquid separation after full reaction, and removing the solvent by using a rotary evaporation method to obtain regenerated ionic liquid; the obtained solid phase is metal, and is washed by deionized water firstly, and then the base metal impurities are washed by nitric acid, so that the pure noble metal is obtained.
7. The method of claim 6, wherein: the noble metal in the catalyst is gold, silver and/or platinum group metal.
8. The method of claim 6 or 7, wherein: the reducing agent is hydrazine hydrate, formic acid or borazane.
9. The method of claim 8, wherein: in the step (5), the reduction temperature is 20-30 ℃, the stirring time is 0.5-5 h, and the stirring speed is 400-1000 r/min.
10. The method of claim 6 or 7, wherein: in the step (5), the concentration of the nitric acid is 5 to 15 wt%.
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