CN111715290A - Process for the cyclic regeneration of catalysts containing transition metals and carbon - Google Patents
Process for the cyclic regeneration of catalysts containing transition metals and carbon Download PDFInfo
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- CN111715290A CN111715290A CN202010422895.3A CN202010422895A CN111715290A CN 111715290 A CN111715290 A CN 111715290A CN 202010422895 A CN202010422895 A CN 202010422895A CN 111715290 A CN111715290 A CN 111715290A
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a cyclic regeneration method of a catalyst containing transition metal and carbon, which comprises the step of regenerating the catalyst after catalytic deactivation, namely mixing the deactivated catalyst with a regeneration liquid, and then placing the mixture in a closed pressure-resistant container for heating and pressurizing regeneration treatment. The regenerated catalyst still has certain catalytic performance, and after it is deactivated again, the above-mentioned method can be used to make further regeneration. The method of the invention is a novel, simple and high-efficiency method for regenerating the catalyst containing transition metal and carbon. Compared with the common high-temperature activation after the catalyst is synthesized, the method of the invention does not need an activation step, thus saving energy consumption; the catalyst regenerated by the method still maintains the catalytic performance; the process has the advantages of breakthrough, can greatly reduce the operation cost of enterprises, is favorable for circular economy and hazardous waste management and disposal, is suitable for popularization and use, and has good comprehensive economic benefit.
Description
Technical Field
The invention relates to a regeneration method of a catalyst, in particular to a regeneration method of a metal and nonmetal composite catalyst, which is applied to the technical field of catalyst regeneration and reuse.
Background
The catalyst plays a vital role in the chemical fields of pharmacy, petrifaction, environmental protection and the like. According to statistics, more than 90% of chemical processes require the participation of various catalysts. Therefore, designing and preparing a high efficiency catalyst is a common concern for a large number of researchers. In decades of development, the chemical and energy environmental protection industries have produced five major classes of catalysts that are most used, namely: solid acid-base catalysts, zeolite molecular sieve catalysts, metal catalysts, non-metal catalysts, and semiconductor catalysts. Among these complex and diverse catalysts, transition metals have been used most widely, such as catalytic epoxidation of olefins, catalytic combustion of acetone and toluene, catalytic trifluoromethylation of carbon-hydrogen bond activation, catalytic o-dichlorobenzene, etc., by using one or a combination of iron, manganese, nickel, copper, zinc, vanadium, titanium, chromium, tungsten, cesium, etc. It can be said that the use of transition metals in the field of catalysis has greatly accelerated the progress of chemical development.
Meanwhile, with the gradual development and use of transition metals, the non-metallic carbon material has the characteristics of large specific surface area and pore volume, chemical inertness, good mechanical stability, adjustable physical/chemical properties, environmental friendliness, low price and the like, and is developed into an adsorbent, a separating agent and a catalyst carrier by researchers. Novel carbon materials such as activated carbon, graphene oxide, carbon nanotubes, etc. have limited catalytic activity, and their regulation and control usually employs transition metal atom doping to improve their catalytic activity.
At present, catalysts containing transition metals and carbon are most widely used. In chemical production, the catalyst can be used for catalyzing the hydrogenation conversion of the synthesis gas to prepare the low-carbon alcohol, namely catalyzing two greenhouse gases (CH)4/CO2) Conversion to synthesis gas (H) useful for clean energy production2CO), this catalytic synthesis method is considered to be a promising advanced technology. In addition, in terms of new energy, a catalyst containing a transition metal and carbon has electrocatalytic oxygen reduction and oxygen evolution catalytic activities, and is an important research object of a cathode catalyst in a fuel cell. In the field of environmental protection, catalysts containing transition metals and carbon exhibit high catalytic reduction performance for NO in the technical application of Selective Catalytic Reduction (SCR) of NO. So to speak, because of its catalytic effectRemarkably, the use of transition metal and carbon containing catalysts is not only widespread but also extensive.
However, when such a catalyst is deactivated, the dangerous waste containing transition metals accumulated outdoors may not only destroy soil environment and atmospheric environment, but also cause water pollution. At present, the centralized treatment work of hazardous wastes is still in an exploration phase. On the one hand, most of the waste is not processed in a centralized way, and the management and disposal are still carried out by using the traditional way. On the other hand, because the hazardous waste treatment equipment is very old, a large amount of capital and energy are required to be invested for maintenance, the cost for hazardous waste treatment is high, and the production cost of enterprises is increased.
Therefore, a new technical means is urgently needed to be found to solve a plurality of problems in the treatment after the deactivation of the catalyst containing the transition metal and the carbon at present, including the problems of environmental pollution, high treatment cost, incomplete treatment technology, resource waste and the like.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art, and provides a cyclic regeneration method of a catalyst containing transition metal and carbon, which solves a plurality of problems in the deactivation post-treatment of the prior catalyst containing transition metal and carbon, repeatedly utilizes transition metal resources and reduces the operation cost of enterprises.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a cyclic regeneration method of a catalyst containing transition metal and carbon is characterized in that firstly, the deactivated catalyst is mixed with a regeneration liquid to form a deactivated catalyst mixed liquid to be treated; then the mixed solution of the deactivated catalyst is put in a closed pressure-resistant container for heating and pressurizing regeneration treatment, so that the catalyst containing transition metal and carbon is circularly regenerated.
As a preferred technical scheme of the invention, the method for circularly regenerating the catalyst containing the transition metal and the carbon comprises the following steps:
(1) putting a catalyst containing transition metal and carbon which is subjected to catalytic deactivation into a regeneration liquid for uniform mixing, wherein the regeneration liquid contains a regenerant, the mass ratio of the deactivated catalyst to the regenerant is 5 (1-4), and preparing a deactivated catalyst mixed liquid; the components of the regenerant contain a carboxylic acid group, a hydroxyl group and a benzene ring, wherein the molar ratio of the carboxylic acid group to the benzene ring is (1-3): 1, and the mole number of the hydroxyl group is at least 1000 times of that of the benzene ring;
(2) putting the deactivated catalyst mixed solution prepared in the step (1) into a closed pressure-resistant container, and heating and pressurizing the deactivated catalyst mixed solution; controlling the temperature to be 120-250 ℃, the pressure to be 101.325-1013.25 kPa and the processing time to be 6-12 h, so that the catalyst containing transition metal and carbon is subjected to cyclic regeneration reaction to obtain a product solution;
(3) separating out a solid product in the product solution obtained in the step (2), and washing the solid product by using deionized water until the pH value of the solution is neutral; the washed solid product is then dried under vacuum at no more than 120 ℃ for at least 8 hours and the dried solid is then ground to below 100 mesh to yield a regenerated transition metal and carbon-containing catalyst material.
In the preferred embodiment of the present invention, in the step (2), the temperature is controlled to be 180 to 250 ℃ when the cyclic regeneration reaction is performed.
In a preferred embodiment of the present invention, in the step (3), the solid product in the product solution obtained in the step (2) is separated, and the waste liquid after the regeneration reaction is poured out, collected and stored for the next round of catalyst recycling, and in the step (1), the waste liquid after the regeneration reaction is used as a regeneration liquid and recycled.
The weight ratio of the transition metal to carbon is preferably (1-5): 10.
Preferably, the transition metal is any one or combination of any several of iron, manganese, nickel, copper, zinc, vanadium, titanium, chromium, tungsten and cesium.
Preferably, the carbon is any one or combination of any several of activated carbon, graphene oxide, graphene and carbon nanotubes.
The above-mentioned regenerant preferably uses a mixed solution of terephthalic acid, N-dimethylformamide and ethanol.
As a preferred technical scheme of the invention, after the regenerated catalyst is deactivated again, the cyclic regeneration method of the catalyst containing the transition metal and the carbon is continuously adopted to carry out the regeneration treatment of the catalyst, so that the catalyst containing the transition metal and the carbon can be continuously used in a catalytic-regeneration-catalytic mode for multiple times.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. compared with the common treatment method of hazardous wastes such as landfill, incineration and the like, the process recycles the waste containing transition metal and carbon after catalytic deactivation, is environment-friendly, achieves the aim of recycling resources and reduces the operation cost of enterprises;
2. compared with the common catalyst which is activated at high temperature after being synthesized, the method of the invention does not need an activation step, thus saving energy consumption;
3. compared with the treatment and disposal process of hazardous wastes, the regeneration process method is simple, and the regeneration liquid can be reused;
4. the catalyst regenerated by the method still maintains the catalytic performance; the process has breakthrough advantages, can greatly reduce the operation cost of enterprises, is favorable for circular economy and hazardous waste management and disposal, and is suitable for popularization and use.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely illustrative of some, but not all, embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example one
In this embodiment, a method for cyclically regenerating a catalyst (Cu-BTC) containing transition metal and carbon includes the steps of placing a certain amount of Cu-BTC sample into a reaction tube, performing Selective Catalytic Reduction (SCR) NO reaction, and regenerating the deactivated catalyst (Cu-BTC) containing transition metal and carbon as follows:
a. after the catalytic reaction is finished, taking out the deactivated catalyst in the reaction tube, placing the catalyst containing transition metal and carbon which is deactivated by catalysis into a regeneration liquid for uniform mixing, wherein the regeneration liquid contains a regenerant, the regenerant adopts a mixed solution of terephthalic acid, N-dimethylformamide and ethanol, the mass ratio of the deactivated catalyst to the regenerant is 5:4, and preparing a deactivated catalyst mixed solution; the components of the regenerant contain a carboxylic acid group, a hydroxyl group and a benzene ring, wherein the molar ratio of the carboxylic acid group to the benzene ring is 3:1, and the molar number of the hydroxyl group is more than 1000 times that of the benzene ring; the weight ratio of the transition metal and the carbon which are subjected to catalytic deactivation is 5: 10;
b. b, mixing and stirring the deactivated catalyst mixed solution prepared in the step a, putting the mixture into a stainless steel autoclave with a polytetrafluoroethylene lining, and heating and pressurizing the mixture; controlling the temperature to be 120 ℃, the pressure to be 1013.25kPa and the processing time to be 12h, thereby enabling the catalyst containing transition metal and carbon to carry out a cyclic regeneration reaction to obtain a product solution;
c. separating out a solid product in the product solution obtained in the step (2), and washing the solid product by using deionized water until the pH value of the solution is neutral; and then drying the washed solid product for 8 hours under the vacuum condition of 120 ℃, and then grinding the dried solid to be below 100 meshes to obtain the regenerated catalyst material containing the transition metal and the carbon.
In this example, the above-mentioned method for recycling the transition metal and carbon-containing catalyst (Cu-BTC) resulted in a regenerated transition metal and carbon-containing catalyst material, which is designated as "recycled first-time regenerated sample" for future use.
In this example, in the step (3), the solid product in the product solution obtained in the step (2) is separated, and the waste liquid after the regeneration reaction is poured out, collected and stored for the next round of catalyst recycling, in the step (1), the waste liquid after the regeneration reaction is used as the regeneration liquid, and is recycled.
And after the first regeneration sample is circulated and deactivated again, the catalyst regeneration treatment is continuously carried out by adopting the method for circularly regenerating the catalyst containing the transition metal and the carbon, so that the catalyst containing the transition metal and the carbon can be continuously used for multiple times of catalysis, regeneration and catalysis.
Experimental test analysis:
the cyclic first regeneration sample of the polytetrafluoroethylene polymer prepared in the embodiment is used as a sample to be subjected to experimental analysis, a certain amount of cyclic first regeneration sample is put into an SCR reaction tube to be subjected to SCR-NO reaction, and after the reaction is finished, the NO removal rate is calculated through the concentration of NO at the inlet and the outlet recorded by an analyzer, the result shows better denitration performance, the inactivated catalyst in the reaction tube is taken out, the next round of synthesis-regeneration-catalysis is carried out, and through continuous repeated cyclic regeneration catalysis experiments, the removal rate of NO by the catalyst containing transition metal and carbon is stabilized from 99.9 percent of the removal rate of NO by the initial first regeneration sample to 60-80 percent of the removal rate after repeated use, the discharged dangerous waste is almost completely consumed, and the gas generated by SCR reaction meets the requirement of the emission standard. After the catalyst regenerated in this example was deactivated again, regeneration was continued using the above method. The method can be applied to the cyclic catalysis-regeneration-catalysis process of the catalyst containing the transition metal and the carbon.
Example two
This embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a method for cyclically regenerating a catalyst (Cu-BTC) containing transition metal and carbon includes the steps of placing a certain amount of Cu-BTC sample into a reaction tube, performing Selective Catalytic Reduction (SCR) NO reaction, and regenerating the deactivated catalyst (Cu-BTC) containing transition metal and carbon as follows:
a. after the catalytic reaction is finished, taking out the deactivated catalyst in the reaction tube, placing the catalyst containing transition metal and carbon which is deactivated by catalysis into a regeneration liquid for uniform mixing, wherein the regeneration liquid contains a regenerant, the regenerant adopts a mixed solution of terephthalic acid, N-dimethylformamide and ethanol, the mass ratio of the deactivated catalyst to the regenerant is 5:1, and preparing a deactivated catalyst mixed solution; the components of the regenerant contain a carboxylic acid group, a hydroxyl group and a benzene ring, wherein the molar ratio of the carboxylic acid group to the benzene ring is 1:1, and the mole number of the hydroxyl group is more than 1000 times that of the benzene ring; the weight ratio of the transition metal and the carbon which are subjected to catalytic deactivation is 1: 10;
b. b, mixing and stirring the deactivated catalyst mixed solution prepared in the step a, putting the mixture into a stainless steel autoclave with a polytetrafluoroethylene lining, and heating and pressurizing the mixture; controlling the temperature to be 250 ℃, the pressure to be 101.325kPa and the processing time to be 6h, thereby carrying out the cyclic regeneration reaction on the catalyst containing the transition metal and the carbon to obtain a product solution;
c. separating out a solid product in the product solution obtained in the step (2), and washing the solid product by using deionized water until the pH value of the solution is neutral; and then drying the washed solid product for 8 hours under the vacuum condition of 120 ℃, and then grinding the dried solid to be below 100 meshes to obtain the regenerated catalyst material containing the transition metal and the carbon.
In this example, the above-mentioned method for recycling the transition metal and carbon-containing catalyst (Cu-BTC) resulted in a regenerated transition metal and carbon-containing catalyst material, which is designated as "recycled first-time regenerated sample" for future use.
In this example, in the step (3), the solid product in the product solution obtained in the step (2) is separated, and the waste liquid after the regeneration reaction is poured out, collected and stored for the next round of catalyst recycling, in the step (1), the waste liquid after the regeneration reaction is used as the regeneration liquid, and is recycled.
And after the first regeneration sample is circulated and deactivated again, the catalyst regeneration treatment is continuously carried out by adopting the method for circularly regenerating the catalyst containing the transition metal and the carbon, so that the catalyst containing the transition metal and the carbon can be continuously used for multiple times of catalysis, regeneration and catalysis.
Experimental test analysis:
the cyclic first regeneration sample of the polytetrafluoroethylene polymer prepared in the embodiment is used as a sample to be subjected to experimental analysis, a certain amount of cyclic first regeneration sample is put into an SCR reaction tube to be subjected to SCR-NO reaction, and after the reaction is finished, the NO removal rate is calculated through the concentration of NO at the inlet and the outlet recorded by an analyzer, the result shows better denitration performance, the inactivated catalyst in the reaction tube is taken out, the next round of synthesis-regeneration-catalysis is carried out, and through continuous repeated cyclic regeneration catalysis experiments, the removal rate of NO by the catalyst containing transition metal and carbon is stabilized from 99.9 percent of the removal rate of NO by the initial first regeneration sample to 60-80 percent of the removal rate after repeated use, the discharged dangerous waste is almost completely consumed, and the gas generated by SCR reaction meets the requirement of the emission standard. After the catalyst regenerated in this example was deactivated again, regeneration was continued using the above method. The method can be applied to the cyclic catalysis-regeneration-catalysis process of the catalyst containing the transition metal and the carbon.
EXAMPLE III
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for cyclically regenerating a catalyst (Cu-BTC) containing transition metal and carbon includes the steps of placing a certain amount of Cu-BTC sample into a reaction tube, performing Selective Catalytic Reduction (SCR) NO reaction, and regenerating the deactivated catalyst (Cu-BTC) containing transition metal and carbon as follows:
a. after the catalytic reaction is finished, taking out the deactivated catalyst in the reaction tube, placing the catalyst containing transition metal and carbon which is deactivated by catalysis into a regeneration liquid for uniform mixing, wherein the regeneration liquid contains a regenerant, the regenerant adopts a mixed solution of terephthalic acid, N-dimethylformamide and ethanol, the mass ratio of the deactivated catalyst to the regenerant is 5:3, and preparing a deactivated catalyst mixed solution; the components of the regenerant contain a carboxylic acid group, a hydroxyl group and a benzene ring, wherein the molar ratio of the carboxylic acid group to the benzene ring is 2:1, and the mole number of the hydroxyl group is 1000 times that of the benzene ring; the weight ratio of the transition metal and the carbon which are subjected to catalytic deactivation is 3: 10;
b. b, mixing and stirring the deactivated catalyst mixed solution prepared in the step a, putting the mixture into a stainless steel autoclave with a polytetrafluoroethylene lining, and heating and pressurizing the mixture; controlling the temperature to be 180 ℃, the pressure to be 202.65kPa and the processing time to be 10h, so that the catalyst containing transition metal and carbon is subjected to cyclic regeneration reaction to obtain a product solution;
c. separating out a solid product in the product solution obtained in the step (2), and washing the solid product by using deionized water until the pH value of the solution is neutral; and then drying the washed solid product for 8 hours under the vacuum condition of 120 ℃, and then grinding the dried solid to be below 100 meshes to obtain the regenerated catalyst material containing the transition metal and the carbon.
In this example, the above-mentioned method for recycling the transition metal and carbon-containing catalyst (Cu-BTC) resulted in a regenerated transition metal and carbon-containing catalyst material, which is designated as "recycled first-time regenerated sample" for future use.
In this example, in the step (3), the solid product in the product solution obtained in the step (2) is separated, and the waste liquid after the regeneration reaction is poured out, collected and stored for the next round of catalyst recycling, in the step (1), the waste liquid after the regeneration reaction is used as the regeneration liquid, and is recycled.
And after the first regeneration sample is circulated and deactivated again, the catalyst regeneration treatment is continuously carried out by adopting the method for circularly regenerating the catalyst containing the transition metal and the carbon, so that the catalyst containing the transition metal and the carbon can be continuously used for multiple times of catalysis, regeneration and catalysis.
Experimental test analysis:
the cyclic first regeneration sample of the polytetrafluoroethylene polymer prepared in the embodiment is used as a sample to be subjected to experimental analysis, a certain amount of cyclic first regeneration sample is put into an SCR reaction tube to be subjected to SCR-NO reaction, and after the reaction is finished, the NO removal rate is calculated through the concentration of NO at the inlet and the outlet recorded by an analyzer, the result shows better denitration performance, the inactivated catalyst in the reaction tube is taken out, the next round of synthesis-regeneration-catalysis is carried out, and through continuous repeated cyclic regeneration catalysis experiments, the removal rate of NO by the catalyst containing transition metal and carbon is stabilized from 99.9 percent of the removal rate of NO by the initial first regeneration sample to 60-80 percent of the removal rate after repeated use, the discharged dangerous waste is almost completely consumed, and the gas generated by SCR reaction meets the requirement of the emission standard. After the catalyst regenerated in this example was deactivated again, regeneration was continued using the above method. The method can be applied to the cyclic catalysis-regeneration-catalysis process of the catalyst containing the transition metal and the carbon.
Example four
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a method for cyclically regenerating a catalyst containing transition metal and carbon includes mixing a deactivated catalyst with a regeneration solution to form a deactivated catalyst mixture to be treated; then the mixed solution of the deactivated catalyst is put in a closed pressure-resistant container for heating and pressurizing regeneration treatment, so that the catalyst containing transition metal and carbon is circularly regenerated. The catalyst containing transition metal and carbon in this embodiment is not only suitable for Cu-BTC, but also the transition metal in this embodiment can be any one or a combination of any several of iron, manganese, nickel, copper, zinc, vanadium, titanium, chromium, tungsten and cesium; the carbon in this embodiment is any one of activated carbon, graphene oxide, graphene, and carbon nanotubes, or a combination of any several of them. After the catalyst regenerated in this example was deactivated again, regeneration was continued using the above method. The method can be applied to the cyclic catalysis-regeneration-catalysis process of the catalyst containing the transition metal and the carbon.
From the above examples, it can be seen that the method for recycling and regenerating a catalyst containing transition metal and carbon comprises the step of regenerating the catalyst after its catalytic deactivation, i.e. mixing the deactivated catalyst with a regeneration liquid, and placing the mixture in a closed pressure-resistant container for heating and pressurizing the mixture. The regenerated catalyst still has certain catalytic performance, and after it is deactivated again, the above-mentioned method can be used to make further regeneration. The method of the embodiment belongs to a novel, simple and efficient method for regenerating the catalyst containing the transition metal and the carbon, is favorable for recycling economy and dangerous waste management and disposal, and is suitable for popularization and use.
While the embodiments of the present invention have been described, the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention may be made in equivalent substitution ways without departing from the technical principle and inventive concept of the cyclic regeneration method of the catalyst containing transition metal and carbon of the present invention.
Claims (9)
1. A process for the cyclic regeneration of a catalyst containing a transition metal and carbon, characterized in that: firstly, mixing the deactivated catalyst with a regeneration liquid to form a deactivated catalyst mixed liquid to be treated; then the mixed solution of the deactivated catalyst is put in a closed pressure-resistant container for heating and pressurizing regeneration treatment, so that the catalyst containing transition metal and carbon is circularly regenerated.
2. A process for the cyclic regeneration of a catalyst containing a transition metal and carbon according to claim 1, comprising the steps of:
(1) putting a catalyst containing transition metal and carbon which is subjected to catalytic deactivation into a regeneration liquid for uniform mixing, wherein the regeneration liquid contains a regenerant, the mass ratio of the deactivated catalyst to the regenerant is 5 (1-4), and preparing a deactivated catalyst mixed liquid; the components of the regenerant contain a carboxylic acid group, a hydroxyl group and a benzene ring, wherein the molar ratio of the carboxylic acid group to the benzene ring is (1-3): 1, and the mole number of the hydroxyl group is at least 1000 times of that of the benzene ring;
(2) putting the deactivated catalyst mixed solution prepared in the step (1) into a closed pressure-resistant container, and heating and pressurizing the deactivated catalyst mixed solution; controlling the temperature to be 120-250 ℃, the pressure to be 101.325-1013.25 kPa and the processing time to be 6-12 h, so that the catalyst containing transition metal and carbon is subjected to cyclic regeneration reaction to obtain a product solution;
(3) separating out a solid product in the product solution obtained in the step (2), and washing the solid product by using deionized water until the pH value of the solution is neutral; the washed solid product is then dried under vacuum at no more than 120 ℃ for at least 8 hours and the dried solid is then ground to below 100 mesh to yield a regenerated transition metal and carbon-containing catalyst material.
3. The process for the cyclic regeneration of a catalyst containing a transition metal and carbon according to claim 2, wherein: in the step (2), the temperature is controlled to be 180-250 ℃ during the cyclic regeneration reaction.
4. The process for the cyclic regeneration of a catalyst containing a transition metal and carbon according to claim 2, wherein: in the step (3), the solid product in the product solution obtained in the step (2) is separated, and the waste liquid after the regeneration reaction is poured out, collected and stored for the next round of the cyclic regeneration of the catalyst, and in the step (1), the waste liquid after the regeneration reaction is used as the regeneration liquid to be recycled.
5. The method for cyclically regenerating a catalyst containing a transition metal and carbon according to any one of claims 1 to 4, wherein: the weight ratio of the catalytically inactive transition metal to the carbon is (1-5): 10.
6. The method for cyclically regenerating a catalyst containing a transition metal and carbon according to any one of claims 1 to 4, wherein: the transition metal is any one or combination of any several of iron, manganese, nickel, copper, zinc, vanadium, titanium, chromium, tungsten and cesium.
7. The method for cyclically regenerating a catalyst containing a transition metal and carbon according to any one of claims 1 to 4, wherein: the carbon is any one or combination of any several of activated carbon, graphene oxide, graphene and carbon nanotubes.
8. The method for cyclically regenerating a catalyst containing a transition metal and carbon according to any one of claims 1 to 4, wherein: the regenerant is a mixed solution of terephthalic acid, N-dimethylformamide and ethanol.
9. The method for cyclically regenerating a catalyst containing a transition metal and carbon according to any one of claims 1 to 4, wherein: after the regenerated catalyst is deactivated again, the catalyst regeneration treatment is carried out by continuously adopting the cyclic regeneration method of the catalyst containing the transition metal and the carbon, so that the catalyst containing the transition metal and the carbon can be continuously used for multiple times of catalytic-regeneration-catalytic circulation.
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| CN113019470A (en) * | 2021-03-18 | 2021-06-25 | 上海大学材料基因组工程(萍乡)研究院 | Method for activating transition metal catalyst |
| CN115430435A (en) * | 2022-09-13 | 2022-12-06 | 珠海格力电器股份有限公司 | Regeneration method of catalytic filter screen |
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| CN113019470A (en) * | 2021-03-18 | 2021-06-25 | 上海大学材料基因组工程(萍乡)研究院 | Method for activating transition metal catalyst |
| CN115430435A (en) * | 2022-09-13 | 2022-12-06 | 珠海格力电器股份有限公司 | Regeneration method of catalytic filter screen |
| CN115430435B (en) * | 2022-09-13 | 2023-09-01 | 珠海格力电器股份有限公司 | Regeneration method of catalytic filter screen |
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