CN111790350A - Preparation method of nitrogen-doped carbon material and application of nitrogen-doped carbon material in removal of sulfur-containing gas - Google Patents
Preparation method of nitrogen-doped carbon material and application of nitrogen-doped carbon material in removal of sulfur-containing gas Download PDFInfo
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Abstract
The invention provides a preparation method of a nitrogen-doped carbon material and application thereof in removing sulfur-containing gas, wherein the preparation method of the nitrogen-doped carbon material comprises the following steps: dropwise adding an aqueous solution of an initiator into a solution of a nitrogen-containing monomer, filtering and washing to be neutral after oxidative polymerization, and drying to obtain a nitrogen-rich polymer; carbonizing the nitrogen-rich polymer under an inert condition to obtain the nitrogen-doped carbon material; wherein, the pH of the water solution of the initiator is 2-3, and the solvent for dissolving the nitrogen-containing monomer is methanol, ethanol, dichloromethane, dichloroethane or the mixed solution of the methanol, the ethanol, the dichloromethane and the dichloroethane with water. By synthesizing a nitrogen-rich polymer, carbonizing, and limiting the pH of an aqueous solution of an initiator and a solvent for dissolving a nitrogen-containing monomer, the nitrogen doping amount in the prepared nitrogen-doped carbon material, namely the alkaline sites and the specific surface area in the material, can be effectively improved, and the adsorption performance of the material is further improved; and the particle size is uniform, and the agglomeration phenomenon is avoided.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a preparation method of a nitrogen-doped carbon material and application of the nitrogen-doped carbon material in removal of sulfur-containing gas.
Background
Sulfur-containing gas widely exists in natural gas, synthesis gas and industrial waste gas, and can seriously corrode production equipment and poison industrial catalysts due to the acidity of the sulfur-containing gas; therefore, the development of high-efficiency desulfurization technology is always the core problem facing petrochemical industry production, and the key is the development of high-performance desulfurizing agent.
The activated carbon is porous carbon, has low bulk density, large specific surface area and good thermal stability, and is a low-temperature desulfurizer which is applied more at present. The active carbon as a desulfurizer has the functions of adsorption and catalysis, and the desulfurization principle of the desulfurizer mainly depends on the catalytic action of the reaction of active group oxygen on the surface of the active carbon and sulfide to achieve the aim of desulfurization. However, the single active carbon desulfurizer has low desulfurization efficiency, low adsorption rate and unsatisfactory desulfurization precision due to chemical inertness of the surface; therefore, the porous carbon is generally chemically modified by impregnation with an alkaline substance or doping with nitrogen atoms to improve its desulfurization performance.
For example, with Na2CO3The alkaline matter can be used as catalyst for catalyzing H after being impregnated with porous carbon2S is converted into S. However, such desulfurizing agents also cause a series of problems: firstly, the impregnation of the alkaline substance can block the pore channels in the porous carbon, reduce the porosity of the porous carbon, provide a reduction in the pore volume for accommodating desulfurization products, and is not beneficial to the improvement of the desulfurization performance of the porous carbon; secondly, in the practical application of the desulfurizer, the bed temperature is increased rapidly due to too fast reaction, and the desulfurizer has the risk of spontaneous combustion. Thus, the porous carbon is chemically modified by impregnation with alkaline substancesThe application is limited.
The porous carbon is doped with nitrogen atoms, namely the surface chemical property of the active carbon and the internal porous structure of the active carbon are changed, so that the adsorption efficiency of the active carbon desulfurizer on sulfides can be obviously improved, the catalytic performance and the adsorption selectivity of the active carbon desulfurizer are further improved, and the application prospect is good.
Currently, nitrogen-doped porous carbon materials can be prepared by in-situ activation, post-treatment, and in-situ synthesis. The in-situ activation method generally selects biomass as a precursor and KOH as an activator, and the nitrogen-doped porous carbon material prepared by the process has the problems of non-uniform particle size, easy agglomeration, low carbon yield and the like. The post-treatment method is obtained by doping nitrogen atoms into the pure carbon material at high temperature by selecting a nitrogen-containing precursor (usually ammonia). The porous carbon material obtained by the method has low nitrogen doping amount, unstable nitrogen-containing functional groups and damaged pore structures. The in-situ synthesis method selects a nitrogen-containing precursor and takes a template agent as a pore-forming agent; the template method is adopted to relate to the preparation of template agent, the impregnation and polymerization of nitrogen-containing precursor, carbonization and the removal of hard template. The method has the advantages of complicated preparation process, long period and high cost.
Therefore, it is an urgent technical problem to develop a method for preparing a nitrogen-doped porous carbon material with simple preparation method, high nitrogen doping amount, high specific surface area and uniform particle size.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of complex preparation method, low nitrogen doping amount, non-uniform particle size, easy agglomeration and the like of the nitrogen-doped porous carbon material in the prior art, thereby providing a preparation method of the nitrogen-doped carbon material and application thereof in removing sulfur-containing gas.
Therefore, the invention provides the following technical scheme:
a preparation method of a nitrogen-doped carbon material comprises the following steps:
dropwise adding an aqueous solution of an initiator into a solution of a nitrogen-containing monomer, filtering and washing to be neutral after oxidative polymerization, and drying to obtain a nitrogen-rich polymer;
carbonizing the nitrogen-rich polymer under an inert condition to obtain the nitrogen-doped carbon material;
wherein the pH value of the aqueous solution of the initiator is 2-3;
the solvent for dissolving the nitrogen-containing monomer is methanol, ethanol, dichloromethane, dichloroethane or a mixture thereof with water.
Further, when the solvent in which the nitrogen-containing monomer is dissolved is a mixed solution, the volume ratio of methanol, ethanol, dichloromethane or dichloroethane to water is (3-5): 2.
Furthermore, the molar ratio of the nitrogen-containing monomer to the initiator is 1 (0.5-2).
Further, the concentration of the aqueous solution of the initiator is 0.4-0.8 g/ml;
the concentration of the solution of the nitrogen-containing monomer is 0.8-1.2 g/ml.
Further, the dropping rate of the aqueous solution of the initiator is 10 to 15 ml/min.
Further, the temperature of oxidative polymerization is 0-10 ℃, and the time is 12-36 h;
the carbonization temperature is 600-; the time is 1-24 h.
Further, the washing agent used for washing is a solvent for dissolving the nitrogen-containing monomer;
drying at 70-100 deg.C for 20-28 h;
the inert condition refers to nitrogen or argon atmosphere.
Further, the initiator is ammonium persulfate or ferric trichloride;
the nitrogen-containing monomer is at least one of aniline, p-phenylenediamine, m-phenylenediamine and pyrrole;
the pH of the aqueous solution of the initiator is adjusted with hydrochloric acid, acetic acid or sulfuric acid.
The invention also provides the nitrogen-doped carbon material prepared by the preparation method.
The invention also provides the application of the nitrogen-doped carbon material prepared by the preparation method of the nitrogen-doped carbon material in removing sulfur-containing gas.
The technical scheme of the invention has the following advantages:
1. according to the preparation method of the nitrogen-doped carbon material, the nitrogen-rich polymer is synthesized firstly, then carbonization is carried out, and the pH of the aqueous solution of the initiator and the solvent for dissolving the nitrogen-containing monomer are limited, so that the nitrogen doping amount in the prepared nitrogen-doped carbon material, namely the alkaline sites and the specific surface area in the material can be effectively improved, and the adsorption performance of the material is further improved; the particle size is uniform, and the agglomeration phenomenon is avoided; in addition, the preparation method is simple and controllable, and the prepared nitrogen-doped carbon material has extremely low corrosion to equipment, has high stability and is convenient to separate from the equipment for recycling.
2. According to the preparation method of the nitrogen-doped carbon material, provided by the invention, the volume ratio of the mixed solution in which the nitrogen-containing monomer is dissolved is limited, so that the specific surface area and the particle size uniformity of the prepared nitrogen-doped carbon material can be further improved.
3. According to the preparation method of the nitrogen-doped carbon material, provided by the invention, the nitrogen doping amount in the prepared nitrogen-doped carbon material can be further increased by limiting the molar ratio of the nitrogen-containing monomer to the initiator.
4. According to the preparation method of the nitrogen-doped carbon material, provided by the invention, the particle size uniformity of the prepared nitrogen-doped carbon material can be further improved by limiting the concentrations of the initiator and the nitrogen-containing monomer and the dropping rate of the aqueous solution of the initiator.
5. According to the preparation method of the nitrogen-doped carbon material, provided by the invention, the specific surface area of the prepared nitrogen-doped carbon material can be further improved by limiting the parameters of oxidative polymerization and carbonization, so that the adsorption performance of the material is improved.
6. According to the preparation method of the nitrogen-doped carbon material, provided by the invention, the particle size uniformity of the prepared nitrogen-doped carbon material can be further improved by limiting the washing agent used for washing and the drying parameters.
7. According to the preparation method of the nitrogen-doped carbon material, provided by the invention, the nitrogen doping amount and the specific surface area of the prepared nitrogen-doped carbon material can be further improved by limiting the initiator, the nitrogen-containing monomer and the acid for regulating the initiator, so that the adsorption performance of the material is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD spectrum of a nitrogen-doped carbon material prepared in examples 3-6 of the present invention;
FIG. 2 shows N of nitrogen-doped carbon materials obtained in examples 1 to 4 of the present invention2Adsorption and desorption curves;
FIG. 3 is a graph showing pore size distribution curves of nitrogen-doped carbon materials prepared in examples 1 to 4 of the present invention;
FIG. 4 is a graph showing hydrogen sulfide adsorption performance of nitrogen-doped carbon materials prepared in examples 1 to 4 of the present invention;
FIG. 5 is a COS adsorption performance curve of the nitrogen-doped carbon material prepared in examples 1-2 of the present invention.
Description of reference numerals:
the numerical references in the figures represent the corresponding examples, 1-corresponding example 1, 2-corresponding example 2, 3-corresponding example 3, 4-corresponding example 4, respectively.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a nitrogen-doped carbon material, and the preparation method comprises the following steps:
adding pyrrole into ethanol and water at a volume ratio of 3: 2 to obtain a solution A; wherein the concentration of pyrrole is 1.2 g/ml;
weighing ammonium persulfate to dissolve in deionized water to obtain an aqueous solution with the concentration of ammonium persulfate of 0.6g/ml, wherein the molar ratio of pyrrole to ammonium persulfate is 1: 1; dropwise adding concentrated sulfuric acid to adjust the pH value of the aqueous solution of ammonium persulfate to 2 to obtain a solution B;
then, after dropping the solution B into the solution A at 0 ℃ at a rate of 12ml/min and oxidatively polymerizing at this temperature for 24 hours, the solution B was polymerized with a solvent in a volume ratio of 3: 2, washing the mixed solution of ethanol and water for three times until the mixed solution is neutral, filtering, and carrying out vacuum drying for 24 hours at the temperature of 80 ℃ to obtain a nitrogen-rich polymer;
and loading the nitrogen-rich polymer into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, and heating to 900 ℃ at the speed of 10 ℃/min under the protection of nitrogen for carbonization for 24 hours to obtain the nitrogen-doped carbon material.
Example 2
The embodiment provides a nitrogen-doped carbon material, and the preparation method comprises the following steps:
adding aniline into methanol and water at a volume ratio of 2: 1 to obtain a solution A; wherein the concentration of the aniline is 0.8 g/ml;
weighing ammonium persulfate and dissolving the ammonium persulfate in deionized water to obtain an aqueous solution with the concentration of ammonium persulfate of 0.6g/ml, wherein the molar ratio of pyrrole to ammonium persulfate is 1: 1; dropwise adding concentrated sulfuric acid to adjust the pH value of the aqueous solution of ammonium persulfate to 2 to obtain a solution B;
then, after dropping the solution B into the solution A at 10 ℃ at a rate of 12ml/min and oxidatively polymerizing at this temperature for 30 hours, the solution B was polymerized in a volume ratio of 2: 1, washing the mixed solution of methanol and water for three times until the mixed solution is neutral, filtering, and carrying out vacuum drying for 24 hours at the temperature of 80 ℃ to obtain a nitrogen-rich polymer;
and loading the nitrogen-rich polymer into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, and heating to 900 ℃ at the speed of 10 ℃/min under the protection of nitrogen for carbonization for 24 hours to obtain the nitrogen-doped carbon material.
Example 3
The embodiment provides a nitrogen-doped carbon material, and the preparation method comprises the following steps:
adding pyrrole into ethanol and water at a volume ratio of 5: 2 to obtain a solution A; wherein the concentration of pyrrole is 1.0 g/ml;
weighing ammonium persulfate to dissolve in deionized water to obtain an aqueous solution with the concentration of ammonium persulfate of 0.7g/ml, wherein the molar ratio of pyrrole to ammonium persulfate is 1: 2; dropwise adding concentrated sulfuric acid to adjust the pH value of the aqueous solution of ammonium persulfate to be 3, so as to obtain a solution B;
then, after dropping the solution B into the solution A at 8 ℃ at a rate of 11ml/min and oxidatively polymerizing at this temperature for 18 hours, the solution B was polymerized in a volume ratio of 5: 2, washing the mixed solution of ethanol and water for three times until the mixed solution is neutral, filtering, and carrying out vacuum drying for 28 hours at the temperature of 70 ℃ to obtain a nitrogen-rich polymer;
and (3) loading the nitrogen-rich polymer into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, and heating to 800 ℃ at the speed of 5 ℃/min under the protection of nitrogen for carbonization for 12 hours to obtain the nitrogen-doped carbon material.
Example 4
The embodiment provides a nitrogen-doped carbon material, and the preparation method comprises the following steps:
adding aniline into ethanol to obtain a solution A; wherein the concentration of the aniline is 0.9 g/ml;
weighing ammonium persulfate and dissolving the ammonium persulfate in deionized water to obtain an aqueous solution with the concentration of 0.5g/ml of ammonium persulfate, wherein the molar ratio of pyrrole to the ammonium persulfate is 1: 2; dropwise adding concentrated sulfuric acid to adjust the pH value of the aqueous solution of ammonium persulfate to be 3, so as to obtain a solution B;
then dropwise adding the solution B into the solution A at the speed of 11ml/min at the temperature of 6 ℃, carrying out oxidative polymerization at the temperature for 20h, washing the solution B for three times by using ethanol until the solution B is neutral, filtering the solution, and carrying out vacuum drying at the temperature of 70 ℃ for 28h to obtain a nitrogen-enriched polymer;
and (3) loading the nitrogen-rich polymer into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, and heating to 800 ℃ at the speed of 5 ℃/min under the protection of nitrogen for carbonization for 12 hours to obtain the nitrogen-doped carbon material.
Example 5
The embodiment provides a nitrogen-doped carbon material, and the preparation method comprises the following steps:
adding pyrrole into dichloroethane to obtain a solution A; wherein the concentration of pyrrole is 1.1 g/ml;
weighing ammonium persulfate to dissolve in deionized water to obtain an aqueous solution with the concentration of ammonium persulfate of 0.8g/ml, wherein the molar ratio of pyrrole to ammonium persulfate is 1: 0.5; dropwise adding concentrated sulfuric acid to adjust the pH value of the aqueous solution of ammonium persulfate to 2.5 to obtain a solution B;
then dropwise adding the solution B into the solution A at the speed of 10ml/min at the temperature of 3 ℃, carrying out oxidative polymerization for 36h at the temperature, washing the solution for three times to neutrality by using dichloroethane, filtering, and carrying out vacuum drying for 20h at the temperature of 100 ℃ to obtain a nitrogen-enriched polymer;
and (3) loading the nitrogen-rich polymer into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, and heating to 700 ℃ at the speed of 8 ℃/min under the protection of nitrogen for 6 hours to obtain the nitrogen-doped carbon material.
Example 6
The embodiment provides a nitrogen-doped carbon material, and the preparation method comprises the following steps:
adding aniline into dichloromethane to obtain a solution A; wherein the concentration of the aniline is 1.0 g/ml;
weighing ferric trichloride, dissolving the ferric trichloride in deionized water to obtain a water solution with the concentration of the ferric trichloride being 0.4g/ml, wherein the molar ratio of pyrrole to the ferric trichloride is 1: 0.5; dropwise adding concentrated sulfuric acid to adjust the pH value of the aqueous solution of ferric trichloride to be 2.8, so as to obtain a solution B;
then dropwise adding the solution B into the solution A at the speed of 10ml/min at the temperature of 5 ℃, carrying out oxidative polymerization for 12h at the temperature, washing the solution for three times by using dichloromethane until the solution is neutral, filtering the solution, and carrying out vacuum drying for 26h at the temperature of 90 ℃ to obtain a nitrogen-enriched polymer;
and (3) loading the nitrogen-rich polymer into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, and heating to 700 ℃ at the speed of 8 ℃/min under the protection of argon for carbonization for 20h to obtain the nitrogen-doped carbon material.
Example 7
The embodiment provides a nitrogen-doped carbon material, and the preparation method comprises the following steps:
adding p-phenylenediamine into methanol to obtain a solution A; wherein the concentration of the p-phenylenediamine is 1.0 g/ml;
weighing ferric trichloride, dissolving the ferric trichloride in deionized water to obtain a water solution with the concentration of the ferric trichloride being 0.4g/ml, wherein the molar ratio of pyrrole to the ferric trichloride is 1: 0.8; dropwise adding acetic acid to adjust the pH value of the aqueous solution of ferric trichloride to 2 to obtain a solution B;
then dropwise adding the solution B into the solution A at the speed of 15ml/min at the temperature of 5 ℃, carrying out oxidative polymerization for 12h at the temperature, washing the solution for three times by using methanol until the solution is neutral, filtering the solution, and carrying out vacuum drying for 24h at the temperature of 80 ℃ to obtain a nitrogen-enriched polymer;
and (3) loading the nitrogen-rich polymer into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, and heating to 600 ℃ at the speed of 7 ℃/min under the protection of argon for carbonization for 1h to obtain the nitrogen-doped carbon material.
Example 8
The embodiment provides a nitrogen-doped carbon material, and the preparation method comprises the following steps:
adding m-phenylenediamine into ethanol to obtain a solution A; wherein the concentration of the m-phenylenediamine is 1.0 g/ml;
weighing ammonium persulfate to dissolve in deionized water to obtain an aqueous solution with the concentration of ammonium persulfate of 0.4g/ml, wherein the molar ratio of pyrrole to ammonium persulfate is 1: 1.5; dropwise adding concentrated hydrochloric acid to adjust the pH value of the aqueous solution of ammonium persulfate to 2 to obtain a solution B;
then dropwise adding the solution B into the solution A at the speed of 15ml/min at the temperature of 5 ℃, carrying out oxidative polymerization for 12h at the temperature, washing the solution B for three times by using ethanol until the solution B is neutral, filtering the solution, and carrying out vacuum drying for 24h at the temperature of 80 ℃ to obtain a nitrogen-enriched polymer;
and (3) loading the nitrogen-rich polymer into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, and heating to 1000 ℃ at the speed of 6 ℃/min under the protection of argon for carbonization for 10 hours to obtain the nitrogen-doped carbon material.
Comparative example 1 (comparison with example 1)
The comparative example provides a nitrogen-doped carbon material, and the preparation method thereof is as follows:
adding pyrrole into deionized water to obtain a solution A; wherein the concentration of pyrrole is 1.2 g/ml;
weighing ammonium persulfate to dissolve in deionized water to obtain an aqueous solution with the concentration of ammonium persulfate of 0.6g/ml, wherein the molar ratio of pyrrole to ammonium persulfate is 1: 1; dropwise adding concentrated sulfuric acid to adjust the pH value of the aqueous solution of ammonium persulfate to 2 to obtain a solution B;
then, after dropping the solution B into the solution A at 0 ℃ at a rate of 12ml/min and oxidatively polymerizing at this temperature for 24 hours, the solution B was polymerized with a solvent in a volume ratio of 3: 2, washing the mixed solution of ethanol and water for three times until the mixed solution is neutral, filtering, and carrying out vacuum drying for 24 hours at the temperature of 80 ℃ to obtain a nitrogen-rich polymer;
and loading the nitrogen-rich polymer into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, and heating to 900 ℃ at the speed of 10 ℃/min under the protection of nitrogen for carbonization for 24 hours to obtain the nitrogen-doped carbon material.
Comparative example 2 (comparison with example 1)
The comparative example provides a nitrogen-doped carbon material, and the preparation method thereof is as follows:
adding pyrrole into ethanol and water at a volume ratio of 3: 2 to obtain a solution A; wherein the concentration of pyrrole is 1.2 g/ml;
weighing ammonium persulfate to dissolve in deionized water to obtain an aqueous solution with the concentration of ammonium persulfate of 0.6g/ml, wherein the molar ratio of pyrrole to ammonium persulfate is 1: 1; dropwise adding concentrated sulfuric acid to adjust the pH value of the aqueous solution of ammonium persulfate to 1 to obtain a solution B;
then, after dropping the solution B into the solution A at 0 ℃ at a rate of 12ml/min and oxidatively polymerizing at this temperature for 24 hours, the solution B was polymerized with a solvent in a volume ratio of 3: 2, washing the mixed solution of ethanol and water for three times until the mixed solution is neutral, filtering, and carrying out vacuum drying for 24 hours at the temperature of 80 ℃ to obtain a nitrogen-rich polymer;
and loading the nitrogen-rich polymer into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, and heating to 900 ℃ at the speed of 10 ℃/min under the protection of nitrogen for carbonization for 24 hours to obtain the nitrogen-doped carbon material.
Experimental example 1
XRD and N are respectively carried out on the nitrogen-doped carbon material prepared in the example2Adsorption and desorption performance, pore diameter distribution performance and H2And (5) detecting the adsorption performance of S and COS.
The XRD adopts an X-ray diffractometer with the model of X' Pert PRO produced by Panalytical in the Netherlands to analyze the structure, the crystal form and the phase of the prepared nitrogen-doped carbon material, and the specific test method comprises the following steps:
the X-ray source is a Cu target, the incident wavelength of K alpha is 0.15418nm, the graphite monochromator has the working voltage of 40kV, the working current of 40mA, the scanning speed of 0.20s/step, the step length of 0.013 degree/step and the scanning range of 20-80 degrees.
The specific surface area and the pore size distribution performance are tested by adopting an ASAP 2020M physical adsorption instrument of Micrometric company in the United states; the specific test method comprises the following steps:
weighing 0.1g of sieved catalyst of 40-60 meshes, degassing at 160 deg.C under high vacuum for 12 hr, and purifying with high purity N2For adsorbates, low temperature N was obtained by testing at liquid nitrogen temperature (-196 ℃ C.)2Absorbing and desorbing the isotherm, and obtaining the specific surface area and the pore size distribution of the catalyst.
Catalyst H was carried out using a TriStar II physical adsorption apparatus, model number, manufactured by Micrometric corporation, USA2And (5) testing the adsorption performance of S. The specific test method comprises the following steps: weighing 100mg of the sieved catalyst of 40-60 meshes respectively, degassing at 160 deg.C under high vacuum for 12H, and purifying with high purity H2S is adsorbate gas and the test temperature is 0 ℃.
The selective adsorption performance of COS of the catalyst was tested using a TriStar II physical adsorption apparatus, model number, manufactured by Micrometric corporation, USA. The specific test method comprises the following steps: weighing 100mg of the sieved catalyst with 40-60 meshes respectively, degassing at 160 ℃ under high vacuum for 12h, taking high-purity COS as adsorbate gas respectively, testing the temperature at 0 ℃, 25 ℃, 50 ℃ and 75 ℃, heating rate at 5 ℃/min, and stabilizing at each temperature point for 60 min.
As can be seen from fig. 1, the nitrogen-doped carbon materials prepared in examples 3 to 6 both have a strong diffraction peak and a weak broad diffraction peak near 24.6 ° and 43.8 °, which correspond to the (002) and (100) crystal planes in the nitrogen-doped carbon material, respectively, indicating that an amorphous carbon network exists, indicating that the nitrogen-doped carbon material has been synthesized, and the (001) crystal plane indicates that the nitrogen-doped carbon material contains abundant structural defects therein, wherein the amorphous carbon network may be due to a lower carbonization temperature.
As can be seen from fig. 2, the nitrogen-doped carbon materials prepared in examples 1 to 4 are all typical IV-type adsorption-desorption isotherms, which indicate that they have a mesoporous structure and exhibit a higher adsorption capacity, i.e., a steep increase tendency, in a low specific pressure region, indicating that a large amount of microporous or ultra-microporous structures exist inside the structure of the nitrogen-doped carbon material.
As can be seen from fig. 3, the nitrogen-doped carbon materials prepared in examples 1 to 4 have a large number of micropores or ultramicropores in the portion below 2nm, and the nitrogen-doped carbon materials prepared in examples 1 to 4 have a uniform particle size distribution, a high specific surface area, a high pore volume, and a rich microporous structure.
The data of the specific surface area, pore volume and average pore diameter of the nitrogen-doped carbon materials prepared in the specific examples and comparative examples are shown in the following table 1.
TABLE 1 Experimental data for Nitrogen-doped carbon materials prepared in the examples and comparative examples
| Specific surface area (m)2/g) | Pore volume (cm)3/g) | Average pore diameter (nm) | |
| Example 1 | 881 | 0.36 | 4.02 |
| Example 2 | 989 | 0.49 | 3.91 |
| Example 3 | 1131 | 0.70 | 2.31 |
| Example 4 | 1252 | 0.76 | 2.53 |
| Example 5 | 934 | 0.49 | 3.98 |
| Example 6 | 905 | 0.42 | 4.01 |
| Example 7 | 1161 | 0.69 | 2.18 |
| Example 8 | 1139 | 0.70 | 2.09 |
| Comparative example 1 | 325 | 0.21 | 6.51 |
| Comparative example 2 | 333 | 0.19 | 6.12 |
As can be seen from the data in the table above, the nitrogen-doped carbon material provided by the invention has higher specific surface area and pore volume, wherein the specific surface area of example 4 is as high as 1252m2/g。
FIG. 4 shows that the nitrogen-doped carbon material provided by the present invention is used for treating acid gas H2S has excellent adsorption capacity.
As can be seen from fig. 5, the nitrogen-doped carbon material provided by the present invention has a good adsorption property for COS at low temperature.
Experimental example 2
The nitrogen-doped carbon materials prepared in each example and comparative example were subjected to nitrogen doping amounts, H, respectively2And (3) detecting the adsorption performance of the S and the COS, wherein specific detection results are shown in table 2.
Wherein, the nitrogen doping amount adopts an EscaLab250XiX ray photoelectron spectrometer which is manufactured by Thermo Fisher Scientific company to analyze the element type, the element chemical valence state and the element relative content of the prepared porous carbon. The obtained XPS spectrogram is corrected by taking sample surface contaminated carbon (C1 s-284.8 eV) as an internal standard, and the result is fitted by a mixture function of Gaussian-Lorentzian and a Boville fitting algorithm in a manner of Shirley deduction;
H2s and COS adsorption performance adopts H produced by Feiyu Petroleum science and technology development Limited of Nantong city2S/COS absorption tank and buffer tank, COS or H in raw material gas and discharged material gas2The concentration of S is tracked by FL-GC9720 gas chromatograph. The specific test method and parameters are as follows:
H2the S adsorption performance raw material gas comprises: 0.5% H2S/0.25％O2，N2Is balance gas; the catalysts prepared in each example and comparative example are respectively crushed to 20-40 meshes, and the loading amount is 0.5 g; the catalyst activity test conditions were: under normal pressure, the flow rate of the raw material gas is 20ml/min, and the space velocity is 6000ml g–1·h–1(ii) a Test temperature of50℃。
The raw material gas with COS adsorption performance comprises: 0.5% COS/0.25% O2，N2Is balance gas; the catalysts prepared in each example and comparative example are respectively crushed to 20-40 meshes, and the loading amount is 0.5 g; the catalyst activity test conditions were: under normal pressure, the flow rate of the raw material gas is 20ml/min, and the space velocity is 6000ml g–1·h–1(ii) a The test temperature was 50 ℃.
H2S desulfurization rate%2Mass of S-H in the effluent gas2Mass of S)/H in feed gas2Mass of S is multiplied by 100%;
COS desulfurization rate = (mass of COS in feed gas-mass of COS in effluent gas)/mass of COS in feed gas × 100%.
TABLE 2 test results
Note: the concentration of the sulfur-containing gas in the feed gas is the inlet concentration; the concentration of the sulfur-containing gas in the outlet gas is the outlet concentration.
As can be seen from the experimental data in the above table, the nitrogen-doped carbon material provided by the present invention has a higher nitrogen doping amount and H2S and COS adsorption performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The preparation method of the nitrogen-doped carbon material is characterized by comprising the following steps of:
dropwise adding an aqueous solution of an initiator into a solution of a nitrogen-containing monomer, filtering and washing to be neutral after oxidative polymerization, and drying to obtain a nitrogen-rich polymer;
carbonizing the nitrogen-rich polymer under an inert condition to obtain the nitrogen-doped carbon material;
wherein the pH value of the aqueous solution of the initiator is 2-3;
the solvent for dissolving the nitrogen-containing monomer is methanol, ethanol, dichloromethane, dichloroethane or a mixture thereof with water.
2. The method for preparing nitrogen-doped carbon material according to claim 1, wherein when the solvent in which the nitrogen-containing monomer is dissolved is a mixed solution, the volume ratio of methanol, ethanol, dichloromethane or dichloroethane to water is (3-5): 2.
3. The method for preparing nitrogen-doped carbon material according to claim 1 or 2, wherein the molar ratio of the nitrogen-containing monomer to the initiator is 1 (0.5-2).
4. The method for preparing nitrogen-doped carbon material according to any one of claims 1 to 3, wherein the concentration of the aqueous solution of the initiator is 0.4 to 0.8 g/ml;
the concentration of the solution of the nitrogen-containing monomer is 0.8-1.2 g/ml.
5. The method for preparing nitrogen-doped carbon material according to any one of claims 1 to 4, wherein the dropping rate of the aqueous solution of the initiator is 10 to 15 ml/min.
6. The process according to any one of claims 1 to 5, wherein the oxidative polymerization is carried out at a temperature of from 0 to 10 ℃ for a time of from 12 to 36 hours;
the carbonization temperature is 600-; the time is 1-24 h.
7. The method for producing nitrogen-doped carbon material according to any one of claims 1 to 6, wherein the washing agent used for washing is a solvent for dissolving the nitrogen-containing monomer;
drying at 70-100 deg.C for 20-28 h;
the inert condition refers to nitrogen or argon atmosphere.
8. The method for preparing a nitrogen-doped carbon material according to any one of claims 1 to 7, wherein the initiator is ammonium persulfate or ferric trichloride;
the nitrogen-containing monomer is at least one of aniline, p-phenylenediamine, m-phenylenediamine and pyrrole;
the pH of the aqueous solution of the initiator is adjusted with hydrochloric acid, acetic acid or sulfuric acid.
9. The nitrogen-doped carbon material produced by the method for producing a nitrogen-doped carbon material according to any one of claims 1 to 8.
10. Use of a nitrogen-doped carbon material prepared by the method of any one of claims 1 to 8 for removing sulfur-containing gases.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113148973A (en) * | 2021-03-29 | 2021-07-23 | 中南大学 | Nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, and preparation and application methods thereof |
| CN114100575A (en) * | 2021-10-25 | 2022-03-01 | 福州大学 | Preparation method and application of nitrogen-containing defect site porous carbon based on microporous organic polymer |
| CN114408894A (en) * | 2022-02-15 | 2022-04-29 | 福州大学 | Nitrogen-doped porous carbon material and preparation method and application thereof |
| CN116020425A (en) * | 2023-01-09 | 2023-04-28 | 福建久策气体股份有限公司 | Preparation method of two-dimensional solid super acid, two-dimensional solid super acid and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923688A (en) * | 2012-11-01 | 2013-02-13 | 中国科学院长春应用化学研究所 | Preparation method and application of nitrogen-doped carbon material |
| US20160001260A1 (en) * | 2012-01-11 | 2016-01-07 | William Marsh Rice University | Porous carbon materials for co2 separation in natural gas |
| CN105870470A (en) * | 2016-04-27 | 2016-08-17 | 四川理工学院 | Nitrogen-rich hierarchical pore carbon material and preparation method |
| CN106082162A (en) * | 2016-06-07 | 2016-11-09 | 同济大学 | A kind of preparation method of the nitrogenous porous carbon materials of ultracapacitor |
| CN108246338A (en) * | 2018-02-13 | 2018-07-06 | 福州大学 | A kind of N doping ordered mesopore carbon catalysis material and its preparation method and application |
| CN110026228A (en) * | 2019-05-22 | 2019-07-19 | 福州大学 | A kind of preparation of nitrogenous porous carbon materials and its H2S selective catalytic oxidation application |
| US10442996B1 (en) * | 2016-08-26 | 2019-10-15 | Saga Fuel Systems, Inc. | Production and use of ultra-clean carbon compounds and uniform heat from carbon-based feedstocks |
-
2020
- 2020-05-26 CN CN202010455387.5A patent/CN111790350B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160001260A1 (en) * | 2012-01-11 | 2016-01-07 | William Marsh Rice University | Porous carbon materials for co2 separation in natural gas |
| CN102923688A (en) * | 2012-11-01 | 2013-02-13 | 中国科学院长春应用化学研究所 | Preparation method and application of nitrogen-doped carbon material |
| CN105870470A (en) * | 2016-04-27 | 2016-08-17 | 四川理工学院 | Nitrogen-rich hierarchical pore carbon material and preparation method |
| CN106082162A (en) * | 2016-06-07 | 2016-11-09 | 同济大学 | A kind of preparation method of the nitrogenous porous carbon materials of ultracapacitor |
| US10442996B1 (en) * | 2016-08-26 | 2019-10-15 | Saga Fuel Systems, Inc. | Production and use of ultra-clean carbon compounds and uniform heat from carbon-based feedstocks |
| CN108246338A (en) * | 2018-02-13 | 2018-07-06 | 福州大学 | A kind of N doping ordered mesopore carbon catalysis material and its preparation method and application |
| CN110026228A (en) * | 2019-05-22 | 2019-07-19 | 福州大学 | A kind of preparation of nitrogenous porous carbon materials and its H2S selective catalytic oxidation application |
Non-Patent Citations (3)
| Title |
|---|
| HUI PENG等: "Facile Synthesis of Poly(p-phenylenediamine)-Derived Three-Dimensional Porous Nitrogen-Doped Carbon Networks for High Performance Supercapacitors", 《J. PHYS. CHEM. C》 * |
| 张可青等: "化学氧化聚合法合成高电导率聚苯胺研究进展", 《化工新型材料》 * |
| 玄哲文等: "化学氧化法制备聚吡咯的最优条件摸索", 《云南民族大学学报：自然科学版》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113148973A (en) * | 2021-03-29 | 2021-07-23 | 中南大学 | Nitrogen-doped porous carbon electrode material for adsorbing hexavalent chromium, and preparation and application methods thereof |
| CN114100575A (en) * | 2021-10-25 | 2022-03-01 | 福州大学 | Preparation method and application of nitrogen-containing defect site porous carbon based on microporous organic polymer |
| CN114408894A (en) * | 2022-02-15 | 2022-04-29 | 福州大学 | Nitrogen-doped porous carbon material and preparation method and application thereof |
| CN116020425A (en) * | 2023-01-09 | 2023-04-28 | 福建久策气体股份有限公司 | Preparation method of two-dimensional solid super acid, two-dimensional solid super acid and application thereof |
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