CN118006901A - Method for recycling metal materials in waste carbon-supported noble metal catalyst by utilizing ionic liquid - Google Patents
Method for recycling metal materials in waste carbon-supported noble metal catalyst by utilizing ionic liquid Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 103
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 55
- 239000002699 waste material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000007769 metal material Substances 0.000 title claims abstract description 15
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 48
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002386 leaching Methods 0.000 claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 230000001588 bifunctional effect Effects 0.000 claims description 19
- 238000006722 reduction reaction Methods 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 14
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000002169 ethanolamines Chemical class 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 23
- 238000000605 extraction Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 19
- 229910052763 palladium Inorganic materials 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 12
- 229910052703 rhodium Inorganic materials 0.000 description 12
- 239000010948 rhodium Substances 0.000 description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000010970 precious metal Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- 150000001350 alkyl halides Chemical class 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229950009390 symclosene Drugs 0.000 description 2
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recycling metal materials in a waste carbon-supported noble metal catalyst by utilizing ionic liquid, and belongs to the technical field of noble metal recycling. The invention uses the polar organic solvent to soak the waste carbon-supported noble metal catalyst, which can dissolve organic pollutants in the waste carbon-supported noble metal catalyst and prevent the existence of the organic pollutants from affecting the recovery rate of noble metals; according to the invention, the particle size of the waste carbon-supported noble metal catalyst is reduced by ball milling, so that the structure in the waste carbon-supported noble metal catalyst is opened, the noble metal embedded in the waste carbon-supported noble metal catalyst is prevented from being insufficiently released, and the recovery rate of the noble metal is further improved; the invention takes the difunctional ethanolamine ionic liquid as the extractant, has better extraction effect on noble metals in powder, and can shorten the extraction time; according to the invention, the noble metal ions can be reduced into the noble metal simple substance by adding the reducing agent into the leaching solution, so that the recovery of the noble metal is realized.
Description
Technical Field
The invention relates to the technical field of noble metal recovery, in particular to a method for recovering a metal material in a waste carbon-supported noble metal catalyst by utilizing an ionic liquid.
Background
Noble metals mainly refer to 8 metal elements such as gold, silver, platinum group metals (ruthenium, rhodium, palladium, osmium, iridium, platinum) and the like. The carbon-supported noble metal has higher catalytic activity and has wide application in petrochemical industry and organic synthesis. However, noble metal catalysts lose activity in the application process due to problems of poisoning, easy construction of carriers, carbon accumulation and the like, and become waste catalysts.
Currently, a common method for recovering precious metals from spent precious metal catalysts involves roasting the spent precious metal catalyst and leaching the precious metal in ionic form using a leaching agent. However, this method has problems of low recovery rate of noble metals and high energy consumption.
The ionic liquid has the advantages of good stability, compatibility and the like, and is widely applied to extracting noble metals, but the high-viscosity ionic liquid enables the extraction process to be in a slow dynamic process, so that a longer balancing time is needed for obtaining remarkable extraction capacity. For example, chinese patent CN 201910797057.1 discloses a precious metal leaching agent and a method for recovering precious metals from waste catalyst, which uses ionic liquid to leach precious metals, the extraction temperature is 30-180 ℃, the extraction time is 12-72 h, and the problem of long extraction time exists. In order to solve the problem of high viscosity of ionic liquid, the method commonly used at present is to add organic solvents such as toluene, chloroform and the like, which can cause environmental pollution.
Therefore, there is a need to provide a method for recycling metal materials in waste carbon-supported noble metal catalysts by using ionic liquids, which has short extraction time and high recovery rate of green and noble metals.
Disclosure of Invention
The invention aims to provide a method for recycling metal materials in waste carbon-supported noble metal catalysts by utilizing ionic liquid.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a method for recycling metal materials in waste carbon-supported noble metal catalysts by utilizing ionic liquid, which comprises the following steps:
(1) Soaking the waste carbon-supported noble metal catalyst in a polar organic solvent, and filtering to obtain filter residues;
(2) Ball milling the filter residue obtained in the step (1) to obtain powder;
(3) Mixing the powder obtained in the step (2) with a bifunctional ethanolamine-based ionic liquid under the irradiation of sunlight to obtain a leaching solution; continuously introducing ozone during the mixing;
(4) And (3) mixing the leaching solution obtained in the step (3) with a reducing agent for reduction reaction to obtain a noble metal simple substance.
Preferably, the polar organic solvent in the step (1) includes methanol, ethanol or dimethyl sulfoxide.
Preferably, the particle size of the powder in the step (2) is 200-300 mesh.
Preferably, the structural formula of the bifunctional ethanolamine-based ionic liquid in the step (3) is shown as formula (I):
Formula (I)
N=0 or 1 in formula (I); x is I.
Preferably, the mass ratio of the powder in the step (3) to the bifunctional ethanolamino ionic liquid is 1 (5-20).
Preferably, the temperature of the mixing in the step (3) is 60-85 ℃.
Preferably, the mixing time is 0.5-2 hours.
Preferably, the reducing agent in the step (4) comprises hydroxylamine hydrochloride, sodium borohydride or hydrazine hydrate.
Preferably, the mass ratio of the powder in the step (3) to the reducing agent in the step (4) is (0.5-1.0): 1.
Preferably, the reduction reaction in the step (4) is performed at room temperature, and the time of the reduction reaction is 0.5-2 h.
The invention provides a method for recycling metal materials in waste carbon-supported noble metal catalysts by utilizing ionic liquid, which comprises the following steps: soaking the waste carbon-supported noble metal catalyst in a polar organic solvent, and filtering to obtain filter residues; ball milling the filter residues to obtain powder; mixing the powder with a bifunctional ethanolamine-based ionic liquid under sunlight irradiation to obtain a leaching solution; continuously introducing ozone during the mixing; and mixing the leaching solution with a reducing agent for reduction reaction to obtain a noble metal simple substance. The invention uses the polar organic solvent to soak the waste carbon-supported noble metal catalyst, which can dissolve organic pollutants in the waste carbon-supported noble metal catalyst and prevent the existence of the organic pollutants from affecting the recovery rate of noble metals; according to the invention, the particle size of the waste carbon-supported noble metal catalyst is reduced by ball milling, so that the structure in the waste carbon-supported noble metal catalyst is opened, the noble metal embedded in the waste carbon-supported noble metal catalyst is prevented from being insufficiently released, and the recovery rate of the noble metal is further improved; the invention takes the difunctional ethanolamine ionic liquid as the extractant, has better wettability, and ozone is introduced during mixing, so that the invention has better extraction effect on noble metals in powder and can shorten the extraction time; according to the invention, the noble metal ions can be reduced into the noble metal simple substance by adding the reducing agent into the leaching solution, so that the recovery of the noble metal is realized. The results of the examples show that the method provided by the invention has the characteristics of short extraction time, green and high recovery rate of noble metals, and the extraction time is 0.5h, the recovery rate of palladium is 99.85%, the recovery rate of platinum is 97.76%, and the recovery rate of rhodium is 94.35%.
Detailed Description
The invention provides a method for recycling metal materials in waste carbon-supported noble metal catalysts by utilizing ionic liquid, which comprises the following steps:
(1) Soaking the waste carbon-supported noble metal catalyst in a polar organic solvent, and filtering to obtain filter residues;
(2) Ball milling the filter residue obtained in the step (1) to obtain powder;
(3) Mixing the powder obtained in the step (2) with a bifunctional ethanolamine-based ionic liquid under the irradiation of sunlight to obtain a leaching solution; continuously introducing ozone during the mixing;
(4) And (3) mixing the leaching solution obtained in the step (3) with a reducing agent for reduction reaction to obtain a noble metal simple substance.
The method provided by the invention is suitable for the conventional waste carbon noble metal-supported catalyst in the field. In the present invention, the noble metal in the spent carbon-supported noble metal catalyst preferably includes one or more of gold, palladium, platinum and rhodium.
The invention is to soak the waste carbon-supported noble metal catalyst in a polar organic solvent and then filter the catalyst to obtain filter residues.
In the present invention, the polar organic solvent preferably includes methanol, ethanol or dimethyl sulfoxide, more preferably ethanol or dimethyl sulfoxide. The invention can dissolve organic impurities in the waste carbon-supported noble metal catalyst by soaking the waste carbon-supported noble metal catalyst in the polar organic solvent.
The invention does not limit the dosage of the polar organic solvent, and the liquid level of the polar organic solvent is higher than that of the waste carbon-carried noble metal catalyst.
In the present invention, the soaking temperature is preferably room temperature; the soaking time is preferably 2-5 hours, more preferably 3-4 hours. The invention controls the soaking temperature and time in the above range, and can fully dissolve organic impurities in the waste carbon-supported noble metal catalyst.
The type of the filter paper used for filtering is not particularly limited, and the conventional filter paper is adopted, so that the noble metal catalyst carried by the waste carbon can be intercepted, and filter residues of the filtrate can be separated.
After the filter residue is obtained, the filter residue is ball-milled to obtain powder.
According to the invention, the particle size of the filter residue can be reduced by ball milling, so that the destroyed structure of the waste filter residue is opened, the noble metal embedded in the filter residue is prevented from being unable to be released, and the recovery rate of the noble metal is further improved.
The ball milling device and the parameters are not particularly limited, and the particle size of the powder obtained after ball milling can be required by adopting the conventional ball milling device and parameters. In the present invention, the particle size of the powder is preferably 200 to 300 mesh, more preferably 200 mesh. The invention is more beneficial to improving the specific surface area of the catalyst and removing impurities in the waste noble metal catalyst by controlling the particle size of the powder in the range.
After the powder is obtained, the powder is mixed with the difunctional ethanolamino ionic liquid under the irradiation of sunlight to obtain leaching solution; ozone is continuously introduced during the mixing.
In the invention, the structural formula of the difunctional ethanolamino ionic liquid is shown as a formula (I):
Formula (I)
N=0 or 1 in formula (I); x is preferably I. The difunctional ethanolamine-based ionic liquid is used as an extractant, has good wettability and has good extraction effect on noble metals in powder.
The preparation method of the difunctional ethanolamine-based ionic liquid is not particularly limited, and the difunctional ethanolamine-based ionic liquid is prepared by adopting a conventional preparation method of the ionic liquid. In the invention, the preparation method of the difunctional ethanolamino ionic liquid preferably comprises the following steps: mixing N, N, N ', N' -tetra (2-hydroxyethyl) ethylenediamine, acetone and haloalkane, and carrying out reflux reaction under nitrogen to obtain the difunctional ethanolamino ionic liquid.
In the present invention, the haloalkane is preferably methyl iodide or ethyl iodide.
In the present invention, the ratio of the amounts of N, N, N ', N' -tetrakis (2-hydroxyethyl) ethylenediamine to haloalkane is preferably 1 (3 to 5), more preferably 1:3. In the present invention, the amount of the acetone to be used as the reaction solvent is not particularly limited, and may be adjusted as needed.
In the present invention, the method of mixing the N, N' -tetrakis (2-hydroxyethyl) ethylenediamine, acetone and haloalkane is preferably stirring.
In the invention, the temperature of the reflux reaction is preferably 60-80 ℃, more preferably 70-8 ℃; the time of the reflux reaction is preferably 8 to 12 hours, more preferably 12 hours.
In the present invention, the mass ratio of the powder to the bifunctional ethanolamines ionic liquid is preferably 1 (5-20), more preferably 1 (10-15). The invention is more favorable for fully extracting noble metals in the powder and improving the recovery rate of the noble metals when the mass ratio of the powder to the bifunctional ethanolamine ionic liquid is controlled in the range.
In the present invention, the method of mixing the powder with the bifunctional ethanolamino ionic liquid under irradiation of sunlight is preferably stirring. In the invention, ozone is continuously introduced during the mixing. The air flow rate of the ozone is not particularly limited, and the ozone can be adjusted according to the needs. The invention is more beneficial to improving the extraction effect of noble metals by stirring and ozone introduction.
In the invention, the mixing temperature is preferably 60-85 ℃, more preferably 70-80 ℃; the mixing time is preferably 0.5 to 2 hours, more preferably 0.5 to 1 hour. The invention can fully extract the noble metal in the waste carbon supported noble metal catalyst at the mixing temperature and the mixing time.
After the leaching solution is obtained, the leaching solution is mixed with a reducing agent for reduction reaction, so that the noble metal simple substance is obtained.
In the present invention, the reducing agent preferably includes hydroxylamine hydrochloride, sodium borohydride, or hydrazine hydrate.
In the present invention, the mass ratio of the powder to the reducing agent is preferably (0.5 to 1.0): 1, more preferably (0.8 to 1.0): 1.
In the present invention, the temperature of the reduction reaction is preferably room temperature; the reduction reaction time is preferably 0.5 to 2 hours, more preferably 1 to 2 hours. The invention can fully reduce noble metal ions in the extract liquid into noble metals under the temperature and the time.
After the reduction reaction is completed, the method preferably filters, washes and dries the products of the reduction reaction in sequence to obtain noble metals. The method for filtering, washing and drying is not particularly limited, and conventional methods for filtering, washing and drying are adopted. In the present invention, the washing reagent is preferably water; the drying temperature is preferably 80-100 ℃, and the drying time is preferably 0.5-2 h, more preferably 1-2 h.
The method provided by the invention does not need high-temperature roasting, has low energy consumption and short extraction time, can fully remove impurities in the waste carbon-supported noble metal catalyst, is beneficial to fully releasing noble metal in the waste carbon-supported noble metal catalyst, and improves the recovery rate of noble metal.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method for recycling metal materials in waste carbon-supported noble metal catalysts by utilizing ionic liquid comprises the following steps:
(1) Placing 500Kg of waste carbon-supported noble metal catalyst into ethanol for soaking, so that the liquid level of the ethanol is higher than that of the powder, soaking for 2 hours, and filtering to obtain filter residues;
(2) Ball milling the filter residue obtained in the step (1), and sieving the filter residue with a 200-mesh sieve to obtain undersize products as powder; sampling and analyzing the content of noble metal in the waste palladium-carbon catalyst; the noble metal in the waste carbon supported noble metal catalyst is that the content of palladium is 2240ppm, platinum is 170ppm and rhodium is 220ppm;
(3) Stirring and mixing the powder obtained in the step (2) with the bifunctional ethanolamine-based ionic liquid under the irradiation of sunlight, continuously introducing ozone during mixing, and obtaining leaching liquid, wherein the mixing temperature is 80 ℃ and the mixing time is 0.5 h;
Wherein the mass ratio of the powder to the bifunctional ethanolamino ionic liquid is 1:5;
The structural formula of the difunctional ethanolamino ionic liquid is as follows:
Wherein n=0, x is I;
(4) According to the mass ratio of the powder in the step (3) to the sodium borohydride of 0.5:1, stirring and mixing the leaching solution obtained in the step (3) with the sodium borohydride for 2 hours to perform a reduction reaction, filtering, washing the obtained filter residues, and drying at 80 ℃ for 0.5 hour to obtain noble metals; the noble metals obtained were analyzed and calculated to give a recovery of 99.66% palladium, 95.42% platinum and 94.28% rhodium.
Example 2
A method for recycling metal materials in waste carbon-supported noble metal catalysts by utilizing ionic liquid comprises the following steps:
(1) Placing 500Kg of waste carbon-supported noble metal catalyst into ethanol for soaking, so that the liquid level of the ethanol is higher than that of the powder, soaking for 2 hours, and filtering to obtain filter residues;
(2) Ball milling the filter residue obtained in the step (1), and sieving the filter residue with a 200-mesh sieve to obtain undersize products as powder; sampling and analyzing the content of noble metal palladium in the waste palladium-carbon catalyst to 2240ppm, 170ppm of platinum and 220ppm of rhodium;
(3) Stirring and mixing the powder obtained in the step (2) with the bifunctional ethanolamine-based ionic liquid under the irradiation of sunlight, continuously introducing ozone during mixing, and obtaining leaching liquid, wherein the mixing temperature is 80 ℃ and the mixing time is 0.5 h;
Wherein the mass ratio of the powder to the bifunctional ethanolamino ionic liquid is 1:8; the structural formula of the difunctional ethanolamino ionic liquid is as follows:
Wherein n=0, x is I;
(4) According to the mass ratio of the powder in the step (3) to the sodium borohydride of 0.5:1, stirring and mixing the leaching solution obtained in the step (3) with the sodium borohydride for 2 hours to perform a reduction reaction, filtering, washing the obtained filter residues, and drying at 80 ℃ for 0.5 hour to obtain noble metals; the noble metals obtained were analyzed and calculated to give a palladium recovery of 99.85%, platinum 97.76% and rhodium 94.35%.
Example 3
A method for recycling metal materials in waste carbon-supported noble metal catalysts by utilizing ionic liquid comprises the following steps:
(1) Placing 500Kg of waste carbon-supported noble metal catalyst into dimethyl sulfoxide for soaking, so that the liquid level of the dimethyl sulfoxide is higher than that of the powder, soaking for 2 hours, and filtering to obtain filter residues;
(2) Ball milling the filter residue obtained in the step (1), and sieving the filter residue with a 200-mesh sieve to obtain undersize products as powder; sampling and analyzing the content of noble metal palladium in the waste palladium-carbon catalyst to 2240ppm, 170ppm of platinum and 220ppm of rhodium;
(3) Stirring and mixing the powder obtained in the step (2) with the bifunctional ethanolamine-based ionic liquid under the irradiation of sunlight, continuously introducing ozone during mixing, and obtaining leaching solution, wherein the mixing temperature is 85 ℃, and the mixing time is 0.5 h;
Wherein the mass ratio of the powder to the bifunctional ethanolamino ionic liquid is 1:10; the structural formula of the difunctional ethanolamino ionic liquid is as follows:
Wherein n=1, x is I;
(4) According to the mass ratio of the powder in the step (3) to the sodium borohydride of 0.5:1, stirring and mixing the leaching solution obtained in the step (3) with the sodium borohydride for 2 hours to perform a reduction reaction, filtering, washing the obtained filter residues, and drying at 80 ℃ for 0.5 hour to obtain noble metals; the noble metal obtained was analyzed, and the recovery rate of palladium was calculated to be 99.45%, 98.65% for platinum and 95.46% for rhodium.
Example 4
A method for recycling metal materials in waste carbon-supported noble metal catalysts by utilizing ionic liquid comprises the following steps:
(1) Placing 500Kg of waste carbon-supported noble metal catalyst into dimethyl sulfoxide for soaking, so that the liquid level of the dimethyl sulfoxide is higher than that of the powder, soaking for 2 hours, and filtering to obtain filter residues;
(2) Ball milling the filter residue obtained in the step (1), and sieving the filter residue with a 200-mesh sieve to obtain undersize products as powder; sampling and analyzing the content of noble metal palladium in the waste palladium-carbon catalyst to 2240ppm, 166ppm of platinum and 213ppm of rhodium;
(3) Stirring and mixing the powder obtained in the step (2) with the bifunctional ethanolamine-based ionic liquid under the irradiation of sunlight, continuously introducing ozone during mixing, and obtaining leaching solution at the mixing temperature of 65 ℃ for 1 h;
Wherein the mass ratio of the powder to the bifunctional ethanolamino ionic liquid is 1:8; the structural formula of the difunctional ethanolamino ionic liquid is as follows:
Wherein n=1, x is I;
(4) According to the mass ratio of the powder in the step (3) to the sodium borohydride of 0.5:1, stirring and mixing the leaching solution obtained in the step (3) with the sodium borohydride for 2 hours to perform a reduction reaction, filtering, washing the obtained filter residues, and drying at 80 ℃ for 0.5 hour to obtain noble metals; the noble metal obtained was analyzed and calculated to give a recovery of 99.62% of palladium, 96.41% of platinum 97.48% of rhodium.
Comparative example 1
A method for recycling metal materials in waste carbon-supported noble metal catalysts by utilizing ionic liquid comprises the following steps:
(1) The method (2) is the same as that of the embodiment 1;
The difference from example 1 is that the mixed solution of tributyl monomethyl ammonium chloride and trichloroisocyanuric acid and acetone, which is an ionic liquid, is adopted in the step (3) to replace the difunctional ethanolamine ionic liquid in example 1; wherein the ratio of the mass of tributyl monomethyl ammonium chloride, the mass of trichloroisocyanuric acid and the volume of acetone is 3g to 0.3g to 5ml;
(4) Stirring and mixing the leaching solution obtained in the step (3) with sodium borohydride for 12 hours to perform a reduction reaction, filtering, washing the obtained filter residue, and drying at 80 ℃ for 0.5 hour to obtain noble metal palladium; the noble metals obtained were analyzed and calculated to give a palladium recovery of 94.32%, platinum 89.85% and rhodium 72.3%.
The result shows that the method provided by the invention can shorten the extraction time and has higher recovery rate of noble metals. The ionic liquid adopted by the invention has better wettability, so that the extraction time can be shortened and the recovery rate of noble metal can be improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for recycling metal materials in waste carbon-supported noble metal catalysts by utilizing ionic liquid comprises the following steps:
(1) Soaking the waste carbon-supported noble metal catalyst in a polar organic solvent, and filtering to obtain filter residues;
(2) Ball milling the filter residue obtained in the step (1) to obtain powder;
(3) Mixing the powder obtained in the step (2) with a bifunctional ethanolamine-based ionic liquid under the irradiation of sunlight to obtain a leaching solution; continuously introducing ozone during the mixing;
(4) And (3) mixing the leaching solution obtained in the step (3) with a reducing agent for reduction reaction to obtain a noble metal simple substance.
2. The method according to claim 1, wherein the polar organic solvent in step (1) comprises methanol, ethanol or dimethyl sulfoxide.
3. The method according to claim 1, wherein the powder in step (2) has a particle size of 200 mesh.
4. The method according to claim 1, wherein the bifunctional ethanolamines ionic liquid in step (3) has a structural formula shown in formula (I):
formula (I)
N=0 or 1 in formula (I); x is I.
5. The method according to claim 1, wherein the mass ratio of the powder to the bifunctional ethanolamines ionic liquid in the step (3) is 1 (5-20).
6. The method of claim 1, wherein the temperature of the mixing in step (3) is 60-85 ℃.
7. The method of claim 6, wherein the mixing is for a period of 0.5 to 2 hours.
8. The method of claim 1, wherein the reducing agent in step (4) is sodium borohydride.
9. The method according to claim 1 or 8, wherein the mass ratio of the powder in step (3) to the reducing agent in step (4) is 0.5:1.
10. The method according to claim 1, wherein the reduction reaction in step (4) is performed at room temperature for a period of 2 hours.
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| US4801329A (en) * | 1987-03-12 | 1989-01-31 | Ensci Incorporated | Metal value recovery from carbonaceous ores |
| CN106319244A (en) * | 2016-09-09 | 2017-01-11 | 山东省医学科学院药物研究所 | Application of functional ionic liquid and method of extracting lithium from salt lake brine |
| CN106478495A (en) * | 2016-09-09 | 2017-03-08 | 山东省医学科学院药物研究所 | Functionalized ion liquid and its synthetic method for lithium extraction |
| CN114150159A (en) * | 2021-12-07 | 2022-03-08 | 山东大学 | Temperature-controlled noble metal separation and extraction agent, preparation method thereof and homogeneous extraction method |
| CN115896456A (en) * | 2022-11-01 | 2023-04-04 | 上海师范大学 | Method for accelerating dissolution of metal by ozone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801329A (en) * | 1987-03-12 | 1989-01-31 | Ensci Incorporated | Metal value recovery from carbonaceous ores |
| CN106319244A (en) * | 2016-09-09 | 2017-01-11 | 山东省医学科学院药物研究所 | Application of functional ionic liquid and method of extracting lithium from salt lake brine |
| CN106478495A (en) * | 2016-09-09 | 2017-03-08 | 山东省医学科学院药物研究所 | Functionalized ion liquid and its synthetic method for lithium extraction |
| CN114150159A (en) * | 2021-12-07 | 2022-03-08 | 山东大学 | Temperature-controlled noble metal separation and extraction agent, preparation method thereof and homogeneous extraction method |
| CN115896456A (en) * | 2022-11-01 | 2023-04-04 | 上海师范大学 | Method for accelerating dissolution of metal by ozone |
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