Method for regenerating activated carbon supported metal catalyst by microwave regeneration technology

Abstract

The invention belongs to the technical field of catalyst regeneration, and discloses a method for regenerating an activated carbon supported metal catalyst by a microwave regeneration technology. The method comprises the following steps: cleaning an inactivated activated carbon supported metal catalyst, and then carrying out microwave roasting and reduction in microwave equipment to obtain a regenerated activated carbon supported metal catalyst. According to the invention, the inactivated catalyst is cleaned with a solvent to remove surface pollutants, and by combining with optimized microwave roasting conditions and utilizing the strong absorption characteristic of activated carbon to microwaves, local hot spots are formed in pores, so that organic pollutants are quickly decomposed without damaging metal active components, efficient decomposition of organic matters in the pores is realized, and the activity of the catalyst is recovered.

Description

Technical Field

[0001] This invention relates to the field of catalyst regeneration technology, and in particular to a method for regenerating activated carbon-supported metal catalysts using microwave regeneration technology. Background Technology

[0002] Activated carbon is characterized by its high specific surface area (500~2000 m²). 2 With its well-developed pore structure and excellent adsorption properties, the activating carbon-supported Ru catalyst is an ideal support for metal catalysts. Its three-dimensional porous network can efficiently disperse active components of noble metals (such as Pt and Pd) or transition metals (such as Cu and Ni), improving the exposure efficiency of catalytic sites. For example, in chemical synthesis, Ru catalysts supported on activated carbon exhibit a conversion rate of over 95% in hydrogenation reactions; in environmental remediation, the adsorption-catalytic degradation efficiency of VOCs by supported activated carbon catalysts can reach over 90%. These support characteristics make it irreplaceable in petrochemical, waste gas treatment, and water treatment applications.

[0003] However, after deactivation of activated carbon-supported metal catalysts, existing regeneration technologies, such as traditional thermal and chemical regeneration, suffer irreversible damage including pore destruction, metal sintering, and the introduction of impurities. Patent CN116920877A employs a combination of chemical cleaning and thermal regeneration, a cumbersome process involving the treatment of acidic and alkaline wastewater, which can easily lead to the loss of active metal components and secondary environmental pollution. Furthermore, it is ineffective for regenerating deactivation caused by metal sintering. These limitations in efficiency and effectiveness restrict the cost-effectiveness and sustainable application of activated carbon-supported metal catalysts throughout their entire lifecycle. Summary of the Invention

[0004] The purpose of this invention is to provide a method for regenerating activated carbon-supported metal catalysts using microwave regeneration technology, which solves the problems of high energy consumption, low efficiency, and metal sintering in traditional catalyst regeneration technologies.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for regenerating activated carbon-supported metal catalysts using microwave regeneration technology, comprising the following steps: The deactivated activated carbon-supported metal catalyst was cleaned and then microwave-calcined and reduced in a microwave device to obtain a regenerated activated carbon-supported metal catalyst.

[0006] Preferably, the activated carbon-supported metal catalyst is any one of Ni5-Fe1 / AC, Ni2-Fe1 / AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / AC, Ni5 / AC, and Co2 / AC.

[0007] Preferably, the cleaning is performed using a solvent; the solvent is ethanol or acetone.

[0008] Preferably, the mass ratio of the deactivated activated carbon-supported metal catalyst to the solvent is 1:1 to 10.

[0009] Preferably, the cleaning time is 0.5 to 8 hours.

[0010] Preferably, the microwave calcination is carried out under a protective atmosphere, which is a nitrogen atmosphere; the reduction is carried out under a reducing atmosphere, which is a hydrogen atmosphere.

[0011] Preferably, the microwave roasting temperature is 250~390℃; the microwave roasting time is 3~6h; the reduction temperature is 250~450℃; and the reduction time is 2~8h.

[0012] As can be seen from the above technical solution, compared with the prior art, the present invention has the following beneficial effects: To address the problems of high energy consumption, low efficiency, and metal sintering in traditional regeneration technologies, this invention removes surface contaminants from the deactivated catalyst using solvent cleaning. Combined with microwave calcination and reduction, and leveraging the strong microwave absorption properties of activated carbon, localized "hot spots" are created within the pores. This rapidly decomposes organic contaminants without damaging the active metal components, achieving highly efficient decomposition of organic matter within the pores and restoring the catalyst's activity. Mechanistically, microwave energy acts directly on the adsorbate rather than the support framework, avoiding metal sintering and pore collapse common in traditional thermal regeneration. Experiments show that the regenerated catalyst exhibits an acetone conversion rate ≥83% and a catalyst activity recovery rate >95% in the acetone-ethanol condensation reaction, demonstrating significant economic benefits and environmental advantages. Detailed Implementation

[0013] This invention provides a method for regenerating activated carbon-supported metal catalysts using microwave regeneration technology, comprising the following steps: The deactivated activated carbon-supported metal catalyst was cleaned and then microwave-calcined and reduced in a microwave device to obtain a regenerated activated carbon-supported metal catalyst.

[0014] In this invention, the activated carbon-supported metal catalyst is preferably any one of Ni5-Fe1 / AC, Ni2-Fe1 / AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / AC, Ni5 / AC, and Co2 / AC. The activated carbon-supported metal catalyst of this invention is a catalyst prepared using the preparation method described in patent CN119016052A.

[0015] In this invention, the cleaning is preferably performed using a solvent; the solvent is preferably ethanol or acetone.

[0016] In this invention, the mass ratio of the deactivated activated carbon-supported metal catalyst to the solvent is preferably 1:1 to 10, more preferably 1:4 to 8, and even more preferably 1:6.

[0017] In this invention, the cleaning time is preferably 0.5 to 8 hours, more preferably 1 to 5 hours, and even more preferably 2 hours; the cleaning temperature is 60 to 80°C, more preferably 70 to 80°C, and even more preferably 80°C.

[0018] In this invention, the microwave roasting is carried out under a protective atmosphere; the protective atmosphere is preferably a nitrogen atmosphere.

[0019] In this invention, the reduction is carried out in a reducing atmosphere; the reducing atmosphere is preferably a hydrogen atmosphere.

[0020] In this invention, the microwave roasting temperature is preferably 250~390℃, more preferably 300~360℃, and even more preferably 350℃; the microwave roasting time is preferably 3~6h, more preferably 3~4h, and even more preferably 3h.

[0021] In this invention, the reduction temperature is preferably 250~450℃, more preferably 300~420℃, and even more preferably 400℃; the reduction time is preferably 2~8h, more preferably 3~6h, and even more preferably 4h.

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] For the preparation method of activated carbon supported metal catalysts (catalysts 1-8), please refer to Examples 1-6 and Examples 8-9 of patent CN119016052A. The substrate feeding table is shown in Table 1.

[0024] Table 1. Substrate feeding table for the preparation of activated carbon supported metal catalysts (catalysts 1-8)

[0025] Example 1

[0026] (1) Add 45g ethanol, 45g acetone and 10g catalyst 1 (Ni5-Fe1 / AC) to a high-pressure reactor in sequence, react at 190℃ for 2h, take a sample at the sampling port, continue the reaction for 180h and then stop the reaction, take a sample and filter out the catalyst to obtain the deactivated catalyst. (2) The deactivated catalyst was washed with 50g of acetone under reflux at 60°C for 2h. The washed catalyst was placed in a microwave device and heated to 300°C at a heating rate of 5°C / min under a nitrogen atmosphere and then calcined for 3h. Nitrogen was stopped and hydrogen was introduced into the microwave device for reduction. The catalyst was heated to 400°C at the same heating rate for 4h to obtain the regenerated catalyst. (3) Add 20g ethanol, 20g acetone and 5g regenerated catalyst to the high-pressure reactor in sequence, react at 190℃ for 2h, and take a sample for testing.

[0027] Example 2

[0028] (1) Add 45g ethanol, 45g acetone and 10g catalyst 2 (Ni2-Fe1 / AC) to a high-pressure reactor in sequence, react at 190℃ for 2h, take a sample at the sampling port, continue the reaction for 180h and then stop the reaction, take a sample and filter out the catalyst to obtain the deactivated catalyst. (2) The deactivated catalyst was washed with 60g of ethanol under reflux at 80°C for 2h. The washed catalyst was placed in a microwave device and calcined at 300°C for 5h under a nitrogen atmosphere at a heating rate of 5°C / min. Nitrogen was stopped and hydrogen was introduced into the microwave device for reduction. The catalyst was heated to 400°C at the same heating rate and calcined for 6h to obtain the regenerated catalyst. (3) Add 20g ethanol, 20g acetone and 5g regenerated catalyst to the high-pressure reactor in sequence, react at 190℃ for 2h, and take a sample for testing.

[0029] Example 3

[0030] (1) Add 45g ethanol, 45g acetone and 10g catalyst 3 (Ni5-Co1 / AC) to a high-pressure reactor in sequence, react at 190℃ for 2h, take a sample at the sampling port, continue the reaction for 180h and then stop the reaction, take a sample and filter out the catalyst to obtain the deactivated catalyst. (2) The deactivated catalyst was washed with 40g of acetone under reflux at 60°C for 2h. The washed catalyst was placed in a microwave device and calcined at 300°C for 6h under a nitrogen atmosphere at a heating rate of 7°C / min. Nitrogen was stopped and hydrogen was introduced into the microwave device for reduction. The catalyst was then calcined at 400°C for 3h under the same heating rate to obtain the regenerated catalyst. (3) Add 20g ethanol, 20g acetone and 5g regenerated catalyst to the high-pressure reactor in sequence, react at 190℃ for 2h, and take a sample for testing.

[0031] Example 4

[0032] (1) Add 45g ethanol, 45g acetone and 10g catalyst 4 (Ni5-Cu1 / AC) to a high-pressure reactor in sequence, react at 190℃ for 2h, take a sample at the sampling port, continue the reaction for 180h and then stop the reaction, take a sample and filter out the catalyst to obtain the deactivated catalyst. (2) The deactivated catalyst was cleaned with 50g of ethanol under reflux at 80°C for 2h. The cleaned catalyst was placed in a microwave device and calcined at 300°C for 3h under a nitrogen atmosphere at a heating rate of 9°C / min. Nitrogen was stopped and hydrogen was introduced into the microwave device for reduction. The catalyst was then calcined at 400°C for 6h at the same heating rate to obtain the regenerated catalyst. (3) Add 20g ethanol, 20g acetone and 5g regenerated catalyst to the high-pressure reactor in sequence, react at 190℃ for 2h, and take a sample for testing.

[0033] Example 5

[0034] (1) Add 45g ethanol, 45g acetone and 10g catalyst 5 (Co5-Zn1 / AC) to a high-pressure reactor in sequence, react at 190℃ for 2h, take a sample at the sampling port, continue the reaction for 180h and then stop the reaction, take a sample and filter out the catalyst to obtain the deactivated catalyst. (2) The deactivated catalyst was washed with 70g of acetone under reflux at 60°C for 2h. The washed catalyst was placed in a microwave device and calcined at 300°C for 4h under a nitrogen atmosphere at a heating rate of 3°C / min. Nitrogen was stopped and hydrogen was introduced into the microwave device for reduction. The catalyst was heated to 400°C at the same heating rate and calcined for 3h to obtain the regenerated catalyst. (3) Add 20g ethanol, 20g acetone and 5g regenerated catalyst to the high-pressure reactor in sequence, react at 190℃ for 2h, and take a sample for testing.

[0035] Example 6

[0036] (1) Add 45g ethanol, 45g acetone and 10g catalyst 6 (Mn5-Cu1 / AC) to a high-pressure reactor in sequence, react at 190℃ for 2h, take a sample at the sampling port, continue the reaction for 180h and then stop the reaction, take a sample and filter out the catalyst to obtain the deactivated catalyst. (2) The deactivated catalyst was washed with 80g of ethanol under reflux at 80°C for 2h. The washed catalyst was placed in a microwave device and calcined at 300°C for 3h under a nitrogen atmosphere at a heating rate of 5°C / min. Nitrogen was stopped and hydrogen was introduced into the microwave device for reduction. The catalyst was then heated to 400°C at the same heating rate and calcined for 4h to obtain the regenerated catalyst. (3) Add 20g ethanol, 20g acetone and 5g regenerated catalyst to the high-pressure reactor in sequence, react at 190℃ for 2h, and take a sample for testing.

[0037] Example 7

[0038] (1) Add 45g ethanol, 45g acetone and 10g catalyst 7 (Ni5 / AC) to a high-pressure reactor in sequence, react at 190℃ for 2h, take a sample at the sampling port, continue the reaction for 180h and then stop the reaction, take a sample and filter out the catalyst to obtain the deactivated catalyst. (2) The deactivated catalyst was cleaned with 50g of ethanol under reflux at 80°C for 2h. The cleaned catalyst was placed in a microwave device and calcined at 300°C for 6h under a nitrogen atmosphere at a heating rate of 5°C / min. Nitrogen was stopped and hydrogen was introduced into the microwave device for reduction. The catalyst was then calcined at 400°C for 2h at the same heating rate to obtain the regenerated catalyst. (3) Add 20g ethanol, 20g acetone and 5g regenerated catalyst to the high-pressure reactor in sequence, react at 190℃ for 2h, and take a sample for testing.

[0039] Example 8

[0040] (1) Add 45g ethanol, 45g acetone and 10g catalyst 8 (Co2 / AC) to a high-pressure reactor in sequence, react at 190℃ for 2h, take a sample at the sampling port, continue the reaction for 180h and then stop the reaction, take a sample and filter out the catalyst to obtain the deactivated catalyst. (2) The deactivated catalyst was washed with 80g of acetone under reflux at 80°C for 2h. The washed catalyst was placed in a microwave device and calcined at 300°C for 4h under a nitrogen atmosphere at a heating rate of 5°C / min. Nitrogen was stopped and hydrogen was introduced into the microwave device for reduction. The catalyst was heated to 400°C at the same heating rate and calcined for 5h to obtain the regenerated catalyst. (3) Add 20g ethanol, 20g acetone and 5g regenerated catalyst to the high-pressure reactor in sequence, react at 190℃ for 2h, and take a sample for testing.

[0041] Table 2 shows the catalytic performance of the alcohol-ketone condensation reaction before catalyst regeneration (referred to as the newly prepared catalyst) and after regeneration (referred to as the regenerated catalyst) in Examples 1-8.

[0042] Table 2 Catalytic performance of alcohol-ketone condensation reaction before and after catalyst regeneration

[0043] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for regenerating activated carbon-supported metal catalysts using microwave regeneration technology, characterized in that, Includes the following steps: The deactivated activated carbon-supported metal catalyst was cleaned and then microwave-calcined and reduced in a microwave device to obtain a regenerated activated carbon-supported metal catalyst.

2. The method for regenerating activated carbon-supported metal catalysts using microwave regeneration technology according to claim 1, characterized in that, The activated carbon-supported metal catalyst is any one of Ni5-Fe1 / AC, Ni2-Fe1 / AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / AC, Ni5 / AC, and Co2 / AC.

3. The method for regenerating activated carbon-supported metal catalysts using microwave regeneration technology according to claim 2, characterized in that, The cleaning is performed using a solvent; the solvent is ethanol or acetone.

4. The method for regenerating activated carbon-supported metal catalysts using microwave regeneration technology according to claim 3, characterized in that, The mass ratio of the deactivated activated carbon-supported metal catalyst to the solvent is 1:1~10.

5. The method for regenerating activated carbon-supported metal catalysts using microwave regeneration technology according to claim 3, characterized in that, The cleaning time is 0.5 to 8 hours.

6. The method for regenerating activated carbon-supported metal catalysts using microwave regeneration technology according to claim 1, characterized in that, The microwave roasting is carried out under a protective atmosphere, namely nitrogen; the reduction is carried out under a reducing atmosphere, namely hydrogen.

7. The method for regenerating activated carbon-supported metal catalysts using microwave regeneration technology according to claim 6, characterized in that, The microwave roasting temperature is 250~390℃; the microwave roasting time is 3~6h; the reduction temperature is 250~450℃; the reduction time is 2~8h.

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