CN113828303A - High-value utilization method of precious metal waste catalyst - Google Patents
High-value utilization method of precious metal waste catalyst Download PDFInfo
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- CN113828303A CN113828303A CN202111080667.3A CN202111080667A CN113828303A CN 113828303 A CN113828303 A CN 113828303A CN 202111080667 A CN202111080667 A CN 202111080667A CN 113828303 A CN113828303 A CN 113828303A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000010970 precious metal Substances 0.000 title claims description 31
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 53
- 238000002386 leaching Methods 0.000 claims abstract description 31
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- 150000002500 ions Chemical class 0.000 claims abstract description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
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- 229910052799 carbon Inorganic materials 0.000 claims description 23
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
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- 238000001035 drying Methods 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
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- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
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- 239000011943 nanocatalyst Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 239000010948 rhodium Substances 0.000 claims 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B01J35/23—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
Abstract
The invention discloses a high-value utilization method of a waste noble metal catalyst, which can realize the high-efficiency leaching of noble metal ions from the waste catalyst and the one-step and continuous preparation of the noble metal catalyst, and belongs to the technical field of noble metal recycling. The method takes a noble metal waste catalyst as a raw material, utilizes a dielectric barrier discharge and impregnation technology to treat the waste catalyst, and then continuously and controllably prepares the noble metal catalyst by coupling a micro-plasma and a micro-channel technology. Compared with the prior art, the method has the advantages of low energy consumption, short time, high purity, low solvent consumption, low pollution, low potential safety hazard and the like. Provides a new idea for recycling the noble metal waste catalyst.
Description
Technical Field
The invention particularly relates to a high-value utilization method of a waste noble metal catalyst, belonging to the technical field of noble metal recycling.
Background
The noble metal catalyst is an indispensable 'industrial vitamin' in the fields of coupling reaction, automobile exhaust purification, petroleum catalytic reforming and the like because of the advantages of high efficiency, high selectivity, small dosage and the like. However, the noble metal catalyst loses activity due to poisoning, carbon deposition, structural change, metal crystal grain aggregation or loss and the like in the using process, and must be replaced in time, so that a large amount of noble metal waste catalysts are generated every year. The waste noble metal catalyst is discharged randomly, which not only wastes valuable resources, but also causes serious pollution to the environment. Therefore, the method effectively extracts the precious metal components from the precious metal waste catalyst and realizes high value-added recycling, thereby not only having extremely high economic value, but also being very important for constructing resource-saving and environment-friendly society.
At present, the precious metals in the waste catalyst are mainly recycled domestically by adopting a hydrometallurgical mode due to the factors of technical level, equipment materials, industrial scale, foreign technology blockade and the like. However, carbon deposition reaction generally exists in the industrial catalysis process, and noble metals are easily oxidized in the catalysis process, so that the surfaces or pore passages of noble metal catalysts are coated and blocked by the respectively generated carbon deposition and noble metal oxides, and high leaching indexes are difficult to obtain through wet metallurgy. Specially for cleaningCN111112295A discloses a pretreatment method and system for a waste catalyst containing precious metals. The waste catalyst is pretreated by supercritical water oxidation reaction, so that the leaching rate of precious metals and the subsequent recovery rate are improved, and the emission is cleaner. Patent CN104878208B shows that the catalyst is first calcined, sulfuric acid, hydrochloric acid, etc. are used as solvent, sodium hypochlorite is added to dissolve noble metal, ruthenium is oxidized into ruthenium tetroxide, and finally, a technology of hydrochloric acid absorption is used, so that a higher leaching index can be obtained. Patent CN109837388A proposes adding cheap and easily available FeCl into the leaching solution3The solution can prevent the loss of noble metals, not only improve the leaching rate of metals, but also reduce the extraction cost.
Although the method can improve the leaching rate of the precious metals, a large amount of acid liquor and chemical reagents have great harm to the environment. The invention first pretreats the waste material, i.e. by plasma in inert gas/H2Generation of H in the atmosphere+、H2+、H*The reducing particles react with carbon deposition and other insoluble pollutants on the surface of the catalyst or in the pore channel to generate CxHyAnd waiting for gaseous molecules, and reducing the noble metal oxide into the noble metal simple substance. Then using the strong coordination characteristic of noble metal atom, using oxidant (such as NaClO, NaClO)3、H2O2Etc.) hydrochloric acid solution or cyanide as leaching solution, so that the noble metal is leached in the form of chloride complex ion or cyanide complex ion, and the use amount of the solvent can be greatly reduced. The invention is expected to provide a new idea for green, efficient and cyclic utilization of the waste catalyst.
Disclosure of Invention
In order to solve the technical problems, the applicant of the invention provides a high-value utilization method of a precious metal waste catalyst, aiming at efficiently leaching precious metal ions from the waste catalyst and continuously preparing the precious metal catalyst in a one-step method by combining a plasma technology based on a selective precious metal dissolving method. The method is simple and easy to implement, green and efficient, and the obtained product has high purity, small diameter and good uniformity.
The technical scheme of the invention is as follows:
a high-value utilization method of a precious metal waste catalyst comprises the following steps:
(1) the method comprises the following steps of taking a precious metal waste catalyst as a raw material, crushing and flatly paving the precious metal waste catalyst in a quartz boat, continuously and stably inputting inert gas/reducing gas into the quartz boat, applying high-voltage alternating current on two sides of the quartz boat to form dielectric barrier discharge plasma after the gas flow is stable, and pretreating the precious metal waste catalyst at room temperature under the action of the plasma;
(2) dissolving precious metals in the pretreatment product by using the selective leaching solution at a certain temperature to obtain a leaching solution;
(3) under the operation of atmospheric pressure and room temperature, a carbon source and leaching solution are used as reaction liquid, placed in a container and then conveyed into a three-way pipe of a plasma reactor through a plunger pump, a stainless steel pipe in the three-way pipe is used as a cathode, a platinum wire is inserted into the three-way pipe to be used as an anode, then alternating current high voltage is applied to the cathode of the plasma reactor under the atmosphere of inert gas/reducing gas, after a plasma arc is stabilized, noble metal ions and the carbon source in the reaction liquid are subjected to reduction reaction simultaneously, and the noble metal/carbon nano catalyst is synthesized in situ in one step;
(4) and centrifuging, washing with deionized water and drying the collected product to obtain the noble metal/carbon catalyst with uniform particle size and stable structural property.
In the step (1), the plasma pretreatment time is 5-120 min.
The noble metal waste catalyst in the step (1) is a platinum-series, palladium-series, gold-series, rhodium-series, silver-series or ruthenium-series noble metal waste catalyst, and further the noble metal waste catalyst is Pt/Al2O3、Pd/Al2O3、Au/Al2O3、Pt/CeO2Or Pt/C; the granularity of the crushed precious metal waste catalyst is 80-400 meshes.
The diameter of the quartz boat in the step (1) is 10-30 cm, and the depth is 3-10 cm.
In the step (3), the length of the cathode tube is 60-120 mm, the inner diameter of the tube is 1.6-3.2 mm, and the outer diameter of the tube is 1.8-3.6 mm; the distance between the cathode and the anode of the plasma reactor is 0.5-3 mm.
Regulating and controlling 10-100 sccm of inert gas and reducing gas mixed gas in the plasma reactor in the steps (1) and (3) by a mass flow controller, introducing the inert gas and reducing gas mixed gas into the plasma reactor, and maintaining for 3-60 min to ensure the inert gas atmosphere in the reactor; the inert gas is one or a mixture of argon and helium; the reducing gas is hydrogen, and the ratio of the inert gas to the reducing gas is 1: 10-10: 1.
The high-voltage alternating current applied in the steps (1) and (3) needs to ensure that the output power is 3-30W so as to generate plasmas at a gas-solid interface and a gas-liquid interface.
The selective leaching solution in the step (2) is a hydrochloric acid solution or a cyanide solution containing an oxidant, and further the selective leaching solution is a NaClO/HCl solution or a NaClO solution3HCl solution or H2O2a/HCN solution.
In the step (2), the concentration of the oxidant in the selective leaching solution is 0.05-5 mol/L, the concentration of the HCl solution is 0.1-5 mol/L, and the concentration of the cyanide solution is 0.1-3 mol/L.
The leaching temperature in the step (2) is 40-100 ℃.
The carbon source in the step (3) is one or the combination of at least two of ethanol, isopropanol, activated carbon, glycerol, acetic acid and propionic acid.
In the step (4), the centrifugal rotating speed is 500-5000 r/min and lasts for 0.5-3 h, the drying temperature is 40-60 ℃, and the drying time lasts for 1-2 h.
The invention has the beneficial effects that:
according to the invention, the noble metal waste catalyst is treated by using the dielectric barrier discharge plasma, active matters in the plasma can effectively permeate into the surface or pore canal of the waste catalyst and rapidly react with carbon deposition, noble metal oxide and other insoluble substances, so that impurities in the waste catalyst are efficiently removed.
The method provided by the invention utilizes a low-temperature plasma technology in cooperation with a selective noble metal dissolving method, so that the leaching rate of noble metal ions is effectively improved, and the reaction is green, environment-friendly, efficient and controllable.
The invention utilizes the low-temperature plasma technology, can continuously prepare the noble metal catalyst by a one-step method, and realizes the high-value conversion of the catalyst waste.
The reactor disclosed by the invention has the advantages of simple structure, small occupied area, low reaction energy consumption, cost saving and no need of a complex post-treatment process. The operation is simple, flexible, efficient, safe and cost-saving.
Note: although the preferred embodiments of the present invention have been described above, it should be understood that they have been presented by way of example only, and not limitation, and that various changes, modifications and improvements can be made therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Drawings
FIG. 1 is a diagram of an experimental apparatus of the present invention.
FIG. 2 is an XRD pattern of a Pt/C catalyst product made in accordance with example 1 of the present invention.
FIG. 3 is an XRD pattern of a Pt/C catalyst product made in accordance with example 2 of the present invention.
FIG. 4 is an XRD pattern of a Pt/C catalyst product made according to example 3 of the present invention.
FIG. 5 is a TEM image of a Pt/C catalyst product obtained in example 3 of the present invention.
FIG. 6 is a TEM image of a Pt/C catalyst product obtained in example 4 of this invention.
FIG. 7 is a TEM image of a Pt/C catalyst product obtained in example 5 of the present invention.
FIG. 8 is a TEM spectrum of a Pt/C catalyst product obtained in comparative example 1 of the present invention.
FIG. 9 is a TEM spectrum of a Pt/C catalyst product obtained in comparative example 2 of the present invention.
FIG. 10 is a TEM spectrum of Pt/C catalyst as a product obtained in example 8 of the present invention
FIG. 11 is a TEM spectrum of Pt/C catalyst as a product obtained in example 9 of the present invention
In the figure: 1 inert gas, 2H23 pipeline one, 4 pipeline two, 5MFC, 6 check valve, 7 reducing joint, 8 pipeline three, 9 gas valve switch 1, 10 gas valve switch 2, 11 line switch 1, 12 current-stabilizing resistor, 13 high-voltage power supply, 14 dielectric barrier discharge reactor, 15 waste catalyst, 16 impregnation system, 17 earthing, 18 line switch 2, 19 computer, 20 optical fiber, 21 spectrometer, 22 wasteCatalyst leaching solution, 23 carbon sources, 24 plunger pumps, 25 pipelines, four 26 tee reactors and 27 collecting bottles.
Detailed Description
The method and effect of the present invention will be further illustrated by the following examples, but the scope of the present invention is not limited thereto.
The following embodiments are implemented using the apparatus of fig. 1:
the device comprises inert gases 1 and H 22. The device comprises a first pipeline 3, a second pipeline 4, an MFC5, a check valve 6, a reducing joint 7, a third pipeline 8, a first air valve switch 9, a second air valve switch 10, a first line switch 11, a current stabilizing resistor 12, a high-voltage power supply 13, a dielectric barrier discharge reactor 14, a waste catalyst 15, an impregnation system 16, a ground 17, a second line switch 18, a computer 19, an optical fiber 20, a spectrometer 21, a waste catalyst leaching solution 22, a carbon source 23, a plunger pump 24, a fourth pipeline 25, a three-way reactor 26 and a collecting bottle 27; the method comprises the following specific steps:
the inert gas 1, H 22 are connected with a three-way valve through pipelines, and the pipelines between the three-way valve are provided with an MFC5, a check valve 6 and a reducing joint 7; the other pipeline of the three-way valve is connected with a second three-way valve; two pipelines of the second three-way valve are respectively connected with the dielectric barrier discharge reactor 14 and the three-way reactor 26; a first gas valve switch 9 is arranged on a pipeline connected with the dielectric barrier discharge reactor 14, a second gas valve switch 10 is arranged on a pipeline connected with the three-way reactor 26, a stainless steel reactor is arranged in the branch of the three-way reactor 26, and the other two branches are common pipelines;
the high-voltage power supply 13, the current-stabilizing resistor 12 and the first line switch 11 are sequentially connected and are connected with the anode of the dielectric barrier discharge reactor 14; the cathode of the dielectric barrier discharge reactor 14 is grounded;
the high-voltage power supply 13, the current stabilizing resistor 12 and the second line switch 18 are sequentially connected and are connected with the anode of the stainless steel reactor in the three-way reactor 26, and the cathode of the stainless steel reactor in the three-way reactor 26 is grounded.
The other two pipelines of the three-way reactor 26 are respectively connected with a collecting bottle 27 and a pipeline four 25, and the pipeline four 25 is respectively connected with the waste catalyst leaching solution 22 and the carbon source 23 through two plunger pumps 24.
In addition, the computer 19, the optical fiber 20 and the spectrometer 21 form a detection system, which can detect active substances generated in the reaction process in real time.
Example 1
Taking a proper amount of ethanol solution, adding deionized water to prepare 80% ethanol water solution as a carbon source. Taking a proper amount of Pt/Al2O3Crushing the waste catalyst, treating the crushed waste catalyst for 30min at room temperature by a plasma reactor by using a dielectric barrier discharge technology, adding the crushed waste catalyst into a mixed solution containing 0.5mol/L HClO and HCl, stirring and treating for 2h at 60 ℃, and diluting by 5 times to obtain an extract. With Ar/H2Adjusting a mass flow meter for working gas, connecting a high-voltage power supply, ensuring that the power of plasma is 20W, respectively introducing the two gases into a three-tube through-type reactor at a flow rate of 30sccm and 50sccm, maintaining the introduced gas for 3min to remove impurity gases in the device, and then introducing the leaching solution and ethanol (carbon source) into the three-tube through-type reactor through a plunger pump in a ratio of 1:1 into a three-tube pass reactor and finally collecting the product at a discharge port. And centrifuging for 1 hour at 500r/min, washing for 2-3 times by using a proper amount of deionized water, and drying for 1 hour at 40 ℃ to obtain the Pt/C catalyst.
Example 2
The treatment process and the operation conditions are the same as those of the example 1, except that the time for treating the noble metal waste catalyst by the dielectric barrier discharge technology is 10 min.
Example 3
The treatment process and the operation conditions are the same as those of the example 1, except that the time for treating the noble metal waste catalyst by the dielectric barrier discharge technology is 1 h.
Example 4
The treatment process and operating conditions were the same as in example 3, except that the ratio of the rates of introduction of the leaching solution and the carbon source was 1: 2.
Example 5
The treatment process and operating conditions were the same as in example 3, except that the ratio of the rates of introduction of the leaching solution and the carbon source was 1: 3.
Comparative example 1
The treatment process and operating conditions were the same as in example 3, except that Pt/Al was used2O3The waste catalyst was crushed and treated in a plasma arc furnace at 1300 ℃ for 30 min.
Comparative example 2
The treatment process and the operation conditions were the same as in example 3, except that the waste noble metal catalyst was Pt/Al2O3The waste catalyst was crushed and treated in a plasma arc furnace at 1500 c for 30 min.
Example 8
The treatment process and the operation conditions were the same as in example 3, except that the waste noble metal catalyst was Ag/Al2O3。
Example 9
The treatment process and the operation conditions were the same as in example 3, except that the waste noble metal catalyst was Au/Al2O3。
As can be seen from the X-ray diffraction patterns of fig. 1, 2, and 3, when the time for treating the noble metal spent catalyst by dielectric barrier discharge is longer, the impurity content in the obtained leachate is lower, and the purity of the further prepared catalyst is higher. And as can be seen from the transmission electron microscope images of fig. 5, 6 and 7, the obtained Pt/C catalyst particles are spherical, the dispersity is good, the particle diameter is 1-3 nm, the product uniformity is good, the purity is high, and the amount of the loaded platinum is reduced along with the increase of the introduction rate ratio of the leaching solution to the carbon source, which shows that the invention can realize the regulation and control of the loading amount of the noble metal. The transmission electron microscope images in fig. 8 and 9 show that the comparison examples of the precious metal waste catalyst recovery treatment in the plasma furnace are commonly used at present, the high-temperature roasting process is more concentrated in heat, the temperature control procedure is complicated, impurities attached to the precious metal waste catalyst are difficult to remove, and the subsequent processes are affected. Meanwhile, the transmission electron microscope images in fig. 10 and 11 show that the invention can also be used for synthesizing noble metal catalysts such as carbon-supported gold and silver. In conclusion, the invention can realize the high-efficiency treatment of the waste noble metal catalyst under the low-temperature condition and can realize the continuous preparation of the high-quality noble metal catalyst.
The above examples are only for the purpose of clearly illustrating the process flow of the present invention. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement and the like made by a person having ordinary skill in the art without departing from the principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. A high-value utilization method of a precious metal waste catalyst is characterized by comprising the following steps:
(1) the method comprises the following steps of taking a precious metal waste catalyst as a raw material, crushing and flatly paving the precious metal waste catalyst in a quartz boat, continuously and stably inputting inert gas/reducing gas into the quartz boat, applying high-voltage alternating current on two sides of the quartz boat to form dielectric barrier discharge plasma after the gas flow is stable, and pretreating the precious metal waste catalyst at room temperature under the action of the plasma;
(2) dissolving precious metals in the pretreatment product by using the selective leaching solution at a certain temperature to obtain a leaching solution;
(3) under the operation of atmospheric pressure and room temperature, a carbon source and leaching solution are used as reaction liquid, placed in a container and then conveyed into a three-way pipe of a plasma reactor through a plunger pump, a stainless steel pipe in the three-way pipe is used as a cathode, a platinum wire is inserted into the three-way pipe to be used as an anode, then alternating current high voltage is applied to the cathode of the plasma reactor under the atmosphere of inert gas/reducing gas, after a plasma arc is stabilized, noble metal ions and the carbon source in the reaction liquid are subjected to reduction reaction simultaneously, and the noble metal/carbon nano catalyst is synthesized in situ in one step;
(4) and centrifuging, washing with deionized water and drying the collected product to obtain the noble metal/carbon catalyst with uniform particle size and stable structural property.
2. The method for high-value utilization of a noble metal waste catalyst according to claim 1, wherein in the step (1), the noble metal waste catalyst is a platinum-based, palladium-based, gold-based, rhodium-based, silver-based or ruthenium-based noble metal waste catalyst or a combination thereof; the granularity of the crushed precious metal waste catalyst is 80-400 meshes; the plasma pretreatment time is 5-120 min; the diameter of the quartz boat is 10-30 cm, and the depth is 3-10 cm.
3. The method for high-value utilization of waste noble metal catalyst as claimed in claim 2, wherein in the step (1), the waste noble metal catalyst is Pt/Al2O3、Pd/Al2O3、Au/Al2O3、Pt/CeO2Or Pt/C.
4. The high-value utilization method of the waste noble metal catalyst according to claim 1, wherein a mixed gas of an inert gas and a reducing gas of 10-100 sccm is regulated and controlled in the plasma reactor in the step (1) and the step (3) through a mass flow controller and is introduced into the plasma reactor, the mixed gas is maintained for 3-60 min, and the inert gas atmosphere in the reactor is ensured; the inert gas is one or a mixture of argon and helium; the reducing gas is hydrogen, and the ratio of the inert gas to the reducing gas is 1: 10-10: 1; the applied high-voltage alternating current needs to ensure that the output power is 3-30W so as to generate plasma on a gas-solid interface and a gas-liquid interface.
5. The method for high-value utilization of a precious metal spent catalyst according to claim 1, wherein the selective leaching solution in the step (2) is an oxidant-containing hydrochloric acid solution or a cyanide solution; in the step (2), the concentration of the oxidant in the selective leaching solution is 0.05-5 mol/L, the concentration of the HCl solution is 0.1-5 mol/L, and the concentration of the cyanide solution is 0.1-3 mol/L.
6. The method for high-value utilization of a precious metal spent catalyst according to claim 5, wherein the selective leaching solution is NaClO/HCl solution, NaClO3HCl solution or H2O2a/HCN solution.
7. The method for high-value utilization of a precious metal spent catalyst according to claim 1, wherein the leaching temperature in the step (2) is 40 to 100 ℃.
8. The method for highly utilizing a noble metal spent catalyst according to claim 1, wherein the cathode in the step (3) has a tube length of 60 to 120mm, a tube inner diameter of 1.6 to 3.2mm, and a tube outer diameter of 1.8 to 3.6 mm; the distance between the cathode and the anode of the plasma reactor is 0.5-3 mm.
9. The method for high-value utilization of a precious metal spent catalyst according to claim 1, wherein the carbon source in the step (3) is one or a combination of not less than two of ethanol, isopropanol, activated carbon, glycerol, acetic acid and propionic acid.
10. The method for high-value utilization of a precious metal spent catalyst according to claim 1, wherein in the step (4), the rotation speed of the centrifugation is 500-5000 r/min for 0.5-3 h, and the drying temperature is 40-60 ℃ for 1-2 h.
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| CN1448522A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Method of recovering noble metal from spent catalyst containing noble metal |
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| CN103691428A (en) * | 2013-12-26 | 2014-04-02 | 大连大学 | Preparation method of carbon-supported noble metal catalyst |
| CN109499565A (en) * | 2019-01-02 | 2019-03-22 | 江南大学 | A kind of method that one-step method prepares carbon supported platinum nano particle |
| CN111940757A (en) * | 2020-08-14 | 2020-11-17 | 江南大学 | Device and method for continuously preparing noble metal and alloy nanoparticles thereof |
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| CN1448522A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Method of recovering noble metal from spent catalyst containing noble metal |
| CN1739854A (en) * | 2005-08-03 | 2006-03-01 | 天津大学 | Physical process of reducing supported metal catalyst |
| CN103691428A (en) * | 2013-12-26 | 2014-04-02 | 大连大学 | Preparation method of carbon-supported noble metal catalyst |
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