CN112758922A - Preparation process and system of high-pyridine nitrogen-doped activated carbon - Google Patents
Preparation process and system of high-pyridine nitrogen-doped activated carbon Download PDFInfo
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Abstract
The invention relates to the technical field of nitrogen-doped activated carbon, in particular to a preparation process and a system of high pyridine nitrogen-doped activated carbon. The preparation process comprises the following steps of doping a carbon material by taking polyvinyl pyridine as a nitrogen source under the heating condition to obtain the high pyridine nitrogen doped activated carbon: 1) preparing polyvinyl pyridine, wherein the polyvinyl pyridine is marked as ppl-1; 2) preparing a carbonized precursor, wherein the carbonized precursor is designated as yk-1; 3) preparing high pyridine nitrogen doped activated carbon: KOH, ppl-1 and yk-1 were mixed in N2And (3) under the atmosphere, activating the mixture by adopting programmed heating, thoroughly washing the activated sample for several times by using hydrochloric acid, removing inorganic salt, washing the sample by using distilled water until the pH value is neutral, and finally drying the sample to obtain the high pyridine nitrogen activated carbon. The invention is prepared by mixing ammonia, ammonia water, melamine or G-C3N4And the traditional nitrogen source is replaced by the polyvinyl pyridine synthesized by the vinyl pyridine, so that the nitrogen-doped activated carbon with higher proportion of pyridine nitrogen functional groups can be obtained, and the cost is lower.
Description
Technical Field
The invention relates to the technical field of nitrogen-doped activated carbon, in particular to a preparation process and a system of high pyridine nitrogen-doped activated carbon.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The activated carbon as a non-metal catalyst is distinguished from a plurality of adsorbents and catalysts by virtue of the advantages of porosity, low cost, wide availability, large surface area, easy design of pore structure, surface functionalization, low requirement on regeneration energy and the like. The method can ensure that the adsorption process is excellent through the modes of rich surface pore structure, large specific surface area, change of reactant electric polarity and the like, and also ensures that electrons are easier to transfer in the reaction process, the activation energy of the reaction is reduced, and the energy barrier is reduced, so that the reaction which is difficult to react or has lower equilibrium conversion rate is easier to carry out, the problems of low equilibrium conversion rate, long time consumption, higher cost and the like of a plurality of redox reactions in industrial production are solved, and the method has been used for removing atmospheric pollutants such as fuel cells, sulfur oxides, nitrogen oxides and the like, and removing CO and the like so far in fuel cells2Adsorption separation, catalytic oxidation-reduction reaction and the like are widely used in many fields.
However, the types, quality, catalytic efficiency, etc. of activated carbon are different, so it is a research object in the art to find an activated carbon with stable catalytic performance. The nitrogen-doped active carbon has good effect in engineering application. The preparation method of the nitrogen-doped activated carbon is simple, the cost is low, and after a nitrogen group is added into a carbon skeleton to establish a surface alkaline site, the N atom is carried on a carbon chain to change the polarity of the original carbon material, so that electrons in the redox reaction are easier to transfer, and the equilibrium conversion rate is higher. Three nitrogen-containing functional groups are generally generated during the nitrogen doping process: pyrrole nitrogen (N-5), pyridine nitrogen (N-6) and graphite type nitrogen (N-Q). It has been proved by scholars that pyridine nitrogen is an active center in general redox reaction, so if the formation of other nitrogen-containing functional groups can be reduced, the polarity of the nitrogen-containing functional groups can be maximally utilized, and the influence of nitrogen doping on the physical parameters of the activated carbon can be relatively reduced. And the preparation of the high pyridine nitrogen activated carbon is also beneficial to calculating the reaction path of the nitrogen-doped activated carbon during catalysis by using a quantum chemical calculation tool, and the research on the catalysis mechanism of the nitrogen-doped activated carbon can be promoted. The inventor finds that most of nitrogen-doped activated carbon has a similar ratio of pyridine nitrogen to pyrrole nitrogen in the research on nitrogen-doped activated carbon at the present stage, and cannot fully utilize the high activity of the pyridine nitrogen. A small number of students use methods such as a water plasma etching method and a magnetron sputtering method to improve the pyridine nitrogen content, but the cost is too large, and the method is difficult to utilize in a common laboratory and industry.
Disclosure of Invention
As discussed in the background art, the ratio of pyridine nitrogen to pyrrole nitrogen in most of nitrogen-doped activated carbon in the prior art is similar, so that the high activity of pyridine nitrogen cannot be fully utilized, and the existing method for increasing the content of pyridine nitrogen has huge cost and is difficult to be utilized in laboratories and industries.
Against the background of the research, the invention aims to provide a preparation process and a system of high pyridine nitrogen doped activated carbon, which are implemented by adding ammonia gas, ammonia water, melamine or G-C3N4And the traditional nitrogen source is replaced by the polyvinyl pyridine synthesized by the vinyl pyridine, so that the nitrogen-doped activated carbon with higher proportion of pyridine nitrogen functional groups can be obtained, and the cost is lower.
Specifically, the technical scheme of the invention is as follows:
in the first aspect of the invention, a preparation process of high pyridine nitrogen-doped activated carbon is provided, wherein a carbon material is doped by taking polyvinyl pyridine as a nitrogen source under a heating condition to obtain the high pyridine nitrogen-doped activated carbon.
Specifically, the preparation process of the high pyridine nitrogen-doped activated carbon comprises the following steps:
1) preparation of polyvinylpyridine:
liquid vinylpyridine is dripped into high-temperature N at constant speed2In the atmosphere, vinyl pyridine vapor is formed, and the vinyl pyridine vapor is mixed with FeCl3Reacting the solution to generate a polyvinyl pyridine precipitate, cleaning and drying the polyvinyl pyridine precipitate by using distilled water to obtain polyvinyl pyridine, wherein the polyvinyl pyridine is marked as ppl-1;
2) preparing a carbonized precursor:
crushing and screening the carbon material, cleaning the carbon material by using deionized water, and drying the carbon material; adding the dried carbon material and deionized water into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle completely, and heating; after the carbon material is cooled, cleaning and drying the carbon material after the hydrothermal reaction to obtain a carbonization precursor for hydrothermal carbonization, which is marked as yk-1;
3) preparing high pyridine nitrogen doped activated carbon:
KOH, ppl-1 and yk-1 were mixed in N2And (3) under the atmosphere, activating the uniformly mixed mixture by adopting programmed temperature rise, thoroughly washing the activated sample for several times by using hydrochloric acid, removing inorganic salt, and washing by using distilled water until the pH value is neutral. And finally drying to obtain the high pyridine nitrogen activated carbon.
In a second aspect of the invention, a high pyridine nitrogen-doped activated carbon prepared by the preparation process of the high pyridine nitrogen-doped activated carbon of the first aspect is provided.
The nitrogen doping amount in the high pyridine nitrogen-doped activated carbon is 4% -10%, and the nitrogen-doped nitrogen element form comprises: pyridine nitrogen, pyrrole nitrogen and graphite type nitrogen, wherein the pyridine nitrogen accounts for 40% -70% of the total nitrogen content, the pyrrole nitrogen accounts for 20% -50% of the total nitrogen content, and the graphite type nitrogen accounts for 2% -20% of the total nitrogen content;
in a third aspect of the present invention, there is provided a system for preparing highly pyridine nitrogen-doped activated carbon, the system comprising:
the device comprises carbon material treatment equipment, a hydrothermal carbonization reaction generating device, a polyvinylpyridine generating device, a mixture reaction generating device and a temperature programming device.
The specific embodiment of the invention has the following beneficial effects:
by adding ammonia, melamine or G-C3N4And the traditional nitrogen source is replaced by the polyvinyl pyridine synthesized by the vinyl pyridine, so that the nitrogen-doped activated carbon with higher proportion of pyridine nitrogen functional groups can be obtained, and the preparation method is lower and has good application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a system for preparing high pyridine nitrogen-doped activated carbon;
FIG. 2 is a graph showing XPS results for high pyridine nitrogen activated carbon prepared in example 1 of the present invention;
FIG. 3 is a graph showing XPS results for high pyridine nitrogen activated carbon prepared in example 2 of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As discussed in the background art, in most of the studies on nitrogen-doped activated carbon at the present stage, the ratio of pyridine nitrogen to pyrrole nitrogen in nitrogen-doped activated carbon is similar, so that the high activity of pyridine nitrogen cannot be fully utilized, and the existing method for increasing the content of pyridine nitrogen is very costly and is difficult to be utilized in laboratories and industries. In view of this, the invention provides a process and a system for preparing high pyridine nitrogen-doped activated carbon, which can obtain nitrogen-doped activated carbon with a high proportion of pyridine nitrogen functional groups at low cost.
In an embodiment of the present invention, a preparation process of a high pyridine nitrogen-doped activated carbon is provided, in which a carbon material is doped with polyvinylpyridine as a nitrogen source under a heating condition, so as to obtain the high pyridine nitrogen-doped activated carbon.
In a specific embodiment, the preparation process of the high pyridine nitrogen-doped activated carbon comprises the following steps:
1) preparation of polyvinylpyridine:
liquid vinylpyridine is dripped into high-temperature N at constant speed2In the atmosphere, vinyl pyridine vapor is formed, and the vinyl pyridine vapor is mixed with FeCl3Reacting the solution to generate a polyvinyl pyridine precipitate, cleaning and drying the polyvinyl pyridine precipitate by using distilled water to obtain polyvinyl pyridine, wherein the polyvinyl pyridine is marked as ppl-1;
preferably, the feeding rate of the liquid vinylpyridine is 0.2-5ml/min, so that the vinylpyridine and FeCl are ensured3The solutions were brought into full contact.
Preferably, the high temperature N2The temperature of (A) is 80-120 ℃;
preferably, the FeCl3The concentration of the solution is 0.3-1.5M;
preferably, the vinylpyridine vapor is reacted with FeCl3The solution reacts under the condition of magnetic stirring, the magnetic stirring time is 0.5-10 h, and the generation efficiency of the polymer is ensured.
2) Preparing a carbonized precursor:
crushing and screening the carbon material, cleaning the carbon material by using deionized water, and drying the carbon material; adding the dried carbon material and deionized water into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle completely, and heating; after the carbon material is cooled, cleaning and drying the carbon material after the hydrothermal reaction to obtain a carbonization precursor for hydrothermal carbonization, which is marked as yk-1;
preferably, the carbon material includes, but is not limited to, biomass carbon material, coal-based carbon material, and high molecular organic carbon material;
preferably, the particle size of the carbon material sieved is as follows: the diameter of the carbon particles is 10-100 meshes;
preferably, the drying temperature is 100-200 ℃;
preferably, the temperature of the hydrothermal reaction is set at 100-300 ℃;
preferably, the carbon material after the hydrothermal reaction is washed with deionized water and absolute ethanol.
3) Preparing high pyridine nitrogen doped activated carbon:
KOH, ppl-1 and yk-1 were mixed in N2And (3) under the atmosphere, activating the uniformly mixed mixture by adopting programmed temperature rise, thoroughly washing the activated sample for several times by using hydrochloric acid, removing inorganic salt, and washing by using distilled water until the pH value is neutral. And finally drying to obtain the high pyridine nitrogen activated carbon.
Preferably, the mass ratio of ppl-1, yk-1 and KOH is 1: 1: 2-8;
preferably, the temperature programming device is heated to 600-1000 ℃ at a constant temperature rise rate of 3-9 ℃/min and is kept for 1-8 h; the temperature raising program is set to improve the nitrogen doping efficiency during activation.
Preferably, the hydrochloric acid concentration is 3 wt% to 20 wt%;
preferably, the oven temperature is 105-.
In one embodiment of the present invention, there is provided a high pyridine nitrogen-doped activated carbon prepared by the above process for preparing a high pyridine nitrogen-doped activated carbon, wherein the nitrogen doping amount in the high pyridine nitrogen-doped activated carbon is 4% to 10%, and the nitrogen-doped nitrogen element form includes: pyridine nitrogen, pyrrole nitrogen and graphite type nitrogen, wherein the pyridine nitrogen accounts for 40% -70% of the total nitrogen content, the pyrrole nitrogen accounts for 20% -50% of the total nitrogen content, and the graphite type nitrogen accounts for 2% -20% of the total nitrogen content.
In one embodiment of the present invention, there is provided a system for preparing pyridine nitrogen-doped activated carbon, the system including:
the device comprises carbon material treatment equipment, a hydrothermal carbonization reaction generating device, a polyvinylpyridine generating device, a mixture reaction generating device and a temperature programming device.
In a specific embodiment, the preparation system of pyridine nitrogen-doped activated carbon further comprises a drying device, a suction filtration system, a magnetic stirrer and a tail gas treatment device.
In one embodiment of the invention, the application of the high pyridine nitrogen-doped activated carbon in xxx is provided.
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific examples and comparative examples.
Example 1
Adding colorless liquid vinylpyridine into injector, and dripping into 80 deg.C N solution at constant speed of 4ml/min under the drive of injection pump2Atmosphere, fast evaporation of vinylpyridine with N2FeCl with the concentration of 1.0M is introduced together3The solution is magnetically stirred for 5 hours; in FeCl3The precipitate in the solution bottle is polypyridine ethylene, which is filtered and separated, washed with great amount of distilled water and dried to obtain polypyridine, named as ppl-1;
crushing and screening coconut shells, and screening out the coconut shells with a porous sieve to obtain carbon particles with the diameter of 40 meshes; washing with deionized water, drying in an electrothermal blowing drying oven set at 105 deg.C. Then adding the dried carbon material and deionized water into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle completely, and then placing the hydrothermal reaction kettle in an electric heating drying box for heating, wherein the temperature of the hydrothermal reaction is set at 240 ℃; cooling, washing off substances such as tar on the surface in a suction filtration device by using deionized water and absolute ethyl alcohol, drying to obtain a carbonization precursor for hydrothermal carbonization, and recording the carbonization precursor as yk-1;
KOH with the mass of 15g, ppl-1 and yk-1 are mixed, and the mass ratio of the ppl-1 to the yk-1 to the KOH is 1: 1: 4; in N2Under the atmosphere, putting the uniformly mixed mixture into a temperature programming device for activation, heating the temperature programming device to 500 ℃ at a constant temperature rising rate of 5 ℃/min,keeping for 4 h; and thoroughly washing the activated sample by using hydrochloric acid with the concentration of 10 wt% for several times, removing inorganic salt, washing the sample by using distilled water until the pH value is neutral, and finally drying the sample at 120 ℃ to obtain the high pyridine nitrogen activated carbon.
The detection proves that the nitrogen doping amount is 6.4%, and the nitrogen doping nitrogen element form comprises: pyridine nitrogen, pyrrole nitrogen and graphite type nitrogen, wherein the pyridine nitrogen accounts for 58.92 percent of the total nitrogen content, the pyrrole nitrogen accounts for 32.28 percent of the total nitrogen content, and the graphite type nitrogen accounts for 5.34 percent of the total nitrogen content;
example 2
Adding colorless liquid vinylpyridine into injector, and dripping N at 105 deg.C under the drive of injection pump at constant speed of 4ml/min2Atmosphere, fast evaporation of vinylpyridine with N2FeCl with a concentration of 1.5M is introduced together3The solution is magnetically stirred for 5 hours; in FeCl3The precipitate in the solution bottle is polypyridine ethylene, which is filtered and separated, washed with great amount of distilled water and dried to obtain polypyridine, named as ppl-1;
crushing and screening coconut shells, and screening out the coconut shells with a porous sieve to obtain carbon particles with the diameter of 40 meshes; washing with deionized water, drying in an electrothermal blowing drying oven set at 120 deg.C. Then adding the dried carbon material and deionized water into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle completely, and then placing the hydrothermal reaction kettle in an electric heating drying box for heating, wherein the temperature of the hydrothermal reaction is set to be 260 ℃; cooling, washing off substances such as tar on the surface in a suction filtration device by using deionized water and absolute ethyl alcohol, drying to obtain a carbonization precursor for hydrothermal carbonization, and recording the carbonization precursor as yk-1;
KOH with the mass of 15g, ppl-1 and yk-1 are mixed, and the mass ratio of the ppl-1 to the yk-1 to the KOH is 1: 1: 6; in N2Under the atmosphere, putting the uniformly mixed mixture into a temperature programming device for activation, heating the temperature programming device to 600 ℃ at a constant heating rate of 8 ℃/min, and keeping the temperature for 5 hours; thoroughly washing the activated sample with 10 wt% hydrochloric acid for several times to remove inorganic salt, washing with distilled water until pH is neutral, and drying at 120 deg.C to obtain high pyridine nitrogen activityAnd (4) charcoal.
The detection proves that the nitrogen doping amount is 4.41%, and the nitrogen doping nitrogen element form comprises: pyridine nitrogen, pyrrole nitrogen and graphite type nitrogen, wherein the pyridine nitrogen accounts for 41.72% of the total nitrogen content, the pyrrole nitrogen accounts for 42.09% of the total nitrogen content, and the graphite type nitrogen accounts for 16.15% of the total nitrogen content;
comparative example 1
Preparing nitrogen-doped activated carbon by taking ammonia water as a nitrogen source:
crushing and screening coconut shells, and screening out the coconut shells with a porous sieve to obtain carbon particles with the diameter of 40 meshes; washing with deionized water, drying in an electrothermal blowing drying oven set at 105 deg.C. Then adding the dried carbon material and deionized water into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle completely, and then placing the hydrothermal reaction kettle in an electric heating drying box for heating, wherein the temperature of the hydrothermal reaction is set at 240 ℃; cooling, washing off tar and other substances on the surface in a suction filtration device by using deionized water and absolute ethyl alcohol, drying to obtain a precursor of the nitrogen-doped carbon material, and adding 25% NH into the precursor3·H2Magnetically stirred in O for 5h and heated at 90 ℃ for 12h to complete the nitrogen incorporation. The resulting solution was then rinsed with water to remove the base and dried to give a dry powder form of the final product.
Through detection, the nitrogen doping amount of the prepared nitrogen-doped activated carbon is 6%, and the nitrogen-doped nitrogen element form comprises: pyridine nitrogen, pyrrole nitrogen and graphite type nitrogen, wherein the pyridine nitrogen accounts for 31.44% of the total nitrogen content, the pyrrole nitrogen accounts for 44.14% of the total nitrogen content, and the graphite type nitrogen accounts for 16.32% of the total nitrogen content;
comparative example 2
Preparing nitrogen-doped activated carbon by taking ammonia gas as a nitrogen source:
crushing and screening coconut shells, and screening out the coconut shells with a porous sieve to obtain carbon particles with the diameter of 40 meshes; washing with deionized water, drying in an electrothermal blowing drying oven set at 105 deg.C. Then adding the dried carbon material and deionized water into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle completely, and then placing the hydrothermal reaction kettle in an electric heating drying box for heating, wherein the temperature of the hydrothermal reaction is setFixing at 240 ℃; cooling, washing off tar and other substances on the surface in a suction filtration device by using deionized water and absolute ethyl alcohol, drying to obtain a precursor of the nitrogen-doped carbon material, and introducing 50% NH3，700℃，3h。
Through detection, the nitrogen doping amount of the prepared nitrogen-doped activated carbon is 6.8%, and the nitrogen-doped nitrogen element form comprises: pyridine nitrogen, pyrrole nitrogen and graphite type nitrogen, wherein the pyridine nitrogen accounts for 29.56% of the total nitrogen content, the pyrrole nitrogen accounts for 48.39% of the total nitrogen content, and the graphite type nitrogen accounts for 15.45% of the total nitrogen content;
comparative example 3
With C3N4Preparation of nitrogen-doped activated carbon for nitrogen source:
crushing and screening coconut shells, and screening out the coconut shells with a porous sieve to obtain carbon particles with the diameter of 40 meshes; washing with deionized water, drying in an electrothermal blowing drying oven set at 105 deg.C. Then adding the dried carbon material and deionized water into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle completely, and then placing the hydrothermal reaction kettle in an electric heating drying box for heating, wherein the temperature of the hydrothermal reaction is set at 240 ℃; cooling, washing off substances such as tar on the surface in a suction filtration device by using deionized water and absolute ethyl alcohol, drying to obtain a nitrogen-doped carbon material precursor, mixing the nitrogen-doped carbon material precursor with melamine according to the mass ratio of 1:10, and annealing for 3 hours at 950 ℃ in a nitrogen atmosphere.
Through detection, the nitrogen doping amount of the prepared nitrogen-doped activated carbon is 5.7%, and the nitrogen-doped nitrogen element form comprises: pyridine nitrogen, pyrrole nitrogen and graphite type nitrogen, wherein the pyridine nitrogen accounts for 43.11% of the total nitrogen content, the pyrrole nitrogen accounts for 26.31% of the total nitrogen content, and the graphite type nitrogen accounts for 25.96% of the total nitrogen content;
the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation process of high pyridine nitrogen doped activated carbon is characterized in that under the heating condition, polyvinyl pyridine is used as a nitrogen source to dope a carbon material to obtain the high pyridine nitrogen doped activated carbon.
2. The process for preparing highly pyridine nitrogen-doped activated carbon according to claim 1, comprising the steps of:
1) preparation of polyvinylpyridine:
liquid vinylpyridine is dripped into high-temperature N at constant speed2In the atmosphere, vinyl pyridine vapor is formed, and the vinyl pyridine vapor is mixed with FeCl3Reacting the solution to generate a polyvinyl pyridine precipitate, cleaning and drying the polyvinyl pyridine precipitate by using distilled water to obtain polyvinyl pyridine, wherein the polyvinyl pyridine is marked as ppl-1;
2) preparing a carbonized precursor:
crushing and screening the carbon material, cleaning the carbon material by using deionized water, and drying the carbon material; adding the dried carbon material and deionized water into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle completely, and heating; after the carbon material is cooled, cleaning and drying the carbon material after the hydrothermal reaction to obtain a carbonization precursor for hydrothermal carbonization, which is marked as yk-1;
3) preparing high pyridine nitrogen doped activated carbon:
KOH, ppl-1 and yk-1 were mixed in N2And (3) under the atmosphere, activating the uniformly mixed mixture by adopting programmed heating, washing the activated sample by using hydrochloric acid, washing the sample by using distilled water until the pH value is neutral, and drying to obtain the high pyridine nitrogen activated carbon.
3. The process for preparing highly pyridine nitrogen-doped activated carbon according to claim 2, wherein in the step (1), the feeding rate of the liquid vinylpyridine is 0.2-5 ml/min;
or, the high temperature N2The temperature of (A) is 80-120 ℃;
alternatively, the FeCl3The concentration of the solution is 0.3-1.5M;
alternatively, vinylpyridine vapor is reacted with FeCl3The solution reacts under the condition of magnetic stirring, and the magnetic stirring time is 2-10 h.
4. The process for preparing highly pyridine nitrogen-doped activated carbon according to claim 2, wherein in the step (2),
the carbon material comprises a biomass carbon material, a coal-based carbon material and a high molecular organic carbon material;
or the particle size of the screened carbon material is as follows: the diameter of the carbon particles is 10-100 meshes;
or, the drying temperature is 100-200 ℃;
or setting the temperature of the hydrothermal reaction at 100-300 ℃;
or when the carbon material after the hydrothermal reaction is cleaned, deionized water and absolute ethyl alcohol are used for cleaning.
5. The process for preparing highly pyridine nitrogen-doped activated carbon according to claim 2, wherein in the step (3), the mass ratio of ppl-1, yk-1 and KOH is 1: 1: 2-8.
6. The process for preparing highly pyridine nitrogen-doped activated carbon according to claim 2, wherein in the step (3),
the temperature programming device is heated to 600-;
or the concentration of the hydrochloric acid is 3-20 wt%;
alternatively, the oven temperature is 105-.
7. The high pyridine nitrogen-doped activated carbon prepared by the preparation process of the high pyridine nitrogen-doped activated carbon according to any one of claims 1 to 6.
8. The highly pyridine nitrogen-doped activated carbon according to claim 7, wherein the nitrogen doping amount in the highly pyridine nitrogen-doped activated carbon is 4% -10%, and the nitrogen-doped nitrogen element form comprises: pyridine nitrogen, pyrrole nitrogen and graphite type nitrogen, wherein the pyridine nitrogen accounts for 40% -70% of the total nitrogen content, the pyrrole nitrogen accounts for 20% -50% of the total nitrogen content, and the graphite type nitrogen accounts for 2% -20% of the total nitrogen content.
9. A system for preparing high pyridine nitrogen-doped activated carbon, which is characterized by comprising: the device comprises carbon material treatment equipment, a hydrothermal carbonization reaction generating device, a polyvinylpyridine generating device, a mixture reaction generating device and a temperature programming device.
10. The system for preparing high pyridine nitrogen-doped activated carbon according to claim 9, further comprising a drying device, a suction filtration system, a magnetic stirrer and a tail gas treatment device.
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|---|---|---|---|---|
| CN116253421A (en) * | 2022-11-29 | 2023-06-13 | 嘉兴沃特泰科环保科技股份有限公司 | Hydrogen peroxide remover for water treatment, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391078A (en) * | 2015-07-31 | 2017-02-15 | 天津大学 | Catalyst used for one-step preparation of vinyl chloride from dichloroethane and acetylene, and preparation method and application thereof |
| CN107159110A (en) * | 2017-05-22 | 2017-09-15 | 江苏大学 | A kind of preparation method and its usage of pomelo peel base multi-stage porous carbon material |
| CN108059145A (en) * | 2017-12-14 | 2018-05-22 | 同济大学 | A kind of preparation method of multi-stage porous N doping porous carbon |
-
2020
- 2020-09-29 CN CN202011052844.2A patent/CN112758922B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391078A (en) * | 2015-07-31 | 2017-02-15 | 天津大学 | Catalyst used for one-step preparation of vinyl chloride from dichloroethane and acetylene, and preparation method and application thereof |
| CN107159110A (en) * | 2017-05-22 | 2017-09-15 | 江苏大学 | A kind of preparation method and its usage of pomelo peel base multi-stage porous carbon material |
| CN108059145A (en) * | 2017-12-14 | 2018-05-22 | 同济大学 | A kind of preparation method of multi-stage porous N doping porous carbon |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116253421A (en) * | 2022-11-29 | 2023-06-13 | 嘉兴沃特泰科环保科技股份有限公司 | Hydrogen peroxide remover for water treatment, preparation method and application |
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