CN114768785A - Production process of activated carbon-based carbon, catalyst using activated carbon-based carbon and production process of catalyst - Google Patents
Production process of activated carbon-based carbon, catalyst using activated carbon-based carbon and production process of catalyst Download PDFInfo
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Abstract
The invention discloses a production process of activated carbon-based carbon, a catalyst using the activated carbon-based carbon and a production process of the catalyst, and relates to the technical field of catalysts. The production process of the activated carbon-based carbon comprises the steps of taking the base carbon, pre-acidifying, alkalizing, pressurizing and isolating air, compound activating, acid washing and alkali washing. The production process of the catalyst using the activated carbon-based carbon comprises the steps of loading stage, obtaining finished products and the like. The vinyl acetate synthesis catalyst is prepared by the production process of the catalyst using the activated carbon-based carbon. The catalyst has the advantages that the specific surface area of the activated carbon-based carbon is improved, the purity of the activated carbon-based carbon is improved, the product performance of the activated carbon-based carbon is improved, and the catalytic activity is higher by adopting the catalyst prepared from the activated carbon-based carbon.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a production process of activated carbon-based carbon, a catalyst using the activated carbon-based carbon and a production process of the catalyst.
Background
Vinyl acetate is mainly used for synthesizing vinylon, and is also used in the fields of adhesive and paint industries and the like. At present, when acetylene method fixed bed gas phase synthesis of vinyl acetate is generally adopted, zinc acetate loaded active carbon Zn (AC) is adopted2As a catalyst. In the fixed bed VAC synthesis reaction process, carrier base carbon obtained by molding and activating a carbonized material is generally selected.
In the related technology, a preparation method of an acetylene method vinyl acetate catalyst is disclosed, and the specific preparation steps are that an excess solution impregnation method is adopted, zinc oxide and acetic acid are used as main raw materials, a small amount of bismuth carbonate is added according to a proportion, activated carbon is impregnated until adsorption balance is achieved, and then the catalyst is dripped and dried for later use.
However, the bismuth carbonate supported on activated carbon is easily overlapped, which is not favorable for coordination of acetylene, and thus the activity of the catalyst is low.
Disclosure of Invention
In order to improve the catalytic activity of the catalyst for synthesizing vinyl acetate, the application provides a production process of activated carbon-based carbon, a catalyst using the activated carbon-based carbon and a production process thereof.
In a first aspect, the production process of the activated carbon provided by the application adopts the following technical scheme:
a production process of activated carbon-based carbon comprises the following steps:
taking the base carbon: crushing the active carbon raw material to 6-10 meshes to obtain active carbon powder;
pre-acidification treatment: adding wood tar and an acidic solution into the activated carbon powder, fully soaking, and heating at the temperature of 120-130 ℃ for 2-3 hours to obtain an acidified mixture;
alkalization treatment: adding an alkaline solution into the acidified mixture, and stirring fully to obtain an alkalified mixture;
pressurizing and isolating air: treating the alkalized mixture under 0.5-1Mpa for 2-4 hr in the absence of air to obtain treated mixture;
and (3) composite activation: activating and expanding the treated mixture under the conditions of no oxygen and 0.3-0.9MPa, standing for 0.8-1.2h at the 1000 ℃ stage of 800-;
acid washing and alkali washing: and (3) acid-washing the activated material at 60-95 ℃, and alkali-washing the activated material at 45-55 ℃ to obtain the activated carbon-based carbon.
By adopting the technical scheme, the active carbon raw material is crushed to 6-10 meshes, which is beneficial to full impregnation in the pre-acidification treatment step; the pre-acidification treatment, the alkalization treatment and the pressurization isolation of air are carried out, the mixed gas of water vapor and carbon dioxide is used for activation, the activation time can be shortened, the working efficiency is improved, in addition, the activation temperature is controlled within 1200-1300 ℃, the pore-forming on the surface of the activated carbon base carbon is facilitated during the pressure relief discharging, and the specific surface area of the activated carbon base carbon is improved. And the activated material is subjected to acid washing and alkali washing within the temperature range, so that impurities in the activated material can be removed, and the purity of the activated carbon-based carbon is improved. Therefore, the activated carbon prepared by the process has larger specific surface area and purity, the product performance of the activated carbon is improved, and the catalyst prepared by the activated carbon has higher catalytic activity.
In a specific possible embodiment, in the acid washing and alkali washing steps, the activating material is subjected to acid washing by using an acid washing solution with the mass fraction of 1% -3%, wherein the acid washing solution is at least one of an acetic acid solution, a hydrochloric acid solution or a nitric acid solution.
By adopting the technical scheme, because the acetic acid solution, the hydrochloric acid solution or the nitric acid solution is adopted in the processes of pre-acidification treatment, alkalization treatment and composite activation treatment, alkaline impurities in the activated material can be removed, and the acid washing solution with the mass fraction of 1-4% is adopted, so that the impurities can be removed, the influence on the property and the surface appearance of the activated material can be reduced, and the prepared activated carbon-based carbon can keep good product performance.
In a specific possible embodiment, in the acid washing and alkali washing steps, 2% -6% by mass of alkali washing liquid is used for reducing and washing the activated material, and the alkali washing liquid is at least one of sodium hydroxide solution, potassium hydroxide solution or barium hydroxide solution.
By adopting the technical scheme, acidic impurities in the activated material can be removed by adopting a sodium hydroxide solution, a potassium hydroxide solution or a barium hydroxide solution, the mass fraction of the alkaline washing solution is controlled within the range, the influence on the property and the surface appearance of the activated material is favorably reduced, and meanwhile, acid-base neutralization can be carried out with the residual acid washing solution component, so that the prepared activated carbon-based carbon keeps good product performance.
In a specific embodiment, in the composite activation step, the volume ratio of the water vapor to the carbon dioxide in the mixed gas of the water vapor and the carbon dioxide is 0.4 to 4.
By adopting the technical scheme, the activating gas is very important for improving the activating effect of the activated carbon-based carbon, compared with traditional activating agents such as phosphoric acid, zinc chloride and water vapor, the inventor adopts the mixed gas of the water vapor and the carbon dioxide as the activating agent, controls the volume ratio of the water vapor to the carbon dioxide within the range, can improve the activating rate and the activating effect, enables the specific surface area of the activated carbon-based carbon to be larger and the purity to be higher, and is beneficial to further improving the product performance of the activated carbon-based carbon.
In a specific embodiment, the flow rate of the mixed gas of water vapor and carbon dioxide is 5-20m3/min。
By adopting the technical scheme, the flow of the mixed gas of the water vapor and the carbon dioxide is controlled within the range, so that the activated carbon raw material powder is activated at a uniform speed, and the prepared activated carbon-based carbon product is more stable in performance.
In a second aspect, the production process of the catalyst using activated carbon-based carbon provided by the present application adopts the following technical scheme:
a production process of a catalyst using activated carbon-based carbon comprises the following steps:
and (3) a loading stage: cooling the activated carbon prepared by the production process of the activated carbon to room temperature, adding zinc acetate and a compound additive solution, stirring, keeping the temperature at 45-55 ℃ for 4-9h, and adsorbing to saturation to obtain a load;
obtaining a finished product: and drying the load to obtain the catalyst using the activated carbon-based carbon.
By adopting the technical scheme, the composite auxiliary agent solution can change the pore structure of the activated carbon-based carbon, and improve the load capacity of zinc acetate, thereby improving the catalytic activity of the catalyst. Keeping the temperature for 4-9 hours at 45-55 ℃, and facilitating the zinc acetate to be loaded on the activated carbon-based carbon.
In a specific possible embodiment, in the loading stage, the composite assistant solution is an ammonium paramolybdate solution.
By adopting the technical scheme, the ammonium paramolybdate solution can change the aperture of the activated carbon-based carbon and increase the pore volume, thereby improving the loading capacity of zinc acetate; meanwhile, the loading rate can be improved, impurities can be reduced, the catalytic activity of the catalyst can be further improved, and the service life of the catalyst can be prolonged.
In a specific possible embodiment, in the loading stage, a complexing auxiliary agent is synchronously added with the composite auxiliary agent solution, and the complexing auxiliary agent comprises K-containing+Acid assistant and La-containing3+Acid assistant, Ba-containing2+At least one of an acidic adjuvant.
By adopting the technical scheme, K+、La3+And Ba2+Can be combined with impurity ions in the catalyst, and is beneficial to the impurity ions in the catalyst, thereby further improving the catalytic activity of the catalyst.
In a third aspect, the catalyst for vinyl acetate synthesis provided by the present application adopts the following technical scheme:
a vinyl acetate synthesis catalyst is prepared by the production process of the catalyst using the activated carbon-based carbon.
By adopting the technical scheme, the catalyst prepared by the process and using the activated carbon-based carbon can be used for the reaction of synthesizing vinyl acetate, and has high catalytic activity and good catalytic effect.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the method has the advantages that through the steps of taking materials from the activated carbon, pre-acidification treatment, alkalization treatment, air pressurization and isolation, composite activation, acid washing, alkali washing and the like, the specific surface area of the activated carbon base carbon is improved, and the purity of the activated carbon base carbon is improved, so that the product performance of the activated carbon base carbon is improved, and the catalyst prepared from the activated carbon base carbon has higher catalytic activity;
2. the method adopts 1-4% of acetic acid solution, hydrochloric acid solution or nitric acid solution and 2-6% of sodium hydroxide solution, potassium hydroxide or barium hydroxide solution by mass fraction, so that impurities can be removed, influence on the property and surface morphology of the activated material can be reduced, and the prepared activated carbon can keep good product performance;
3. according to the method, the pore structure of the activated carbon-based carbon can be changed through the steps of loading stage, obtaining of finished products and the like, and the loading capacity of zinc acetate is improved, so that the catalytic activity of the catalyst is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
The active carbon raw material is any one or free combination of more of coconut shell carbonized material powder, saw dust, coal powder, petroleum coke, apricot shells or bamboo processing scraps, and the active carbon raw material adopted in the specific implementation mode of the application is the coconut shell carbonized material powder; the CAS number of the wood tar is 8001-58-9, and the content is more than or equal to 99%; containing K+The acid auxiliary agent is potassium acetate solution with the mass fraction of 10 percent and contains La3+The acid additive is 10 percent lanthanum acetate solution by mass and contains Ba2+The acid auxiliary agent is a barium acetate solution with the mass fraction of 10%.
Preparation example of Pickling solution
Preparation example 1
The preparation example provides a pickling solution, which is prepared according to the following steps: 1kg of 2% acetic acid solution, 1kg of 2% hydrochloric acid solution and 1kg of 2% nitric acid solution are uniformly mixed to obtain the pickling solution.
Preparation example of alkali washing solution
Preparation example 2
The preparation example provides an alkaline washing solution, which is prepared according to the following steps: 1kg of sodium hydroxide solution with the mass fraction of 3.5%, 1kg of potassium hydroxide with the mass fraction of 3.5% and 1kg of barium hydroxide solution with the mass fraction of 3.5% are uniformly mixed to obtain the alkaline washing liquid.
Examples
Example 1
The embodiment provides a production process of activated carbon-based carbon, which comprises the following steps:
taking the base carbon: adding the activated carbon raw material into a pulverizer, and pulverizing to 8 meshes to obtain activated carbon powder;
pre-acidification treatment: then adding 3kg of activated carbon powder into a reaction kettle, adding 1.5kg of wood tar and 1.5kg of acid solution into the reaction kettle, fully soaking, heating the reaction kettle to 125 ℃, and heating for 2.5 hours to obtain an acidified mixture;
alkalization treatment: adding 2kg of alkaline solution into the acidified mixture in the reaction kettle, and fully stirring to obtain an alkalized mixture;
pressurizing and isolating air: introducing nitrogen into the reaction kettle to remove air in the reaction kettle, adjusting the pressure in the reaction kettle to 0.8Mpa, sealing the reaction kettle and isolating the air, and keeping the pressure in the reaction kettle at 0.8Mpa for 3 hours to obtain a disposal mixture;
and (3) composite activation: keeping the reaction kettle in an anaerobic environment, adjusting the pressure in the reaction kettle to 0.6MPa, activating and expanding the volume, wherein the activation and expansion operation comprises adjusting the temperature in the reaction kettle to 900 ℃, staying at 900 ℃ for 1h, then heating the temperature in the reaction kettle to 1250 ℃, staying at 1250 ℃ for 2h, and then taking 12m as the volume3Introducing mixed gas of water vapor and carbon dioxide into the reaction kettle at a flow rate of/min, maintaining the pressure in the reaction kettle at 0.6MPa, stopping introducing the mixed gas of water vapor and carbon dioxide after activation is finished to obtain an activated material, and taking out the activated material after the reaction kettle is decompressed; acid washing and alkali washing: the activating material is put into a container, the temperature of the container is adjusted to 80 ℃, the pickling solution prepared in the preparation example 1 is added into the container to pickle the activating material, and thenAnd then filtering, adding the filtered activated material and the alkaline washing solution prepared in the preparation example 2 into a container, adjusting the temperature of the container to 50 ℃, carrying out alkaline washing on the activated material, and then filtering to obtain the activated carbon-based carbon.
Wherein the acid solution is an acetic acid solution with the mass fraction of 2%, the alkaline solution is a sodium hydroxide solution with the mass fraction of 4%, and the mixed gas of water vapor and carbon dioxide is the water vapor and the carbon dioxide with the volume ratio of 2.5.
Example 2
The present embodiment provides a process for producing activated carbon-based carbon, and the difference between the present embodiment and embodiment 1 is that in the step of taking out the activated carbon, the activated carbon raw material is crushed to 6 meshes.
Example 3
This example provides a process for producing activated carbon-based char, and differs from example 1 in that in the step of taking out the activated carbon material, the activated carbon raw material is pulverized to 10 mesh.
Example 4
This example provides a process for producing activated carbon-based carbon, and differs from example 1 in that in the preliminary acidification step, the reaction kettle is heated to 130 ℃ and an acidified mixture is obtained after heating for 2 hours.
Example 5
This example provides a process for producing activated carbon-based carbon, and differs from example 1 in that in the preliminary acidification step, the reaction kettle is heated to 120 ℃ and an acidified mixture is obtained after heating for 3 hours.
Example 6
This example provides a process for producing activated carbon-based carbon, which is different from example 1 in that in the preliminary acidification step, the reaction kettle is heated to 120 ℃ and an acidified mixture is obtained after 3 hours of heating.
Example 7
This example provides a process for producing activated carbon-based carbon, which is different from example 1 in that in the step of pressurizing and isolating air, the pressure in the reaction kettle is adjusted to 0.5Mpa, and after the pressure in the reaction kettle is maintained at 0.5Mpa for 4 hours, a disposal mixture is obtained.
Example 8
This example provides a process for producing activated carbon-based carbon, which is different from example 1 in that in the step of pressurizing and isolating air, the pressure in the reaction kettle is adjusted to 1Mpa, and after the pressure in the reaction kettle is maintained at 1Mpa for 2 hours, a disposal mixture is obtained.
Example 9
This example provides a process for producing activated carbon-based carbon, which is different from example 1 in that, in the composite activation step, the pressure in the reaction kettle is adjusted to 0.3MPa, and then activation and expansion are performed, wherein the activation and expansion are performed by adjusting the temperature in the reaction kettle to 800 ℃ and staying at 800 ℃ for 1.2 hours, then raising the temperature in the reaction kettle to 1200 ℃ and staying at 1200 ℃ for 2.5 hours, and then increasing the temperature by 20m3Introducing mixed gas of water vapor and carbon dioxide into the reaction kettle at a flow rate of/min, maintaining the pressure in the reaction kettle at 0.3MPa, stopping introducing the mixed gas of water vapor and carbon dioxide after activation is finished to obtain an activated material, and taking out the activated material after the reaction kettle is decompressed.
Example 10
This example provides a process for producing activated carbon-based carbon, which differs from example 1 in that, in the composite activation step, the pressure in the reaction kettle is adjusted to 0.9MPa, and then activation and expansion are performed, wherein the activation and expansion operation is performed by adjusting the temperature in the reaction kettle to 1000 ℃ and staying at 1000 ℃ for 0.8h, then heating the temperature in the reaction kettle to 1300 ℃ and staying at 1300 ℃ for 1.5h, and then heating to 5m3Introducing mixed gas of water vapor and carbon dioxide into the reaction kettle at a flow rate of/min, maintaining the pressure in the reaction kettle at 0.9MPa, stopping introducing the mixed gas of water vapor and carbon dioxide after activation is finished to obtain an activated material, and taking out the activated material after the reaction kettle is decompressed.
Example 11
The embodiment provides a production process of activated carbon-based carbon, and the difference between the embodiment and the embodiment 1 is that in the steps of acid washing and alkali washing, an activated material is put into a container, the temperature of the container is adjusted to 60 ℃, acid washing liquid prepared in the preparation 1 is added into the container to carry out acid washing on the activated material, then filtration is carried out, the filtered activated material and alkali washing liquid prepared in the preparation 2 are added into the container, the temperature of the container is adjusted to 45 ℃, alkali washing is carried out on the activated material, and then filtration is carried out to obtain the activated carbon-based carbon.
Example 12
The embodiment provides a production process of activated carbon-based carbon, and the difference between the embodiment and the embodiment 1 is that in the steps of acid washing and alkali washing, an activated material is put into a container, the temperature of the container is adjusted to 95 ℃, acid washing liquid prepared in the preparation 1 is added into the container to carry out acid washing on the activated material, then filtration is carried out, the filtered activated material and alkali washing liquid prepared in the preparation 2 are added into the container, the temperature of the container is adjusted to 55 ℃, alkali washing is carried out on the activated material, and then filtration is carried out to obtain the activated carbon-based carbon.
Example 13
This example provides a process for producing activated carbon-based carbon, and differs from example 1 in that the acid washing solution is an acetic acid solution with a mass fraction of 1% in the acid washing and alkali washing steps.
Example 14
This example provides a process for producing activated carbon-based carbon, and differs from example 1 in that in the acid washing and alkali washing steps, the acid washing solution is an acetic acid solution with a mass fraction of 3%.
Example 15
This example provides a process for producing activated carbon-based carbon, and differs from example 1 in that in the acid washing and alkali washing steps, the acid washing solution is a hydrochloric acid solution with a mass fraction of 1%.
Example 16
This example provides a process for producing activated carbon-based carbon, and differs from example 1 in that in the acid washing and alkali washing steps, the alkali washing solution is a sodium hydroxide solution with a mass fraction of 2%.
Example 17
This example provides a process for producing activated carbon-based carbon, and differs from example 1 in that in the acid washing and alkali washing steps, the alkali washing solution is a sodium hydroxide solution with a mass fraction of 6%.
Example 18
This example provides a process for producing activated carbon-based carbon, and differs from example 1 in that the volume ratio of water vapor to carbon dioxide in the mixed gas of water vapor and carbon dioxide in the composite activation step is 0.4.
Example 19
This example provides a process for producing an activated carbon-based carbon, and differs from example 1 in that the volume ratio of water vapor to carbon dioxide in a mixed gas of water vapor and carbon dioxide in the combined activation step is 4.
Application example
Application example 1
The present application provides a catalyst for vinyl acetate synthesis and a process for producing a catalyst using activated carbon-based carbon, and the catalyst for vinyl acetate synthesis is prepared according to the process for producing a catalyst using activated carbon-based carbon.
The production process of the catalyst using the activated carbon-based carbon includes the following steps,
and (3) a loading stage: cooling the activated carbon-based carbon prepared in the embodiment 1 to room temperature, adding the cooled activated carbon-based carbon into a reaction kettle, adding zinc acetate and a compound assistant solution into the reaction kettle, uniformly stirring, adjusting the temperature of the reaction kettle to 50 ℃, keeping the temperature for 6 hours, and obtaining a load after adsorption saturation;
obtaining a finished product: and drying the load to obtain the catalyst using the activated carbon-based carbon, wherein the catalyst using the activated carbon-based carbon is the catalyst for synthesizing the vinyl acetate.
Wherein the compound additive solution is ammonium paramolybdate solution.
Application example 2
The application example provides a vinyl acetate synthesis catalyst and a production process of the catalyst using activated carbon-based carbon, and the application example is different from the application example 1 in that in a loading stage, the temperature of a reaction kettle is adjusted to 45 ℃, the temperature is kept for 9 hours, and a load is obtained after adsorption saturation.
Application example 3
The application example provides a vinyl acetate synthesis catalyst and a production process of the catalyst using activated carbon-based carbon, and the application example is different from the application example 1 in that in a loading stage, the temperature of a reaction kettle is adjusted to 55 ℃, the temperature is kept for 4 hours, and a load is obtained after adsorption saturation.
Application examples 4 to 21
Application examples 4 to 21 each provide a catalyst for vinyl acetate synthesis and a process for producing a catalyst using activated carbon-based carbon, and application examples 4 to 22 are different from application example 1 in that the activated carbon-based carbon prepared in examples 2 to 19 is used in sequence in application examples 4 to 22.
Application example 22
The difference between the application example and the application example 1 is that in the loading stage, a complexing auxiliary agent and zinc acetate are added simultaneously, and the complexing auxiliary agent contains K+And (3) an acidic auxiliary agent.
Application example 23
The difference between the application example and the application example 1 is that in the loading stage, a complexing auxiliary agent and zinc acetate are added simultaneously, and the complexing auxiliary agent contains Ba2+And (3) an acidic auxiliary agent.
Application example 24
The application example provides a vinyl acetate synthesis catalyst and a production process of a catalyst using activated carbon-based carbon, and the application example is different from the application example 1 in that a complexing auxiliary agent and zinc acetate are added simultaneously in a loading stage, and the complexing auxiliary agent contains La3+And (3) an acidic auxiliary agent.
Comparative example
Comparative example 1
This comparative example, which is different from example 1 in that acid washing and alkali washing operations in the acid washing and alkali washing steps are not included, provides a process for producing an activated carbon-based carbon.
Comparative example 2
This comparative example, which is different from example 1 in that acid washing operation in the acid washing and alkali washing steps is not included, provides a process for producing an activated carbon-based carbon.
Comparative example 3
This comparative example, which is different from example 1 in that the alkali washing operation in the acid washing and alkali washing steps is not included, provides a process for producing an activated carbon-based carbon.
Comparative application example
Comparative application examples 1 to 3
Comparative application examples 1 to 3 each provide a catalyst for vinyl acetate synthesis and a process for producing a catalyst using activated carbon-based carbon, and comparative application examples 1 to 3 are different from application example 1 in that comparative application examples 1 to 3 successively use activated carbon-based carbon prepared in comparative examples 1 to 3
The performance test was conducted as follows with respect to the vinyl acetate synthesis catalysts provided in application examples 1 to 24 and comparative application examples 1 to 3.
Weighing 0.1000g of sample on an electronic balance, crushing to 71 microns, putting into a triangular flask, adding 100ml of deionized water into the triangular flask, adding 2ml of hydrochloric acid solution with the mass fraction of 1%, heating to 100 ℃, continuing to heat for 5 minutes, filtering the mixture in the triangular flask into a conical flask, washing filter residue with 50 ℃ water for three times, cooling to room temperature, adding 10ml of buffer solution with the pH value of 10 into the conical flask, adding 2 drops of chrome black T indicator, titrating to blue with 0.0250mol/L of EDTA standard solution, and recording the consumption number V of the EDTA standard solution.
The buffer solution is prepared by the following steps: 54g of NH4Cl was dissolved in water, and the solution was diluted to 1000ml with 350ml of aqueous ammonia to obtain a buffer solution.
Calculated according to the following formula: zn (AC)2% ═ v (edta) × c (edta) × 183.48/10 m. Wherein, Zn (AC)2% is the content of zinc acetate in the catalyst; v (EDTA) is the volume of EDTA solution consumed by titration, in ml; c (EDTA) is the concentration of EDTA in mol/L; m is the weighed sample mass, unit g; 183.48 is the molecular weight of zinc acetate. The results are shown in the table.
TABLE 1 test result tables of application examples 1 to 24 and comparative application examples 1 to 3
As can be seen by combining application example 1 and comparative application examples 1 to 3 with Table 1, Zn (AC) of the catalysts of comparative application examples 1 to 3 was compared with that of application example 12The% values are significantly smaller, indicating that the addition of an acid wash and an alkaline wash step after the composite activation step contributes to the increase of Zn (AC)2% values, which are advantageous for increasing the catalytic activity of the catalyst. The catalyst prepared by the preparation process of the catalyst has higher catalytic activity.
As can be seen by combining application examples 1 to 3 with Table 1, Zn (AC) was compared with the catalysts of application examples 1 to 32The% values are unchanged, which shows that the catalysts prepared by the preparation process of the catalyst have higher catalytic activity.
As can be seen by combining application example 1 and application examples 4 to 21 with Table 1, Zn (AC) of the catalyst of application examples 4 to 21 as compared with application example 12The% values were less than 41%, and were all greater than Zn (AC) of the catalysts of comparative application examples 1-32% of the total weight of the composition. This shows that the activated carbon prepared by the preparation process of the activated carbon of the present application all contribute to the improvement of the catalytic activity of the catalyst.
As can be seen from a combination of application example 1 and application examples 22 to 24 and Table 1, Zn (AC) of the catalyst of application examples 22 to 24 as compared with application example 12The% values are all larger. This indicates that the addition of the complexing agent contributes to a further increase in Zn (AC)2% values, which are advantageous for increasing the catalytic activity of the catalyst.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The production process of the activated carbon-based carbon is characterized by comprising the following steps of,
taking the base carbon: crushing the active carbon raw material to 6-10 meshes to obtain active carbon powder;
pre-acidification treatment: adding wood tar and an acidic solution into the activated carbon powder, fully soaking, and heating at the temperature of 120-130 ℃ for 2-3 hours to obtain an acidified mixture;
alkalization treatment: adding an alkaline solution into the acidified mixture, and stirring fully to obtain an alkalified mixture;
pressurizing and isolating air: treating the alkalized mixture under 0.5-1Mpa for 2-4 hr in the absence of air to obtain treated mixture;
and (3) composite activation: activating and expanding the treated mixture under the conditions of no oxygen and 0.3-0.9MPa, standing for 0.8-1.2h at the stage of 800-;
acid washing and alkali washing: and (3) acid-washing the activated material at 60-95 ℃, and then alkali-washing the activated material at 45-55 ℃ to obtain the activated carbon-based carbon.
2. The process for producing activated carbon-based carbon according to claim 1, characterized in that: in the acid washing and alkali washing steps, 1-3% by mass of acid washing liquid is adopted to carry out acid washing on the activated material, and the acid washing liquid is at least one of acetic acid solution, hydrochloric acid solution or nitric acid solution.
3. The process for producing activated carbon-based carbon according to claim 2, wherein: in the acid washing and alkali washing steps, 2-6% of alkali washing liquid by mass is adopted to carry out subtractive washing on the activated material, and the alkali washing liquid is at least one of sodium hydroxide solution, potassium hydroxide or barium hydroxide solution.
4. The process for producing activated carbon-based carbon according to claim 1, wherein: in the composite activation step, the volume ratio of the water vapor to the carbon dioxide in the mixed gas of the water vapor and the carbon dioxide is 0.4-4.
5. The process for producing activated carbon-based carbon according to claim 1, characterized in that: the flow rate of the mixed gas of the water vapor and the carbon dioxide is 5-20 m/min.
6. A production process of a catalyst using activated carbon-based carbon is characterized by comprising the following steps,
and (3) a loading stage: cooling the activated carbon prepared by the activated carbon production process according to any one of claims 1 to 5 to room temperature, adding zinc acetate and a compound assistant solution, stirring, keeping the temperature at 45 to 55 ℃ for 4 to 9 hours, and adsorbing to saturation to obtain a load;
obtaining a finished product: and drying the load to obtain the catalyst using the activated carbon-based carbon.
7. The process for producing a catalyst using activated carbon-based carbon according to claim 6, wherein: in the loading stage, the composite additive solution is an ammonium paramolybdate solution.
8. The process for producing a catalyst using activated carbon-based carbon according to claim 6, wherein: and in the loading stage, synchronously adding a complexing aid and a composite aid solution, wherein the complexing aid comprises at least one of a K + acid-containing aid, a La3+ acid-containing aid and a Ba2+ acid-containing aid.
9. A catalyst for synthesizing vinyl acetate is characterized in that: the catalyst is prepared by the production process of the catalyst using the activated carbon-based carbon of any one of claims 6 to 8.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115228435A (en) * | 2022-07-29 | 2022-10-25 | 山东省科学院能源研究所 | Method for circularly and continuously preparing and regenerating activated carbon adsorbent |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269810A (en) * | 2008-05-06 | 2008-09-24 | 同方炭素科技有限公司 | Absorbent charcoal fine purification technique |
| CN102343270A (en) * | 2010-07-28 | 2012-02-08 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal components in layered distribution and preparation method thereof |
| CN103111325A (en) * | 2011-11-16 | 2013-05-22 | 上海浦景化工技术有限公司 | Process for synthesizing vinyl acetate catalyst through acetylene method |
| CN204917988U (en) * | 2015-08-28 | 2015-12-30 | 木林森活性炭江苏有限公司 | High specific surface is used for production system of synthetic vinyl acetate carrier active carbon of acetylene method |
| CN106268764A (en) * | 2015-05-11 | 2017-01-04 | 中国石油化工股份有限公司 | Prepare the catalyst used by acetylene method vinyl acetate |
| CN107362815A (en) * | 2017-07-26 | 2017-11-21 | 湖北随州双星生物科技有限公司 | A kind of technique and device for producing synthesis vinyl chloride thereof low mercury catalyst |
| CN108636392A (en) * | 2018-04-17 | 2018-10-12 | 木林森活性炭江苏有限公司 | A kind of efficient fixed bed vinyl acetate synthesis catalysts preparation method |
| CN111715246A (en) * | 2020-06-18 | 2020-09-29 | 那珊 | Industrial mercury-free catalyst synthesized from vinyl chloride, and preparation method and application thereof |
-
2022
- 2022-03-29 CN CN202210319104.3A patent/CN114768785A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269810A (en) * | 2008-05-06 | 2008-09-24 | 同方炭素科技有限公司 | Absorbent charcoal fine purification technique |
| CN102343270A (en) * | 2010-07-28 | 2012-02-08 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal components in layered distribution and preparation method thereof |
| CN103111325A (en) * | 2011-11-16 | 2013-05-22 | 上海浦景化工技术有限公司 | Process for synthesizing vinyl acetate catalyst through acetylene method |
| CN106268764A (en) * | 2015-05-11 | 2017-01-04 | 中国石油化工股份有限公司 | Prepare the catalyst used by acetylene method vinyl acetate |
| CN204917988U (en) * | 2015-08-28 | 2015-12-30 | 木林森活性炭江苏有限公司 | High specific surface is used for production system of synthetic vinyl acetate carrier active carbon of acetylene method |
| CN107362815A (en) * | 2017-07-26 | 2017-11-21 | 湖北随州双星生物科技有限公司 | A kind of technique and device for producing synthesis vinyl chloride thereof low mercury catalyst |
| CN108636392A (en) * | 2018-04-17 | 2018-10-12 | 木林森活性炭江苏有限公司 | A kind of efficient fixed bed vinyl acetate synthesis catalysts preparation method |
| CN111715246A (en) * | 2020-06-18 | 2020-09-29 | 那珊 | Industrial mercury-free catalyst synthesized from vinyl chloride, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 宁平等: "《生物质活性炭催化剂的制备及脱硫应用》", 31 January 2020, 北京：冶金工业出版社 * |
| 郭秀玲等: ""乙炔气相法合成乙酸乙烯催化剂的研究进展"", 《化工进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115228435A (en) * | 2022-07-29 | 2022-10-25 | 山东省科学院能源研究所 | Method for circularly and continuously preparing and regenerating activated carbon adsorbent |
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