CN111715290B - Method for recycling catalyst containing transition metal and carbon - Google Patents
Method for recycling catalyst containing transition metal and carbon Download PDFInfo
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- CN111715290B CN111715290B CN202010422895.3A CN202010422895A CN111715290B CN 111715290 B CN111715290 B CN 111715290B CN 202010422895 A CN202010422895 A CN 202010422895A CN 111715290 B CN111715290 B CN 111715290B
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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 method for recycling catalyst containing transition metal and carbon, which comprises the steps of regenerating the catalyst after catalytic deactivation, namely, mixing the deactivated catalyst with a regenerating liquid, and then placing the mixture in a closed compression-resistant container for heating and pressurizing regeneration treatment. The regenerated catalyst still has certain catalytic performance, and after the catalyst is deactivated again, the catalyst can be regenerated continuously by using the method. The method is a novel, simple and efficient method for regenerating the catalyst containing the transition metal and the carbon. Compared with the common catalyst synthesized by high-temperature activation, the method does not need an activation step, and saves energy consumption; the catalyst regenerated by the method still has catalytic performance; the process has the breakthrough advantages of greatly reducing the running cost of enterprises, being beneficial to recycling economy and dangerous waste management and disposal, being suitable for popularization and use and having good comprehensive economic benefit.
Description
Technical Field
The invention relates to a catalyst regeneration method, in particular to a metal and nonmetal composite catalyst regeneration method, 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, petrochemical industry, environmental protection and the like. It is counted that more than 90% of chemical processes require the participation of various catalysts. Therefore, designing and preparing efficient catalysts is a general concern for large researchers. In decades of development, the chemical and energy environment protection industries have produced five most widely used classes of catalysts, 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 are most widely used, such as by one or a combination of several of iron, manganese, nickel, copper, zinc, vanadium, titanium, chromium, tungsten, cesium, etc., to catalyze olefin epoxidation, to catalyze the combustion of acetone and toluene, to catalyze hydrocarbon bond-activated trifluoromethyl, to catalyze ortho-dichlorobenzene, and the like. The use of transition metals in the catalytic field can be said to greatly accelerate the progress of chemical development.
Meanwhile, with the gradual development and use of transition metals, nonmetallic carbon materials are developed into adsorbents, separating agents and catalyst carriers by researchers due to 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. Novel carbon materials such as activated carbon, graphene oxide, carbon nanotubes and the like have limited catalytic effects, and transition metal atom doping is generally used for controlling the carbon materials to improve the catalytic activity of the carbon materials.
Currently, catalysts containing transition metals and carbon are most widely used. In chemical production, the catalyst can catalyze the hydrogenation conversion of synthesis gas to prepare low-carbon alcohol, namely, catalyze two greenhouse gases (CH 4 /CO 2 ) Conversion to synthesis gas (H) useful for clean energy production 2 CO), this catalytic synthesis method is considered to be a very promising advanced technology. In addition, in the aspect of new energy sources, the catalyst containing transition metal and carbon has electrocatalytic oxygen reduction and oxygen evolution catalytic activity, and is an important research object of cathode catalysts in fuel cells. In the field of environmental protection, catalysts containing transition metals and carbon exhibit efficient catalytic reduction performance on NO in the technical application of Selective Catalytic Reduction (SCR) of NO. It can be said that the use of a catalyst containing a transition metal and carbon is not only widespread but also massive because of its remarkable catalytic effect.
However, when such catalysts are deactivated, the accumulation of these dangerous wastes containing transition metals outdoors can destroy the soil environment and the atmospheric environment, and also can cause water pollution. At present, dangerous waste centralized treatment work is still in an exploration stage. On the one hand, most of the waste is not treated in a centralized way, and is still managed and disposed of in a conventional way. On the other hand, because the hazardous waste treatment equipment is very old, a great deal of funds and energy are needed to be invested for maintenance, the cost of hazardous waste treatment is high, and therefore the production cost of enterprises is increased.
Therefore, a new technical means is needed to solve the problems of the prior catalyst containing transition metal and carbon in the deactivation post-treatment, including the problems of environmental pollution, high treatment cost, imperfect 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 of the prior art, provide a method for recycling catalyst containing transition metal and carbon, solve a plurality of problems in the prior catalyst deactivation post-treatment containing transition metal and carbon, recycle transition metal resources and reduce the running cost of enterprises.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for recycling catalyst containing transition metal and carbon comprises mixing deactivated catalyst with regeneration liquid to form mixed liquid of deactivated catalyst to be treated; and then placing the deactivated catalyst mixed solution in a closed compression-resistant container, and carrying out heating and pressurizing regeneration treatment to circularly regenerate the catalyst containing transition metal and carbon.
As a preferred technical scheme of the invention, the method for circularly regenerating the catalyst containing transition metal and carbon comprises the following steps:
(1) Placing the catalyst containing transition metal and carbon which are subjected to catalytic deactivation into a regeneration liquid for uniform mixing, wherein the regeneration liquid contains a regenerant, and the mass ratio of the deactivated catalyst to the regenerant is 5 (1-4), so as to prepare a deactivated catalyst mixed liquid; the components of the regenerant comprise carboxylic acid groups, hydroxyl groups and benzene rings, wherein the molar ratio of the carboxylic acid groups to the benzene rings is (1-3) 1, and the molar number of the hydroxyl groups is at least 1000 times of that of the benzene rings;
(2) Placing the mixed solution of the deactivated catalyst prepared in the step (1) into a closed compression-resistant container, and heating and pressurizing; the temperature is controlled to be 120-250 ℃, the pressure is controlled to be 101.325-1013.25 kPa, and the treatment time is controlled to be 6-12 hours, so that the catalyst containing transition metal and carbon is subjected to cyclic regeneration reaction to obtain a product solution;
(3) Separating solid products in the product solution obtained in the step (2), and cleaning the solid products by using deionized water until the pH of the solution is neutral; and then drying the washed solid product for at least 8 hours under vacuum condition not higher than 120 ℃, and grinding the dried solid to below 100 meshes to obtain the regenerated catalyst material containing transition metal and carbon.
As a preferable technical scheme of the invention, in the step (2), when the cyclic regeneration reaction is carried out, the temperature is controlled to be 180-250 ℃.
In the 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 and collected and stored, so that the waste liquid after the regeneration reaction is recycled as a regeneration liquid in the step (1) when the catalyst is recycled for the next round.
The weight ratio of the transition metal to carbon is preferably (1 to 5): 10.
Preferably, the transition metal is any one or a combination of any several of iron, manganese, nickel, copper, zinc, vanadium, titanium, chromium, tungsten and cesium.
Preferably, the carbon is any one or a combination of any several of activated carbon, graphene oxide, graphene and carbon nanotubes.
The regenerating agent is preferably a mixed solution of p-benzene tricarboxylic acid, N-dimethylformamide and ethanol.
As a preferable technical scheme of the invention, after the regenerated catalyst is deactivated again, the catalyst regeneration treatment is carried out by adopting the circulating 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 catalyzed, regenerated and catalyzed for multiple times.
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. compared with the common hazardous waste treatment methods such as landfill and incineration, the method of the invention circularly regenerates the waste containing transition metal and carbon after catalytic deactivation, thereby being environment-friendly, achieving the aim of recycling resources and reducing the running cost of enterprises;
2. compared with the common catalyst synthesized by high-temperature activation, the method does not need an activation step, and saves energy consumption;
3. compared with the treatment and disposal process of hazardous waste, the method of the invention has simple regeneration process and the regenerated liquid can be reused;
4. the catalyst regenerated by the method still has catalytic performance; the process has the breakthrough advantage of greatly reducing the running cost of enterprises, is beneficial to recycling economy and dangerous waste management and disposal, and is suitable for popularization and use.
Detailed Description
For the purpose of making the technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. It will be apparent that the described examples are only some, but not all embodiments of the invention. All other embodiments, based on the examples of the invention, which are within the scope of the invention as claimed by a person of ordinary skill in the art without any inventive effort.
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
example 1
In this embodiment, a method for recycling a catalyst (Cu-BTC) containing a transition metal and carbon, taking a certain amount of Cu-BTC sample, placing the sample in a reaction tube, and performing a Selective Catalytic Reduction (SCR) NO reaction, where the steps of the method for recycling the deactivated catalyst (Cu-BTC) containing a transition metal and carbon are as follows:
a. after the catalytic reaction is finished, taking out the deactivated catalyst in the reaction tube, placing the catalyst which is subjected to catalytic deactivation and contains transition metal and carbon in a regeneration liquid for uniform mixing, wherein the regeneration liquid contains a regenerant, and the regenerant adopts a mixed solution of terephthalic acid, N-dimethylformamide and ethanol, so that the mass ratio of the deactivated catalyst to the regenerant is 5:4, and preparing an inactivated catalyst mixed liquid; the components of the regenerant comprise carboxylic acid groups, hydroxyl groups and benzene rings, wherein the molar ratio of the carboxylic acid groups to the benzene rings is 3:1, and the molar number of the hydroxyl groups is more than 1000 times of the molar number of the benzene rings; the weight ratio of the catalytically inactive transition metal to carbon is 5:10;
b. c, mixing and stirring the mixed solution of the deactivated catalyst prepared in the step a, and then placing the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining for heating and pressurizing treatment; the temperature is controlled to be 120 ℃, the pressure is controlled to be 1013.25kPa, and the treatment time is controlled to be 12 hours, so that the catalyst containing transition metal and carbon is subjected to cyclic regeneration reaction to obtain a product solution;
c. separating solid products in the product solution obtained in the step (2), and cleaning the solid products by using deionized water until the pH of the solution is neutral; and then drying the cleaned solid product for 8 hours under the vacuum condition of 120 ℃, and grinding the dried solid to below 100 meshes to obtain the regenerated catalyst material containing the transition metal and the carbon.
In this example, the above-described method for recycling catalyst containing transition metal and carbon (Cu-BTC) yielded a recycled catalyst material containing transition metal and carbon, with the standard "recycle first recycle sample" for use.
In this embodiment, 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, and when the catalyst is regenerated in the next cycle, the waste liquid after the regeneration reaction is recycled as the regeneration liquid in the step (1).
After the recycled first regeneration sample is deactivated again, the catalyst regeneration treatment is carried out by continuously adopting the recycling 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 catalyzed, regenerated and catalyzed for multiple times.
Experimental test analysis:
taking a circulating first regenerated sample of the polytetrafluoroethylene polymer prepared in the embodiment as a sample, performing experimental analysis, taking a certain amount of the circulating first regenerated sample, putting the sample into an SCR reaction tube, performing SCR-NO reaction, calculating the NO removal rate through the concentration of inlet and outlet NO recorded by an analyzer after the reaction is finished, and finally, showing good denitration performance, taking out the deactivated catalyst in the reaction tube, and performing next round of synthesis-regeneration-catalysis. After the catalyst regenerated in this example was once again deactivated, regeneration was continued using the above method. The method of the embodiment can be applied to a cyclic catalysis-regeneration-catalysis process of a catalyst containing transition metal and carbon.
Example two
This embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a method for recycling a catalyst (Cu-BTC) containing a transition metal and carbon, taking a certain amount of Cu-BTC sample, placing the sample in a reaction tube, and performing a Selective Catalytic Reduction (SCR) NO reaction, where the steps of the method for recycling the deactivated catalyst (Cu-BTC) containing a transition metal and carbon are as follows:
a. after the catalytic reaction is finished, taking out the deactivated catalyst in the reaction tube, placing the catalyst which is subjected to catalytic deactivation and contains transition metal and carbon in a regeneration liquid for uniform mixing, wherein the regeneration liquid contains a regenerant, and the regenerant adopts a mixed solution of terephthalic acid, N-dimethylformamide and ethanol, so that the mass ratio of the deactivated catalyst to the regenerant is 5:1, and preparing an inactivated catalyst mixed liquid; the components of the regenerant comprise carboxylic acid groups, hydroxyl groups and benzene rings, wherein the molar ratio of the carboxylic acid groups to the benzene rings is 1:1, and the molar number of the hydroxyl groups is more than 1000 times of the molar number of the benzene rings; the weight ratio of the catalytically inactive transition metal to carbon is 1:10;
b. c, mixing and stirring the mixed solution of the deactivated catalyst prepared in the step a, and then placing the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining for heating and pressurizing treatment; the temperature is controlled to be 250 ℃, the pressure is controlled to be 101.325kPa, and the treatment time is controlled to be 6 hours, so that the catalyst containing transition metal and carbon is subjected to cyclic regeneration reaction to obtain a product solution;
c. separating solid products in the product solution obtained in the step (2), and cleaning the solid products by using deionized water until the pH of the solution is neutral; and then drying the cleaned solid product for 8 hours under the vacuum condition of 120 ℃, and grinding the dried solid to below 100 meshes to obtain the regenerated catalyst material containing the transition metal and the carbon.
In this example, the above-described method for recycling catalyst containing transition metal and carbon (Cu-BTC) yielded a recycled catalyst material containing transition metal and carbon, with the standard "recycle first recycle sample" for use.
In this embodiment, 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, and when the catalyst is regenerated in the next cycle, the waste liquid after the regeneration reaction is recycled as the regeneration liquid in the step (1).
After the recycled first regeneration sample is deactivated again, the catalyst regeneration treatment is carried out by continuously adopting the recycling 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 catalyzed, regenerated and catalyzed for multiple times.
Experimental test analysis:
taking a circulating first regenerated sample of the polytetrafluoroethylene polymer prepared in the embodiment as a sample, performing experimental analysis, taking a certain amount of the circulating first regenerated sample, putting the sample into an SCR reaction tube, performing SCR-NO reaction, calculating the NO removal rate through the concentration of inlet and outlet NO recorded by an analyzer after the reaction is finished, and finally, showing good denitration performance, taking out the deactivated catalyst in the reaction tube, and performing next round of synthesis-regeneration-catalysis. After the catalyst regenerated in this example was once again deactivated, regeneration was continued using the above method. The method of the embodiment can be applied to a cyclic catalysis-regeneration-catalysis process of a catalyst containing transition metal and carbon.
Example III
This embodiment is substantially identical to the previous embodiment, except that:
in this embodiment, a method for recycling a catalyst (Cu-BTC) containing a transition metal and carbon, taking a certain amount of Cu-BTC sample, placing the sample in a reaction tube, and performing a Selective Catalytic Reduction (SCR) NO reaction, where the steps of the method for recycling the deactivated catalyst (Cu-BTC) containing a transition metal and carbon are as follows:
a. after the catalytic reaction is finished, taking out the deactivated catalyst in the reaction tube, placing the catalyst which is subjected to catalytic deactivation and contains transition metal and carbon in a regeneration liquid for uniform mixing, wherein the regeneration liquid contains a regenerant, and the regenerant adopts a mixed solution of terephthalic acid, N-dimethylformamide and ethanol, so that the mass ratio of the deactivated catalyst to the regenerant is 5:3, and preparing an inactivated catalyst mixed liquid; the components of the regenerant comprise carboxylic acid groups, hydroxyl groups and benzene rings, wherein the molar ratio of the carboxylic acid groups to the benzene rings is 2:1, and the molar number of the hydroxyl groups is 1000 times of that of the benzene rings; the weight ratio of the catalytically inactive transition metal to carbon is 3:10;
b. c, mixing and stirring the mixed solution of the deactivated catalyst prepared in the step a, and then placing the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining for heating and pressurizing treatment; the temperature is controlled to be 180 ℃, the pressure is controlled to be 202.65kPa, and the treatment time is controlled to be 10 hours, so that the catalyst containing transition metal and carbon is subjected to cyclic regeneration reaction to obtain a product solution;
c. separating solid products in the product solution obtained in the step (2), and cleaning the solid products by using deionized water until the pH of the solution is neutral; and then drying the cleaned solid product for 8 hours under the vacuum condition of 120 ℃, and grinding the dried solid to below 100 meshes to obtain the regenerated catalyst material containing the transition metal and the carbon.
In this example, the above-described method for recycling catalyst containing transition metal and carbon (Cu-BTC) yielded a recycled catalyst material containing transition metal and carbon, with the standard "recycle first recycle sample" for use.
In this embodiment, 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, and when the catalyst is regenerated in the next cycle, the waste liquid after the regeneration reaction is recycled as the regeneration liquid in the step (1).
After the recycled first regeneration sample is deactivated again, the catalyst regeneration treatment is carried out by continuously adopting the recycling 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 catalyzed, regenerated and catalyzed for multiple times.
Experimental test analysis:
taking a circulating first regenerated sample of the polytetrafluoroethylene polymer prepared in the embodiment as a sample, performing experimental analysis, taking a certain amount of the circulating first regenerated sample, putting the sample into an SCR reaction tube, performing SCR-NO reaction, calculating the NO removal rate through the concentration of inlet and outlet NO recorded by an analyzer after the reaction is finished, and finally, showing good denitration performance, taking out the deactivated catalyst in the reaction tube, and performing next round of synthesis-regeneration-catalysis. After the catalyst regenerated in this example was once again deactivated, regeneration was continued using the above method. The method of the embodiment can be applied to a cyclic catalysis-regeneration-catalysis process of a catalyst containing transition metal and carbon.
Example IV
This embodiment is substantially identical to the previous embodiment, except that:
in the embodiment, a method for circularly regenerating a catalyst containing transition metal and carbon comprises the steps of firstly mixing an inactivated catalyst with a regeneration liquid to form an inactivated catalyst mixed liquid to be treated; and then placing the deactivated catalyst mixed solution in a closed compression-resistant container, and carrying out heating and pressurizing regeneration treatment to circularly regenerate the catalyst containing transition metal and carbon. The catalyst containing the transition metal and carbon is not only suitable for Cu-BTC, but also any one or the combination of any several of iron, manganese, nickel, copper, zinc, vanadium, titanium, chromium, tungsten and cesium; the carbon in this embodiment is any one or a combination of any several of activated carbon, graphene oxide, graphene, and carbon nanotubes. After the catalyst regenerated in this example was once again deactivated, regeneration was continued using the above method. The method of the embodiment can be applied to a cyclic catalysis-regeneration-catalysis process of a catalyst containing transition metal and carbon.
In summary, the embodiments show that the method for recycling catalyst containing transition metal and carbon comprises the steps of catalyst deactivation and regeneration, namely, mixing the deactivated catalyst with a regeneration liquid, and then placing the mixture in a closed compression-resistant container for heating and pressurizing regeneration treatment. The regenerated catalyst still has certain catalytic performance, and after the catalyst is deactivated again, the catalyst can be regenerated continuously by using the method. 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 beneficial to recycling economy and dangerous waste management and disposal, and is suitable for popularization and use.
The embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made under the spirit and principle of the technical solution of the present invention can be made according to the present invention, and the present invention is not limited to the above embodiments, as long as the technical principle and the inventive concept of the cyclic regeneration method of the catalyst containing transition metal and carbon of the present invention are satisfied, and all the changes, modifications, substitutions, combinations or simplifications should be equivalent substitution.
Claims (3)
1. A method for the cyclic regeneration of a catalyst comprising a transition metal and carbon, characterized in that: firstly, mixing an inactivated catalyst with a regeneration liquid to form an inactivated catalyst mixed liquid to be treated; then placing the deactivated catalyst mixed solution in a closed compression-resistant container, and carrying out heating and pressurizing regeneration treatment to circularly regenerate the catalyst containing transition metal and carbon;
the weight ratio of the transition metal to the carbon is (1-5) 10;
the transition metal is any one or the combination of any several of iron, manganese, nickel, copper, zinc, vanadium, titanium, chromium, tungsten and cesium;
the carbon is any one or the combination of any several of active carbon, graphene oxide, graphene and carbon nano tubes;
the cyclic regeneration method of the catalyst containing transition metal and carbon comprises the following steps:
(1) Placing the catalyst containing transition metal and carbon which are subjected to catalytic deactivation into a regeneration liquid for uniform mixing, wherein the regeneration liquid contains a regenerant, and the mass ratio of the deactivated catalyst to the regenerant is 5 (1-4), so as to prepare a deactivated catalyst mixed liquid; the components of the regenerant contain carboxyl, hydroxyl and benzene ring, wherein the molar ratio of the carboxyl to the benzene ring is (1-3) 1, and the molar number of the hydroxyl is at least 1000 times of that of the benzene ring; the regenerant adopts a mixed solution of p-benzene tricarboxylic acid, N-dimethylformamide and ethanol;
(2) Placing the mixed solution of the deactivated catalyst prepared in the step (1) into a closed compression-resistant container, and heating and pressurizing; the temperature is controlled to be 120-250 ℃, the pressure is controlled to be 101.325-1013.25 kPa, and the treatment time is controlled to be 6-12 hours, so that the catalyst containing transition metal and carbon is subjected to cyclic regeneration reaction to obtain a product solution;
(3) Separating solid products in the product solution obtained in the step (2), and cleaning the solid products by using deionized water until the pH of the solution is neutral; the washed solid product is then dried under vacuum at a temperature of no more than 120 ℃ for at least 8h, and the dried solid is then ground to below 100 mesh to yield a regenerated transition metal and carbon containing catalyst material.
2. The method for recycling catalyst containing transition metal and carbon according to claim 1, characterized in that: in the step (2), the temperature is controlled to be 180-250 ℃ when the cyclic regeneration reaction is carried out.
3. The method for recycling a catalyst containing a transition metal and carbon according to claim 1 or 2, characterized in that: and after the regenerated catalyst is deactivated again, the catalyst regeneration treatment is carried out by adopting the circulating 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 catalyzed, regenerated and catalyzed for multiple times.
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| CN110354914A (en) * | 2019-08-09 | 2019-10-22 | 华北电力大学 | A kind of inactivation SCR denitration catalyst reuse method |
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