CN114408894A - Nitrogen-doped porous carbon material and preparation method and application thereof - Google Patents
Nitrogen-doped porous carbon material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 230000009286 beneficial effect Effects 0.000 abstract description 5
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- 238000001816 cooling Methods 0.000 description 5
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- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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Abstract
The invention particularly relates to a nitrogen-doped porous carbon material and a preparation method and application thereof. The nitrogen-doped porous carbon material is prepared by mixing and grinding pyrrole and oxide by a solvent-free mechanical grinding method to synthesize polypyrrole, then performing high-temperature carbonization by taking the polypyrrole as a precursor, and washing and drying. The method has the advantages of simple synthesis conditions, rapid reaction, short time consumption, high yield and reduced use cost of raw materials. The carbon material prepared by the method has rich nitrogen sites, larger specific surface area and hierarchical pore structure, is beneficial to the adsorption of hydrogen sulfide gas, can effectively promote the catalytic conversion of the hydrogen sulfide gas, and has wide application prospect in the selective oxidation and catalysis of the hydrogen sulfide gas.
Description
Technical Field
The invention belongs to the technical field of porous carbon materials, and particularly relates to a preparation method of a nitrogen-doped porous carbon material and efficient selective catalytic oxidation of hydrogen sulfide.
Background
Hydrogen sulfide (H)2S) is a highly toxic, malodorous, flammable and corrosive gas, which has H in various chemical processes such as industrial waste gas stream, natural gas processing and biogas purification2And (4) discharging the S. From the viewpoint of environmental protection and resource regeneration, H2The toxicity, corrosiveness and extremely low odor threshold of S require the urgent development of efficient desulfurization processes. In particular, due to thermodynamic limitations, it is difficult to completely remove H from tail gases having concentrations of 3000-2And S. Residual H in the tail gas2S causes the human olfactory impairment even at a low concentration, and therefore, it is necessary to develop a method for treating H at a low concentration2And S is a new technology. At present, dry-wet adsorption method, reduction adsorption method or H is mainly adopted2S selective catalytic oxidation (H)2S-SCO) method for removing low-concentration H in tail gas2And S. Based on the use of O2Oxidation of H2S to elemental sulfur H2The S-SCO route is a promising, environmentally friendly and cost-effective approach. The selective catalytic oxidation process can be divided into two types, i.e., a discontinuous process and a continuous process, according to reaction conditions. The discontinuous process has been widely used at low temperatures (<Elimination of H at 180 ℃ C2And S. However, since the relatively humid conditions of the discontinuous process cause sulfur to be deposited on the surface or in the micropores of the catalyst, the durability of the catalyst cannot be secured. Therefore, in a discontinuous process, the catalyst needs to be periodically regenerated to remove condensed sulfur to maintain conversion efficiency. In contrast, a continuous selective catalytic oxidation process can directly oxidize H in the absence of water vapor2S gaseous species are oxidized to elemental sulfur at relatively high reaction temperatures: (>Operating at 180 ℃ and precipitatingThe sulfur deposits can be conveniently removed by sublimation of the sulfur (the dew point temperature of the sulfur is about 160 ℃).
In general, the key to the selective catalytic oxidation process of hydrogen sulfide is the design of a highly efficient catalytic system with rich active sites and robust durability. In addition to transition metal oxide-based catalysts (e.g. CuO, V)2O5And Fe2O3) In addition, carbon-based catalysts (including activated carbon, carbon nanotubes, carbon nanofibers, etc.) are also considered promising materials because of their large surface area, high pore volume, excellent sulfur resistance, and excellent thermal stability. In addition to the structural and porous nature, the surface properties of the carbon catalyst are believed to play a critical role in the selective catalytic oxidation of hydrogen sulfide. The catalyst is recently used to increase the basicity of the catalyst by supporting the catalyst with a basic substance, wherein the supported basic substance can enhance H on a carbon-based catalyst2Absorption and dissociation of S. However, the rapid exhaustion of the basic substance drastically deactivates the performance of the carbon catalyst and causes secondary pollution of the deactivated catalyst solid waste. Alternatively, doping the carbon substrate with nitrogen atoms is a good option because isolated electron pairs on the nitrogen atoms can serve as basic sites in place of the basic reagent. The incorporation of nitrogen on the carbon catalyst allows the surface electronic structure of the carbon catalyst to be optimized, which promotes H2Catalytic performance and selectivity of S removal and further reduction of secondary solid contaminants by extending catalyst life. Although promising, the introduction of nitrogen atoms in large quantities on carbon catalysts remains challenging, requiring extreme conditions such as high heat treatment temperatures (700-. Therefore, for hydrogen sulfide selective catalytic oxidation to continue to operate efficiently, it is important to develop a cost-effective strategy for making nitrogen-doped carbon catalysts. Polypyrrole, which consists of two species, carbon and nitrogen, is a readily available polymer that can be simply carbonized at high temperatures to achieve uniform building of nitrogen active sites on the carbon matrix.
Based on the method, in order to enhance the nitrogen doping capacity of the carbon nano material and reasonably control the nitrogen sites of the carbon nano material, the invention provides a novel solvent-free method for quickly synthesizing the nitrogen-doped porous carbon material, wherein pyrrole and an oxidant are quickly ground to synthesize polypyrrole, and the polypyrrole is carbonized at high temperature, washed and dried to obtain the nitrogen-doped porous carbon material. The nitrogen-doped porous carbon material has large specific surface area and hierarchical porosity, rich and high pyridine-N sites are exposed on a carbon shell, and excellent performance is shown in selective catalytic oxidation of hydrogen sulfide.
Disclosure of Invention
The invention aims to provide a nitrogen-doped porous carbon material and a preparation method and application thereof. The porous nitrogen-doped porous carbon material is prepared by grinding pyrrole and an oxidant according to a certain proportion, carbonizing at high temperature, and then washing and drying. The preparation method has simple and easy operation steps and small loss, and the prepared porous carbon material has rich nitrogen sites and large specific surface, is beneficial to catalytic reaction of hydrogen sulfide, can improve the selectivity of the hydrogen sulfide, and has important application potential in the field of carbon materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a nitrogen-doped porous carbon material, which comprises the following steps:
(1) putting pyrrole and an oxidant into an agate mortar, uniformly mixing and grinding into powder;
(2) putting the powder obtained in the step (1) into a crucible, and carbonizing at high temperature in a nitrogen atmosphere;
(3) and (3) washing the sample carbonized in the step (2) with acid liquor, washing with deionized water to be neutral, and drying to obtain the nitrogen-doped porous carbon material.
Further, in the step (1) of the preparation method, the molar ratio of the pyrrole to the oxidant is 1:1-1:2, the oxidant is any one of ammonium persulfate and anhydrous ferric chloride, and the grinding time is 2-10 min.
Further, in the step (2) of the preparation method, the high temperature carbonization condition is increased from room temperature to 600-900 ℃ at a speed of 1-3 ℃/min and is maintained for 30-90 min.
Further, in the step (3) of the preparation method, the acid liquor is 0.2-2 mol/L H2SO4Any one of a solution and 0.2-2 mol/L HCl solution, wherein the mass volume ratio of the carbonized sample to the acid solution is 1-3: 100 g/ml, and the drying condition is 60-120 ℃ and 12-48 h.
The invention also provides a nitrogen-doped porous carbon material prepared by the preparation method.
The invention also provides application of the nitrogen-doped porous carbon material in selective catalytic oxidation of hydrogen sulfide gas.
The invention has the following remarkable advantages:
(1) the nitrogen-doped porous carbon material is low in cost, simple to operate and controllable in preparation process;
(2) the nitrogen-doped porous carbon material prepared by the invention has rich hierarchical pore structures, and is beneficial to the material transmission of hydrogen sulfide and oxygen molecules among pore channels;
(3) the nitrogen-doped porous carbon material prepared by the invention has high-efficiency large-scale transportation; meanwhile, the active site is a nitrogen site, and the corrosion of strong acid and strong alkali to equipment is small; the material is powdery and stable in physicochemical property, and can be easily separated from the reaction medium, so that the material can be recycled;
(4) the nitrogen-doped porous carbon material prepared by the invention has larger specific surface area and abundant pyridine nitrogen doping, is beneficial to the interaction with hydrogen sulfide gas, has efficient selective catalytic oxidation on the hydrogen sulfide gas, and has high H content of 100 percent2The S conversion rate is suitable for the selective catalytic oxidation of the hydrogen sulfide.
Drawings
FIG. 1 is an XRD spectrum of nitrogen-doped porous carbon materials prepared in examples 1-4.
FIG. 2 is a Raman spectrum of nitrogen-doped porous carbon materials prepared in examples 1-4.
FIG. 3 is an SEM spectrum of nitrogen-doped porous carbon materials prepared in examples 1-4.
FIG. 4 is a graph showing the results obtained in examples 1 to 4N of nitrogen-doped porous carbon material2Adsorption-desorption isotherms and pore size distributions.
FIG. 5 is a graph showing H values of nitrogen-doped porous carbon materials prepared in examples 1 to 4 and comparative examples 1 to 22S selective catalytic oxidation activity curve.
Detailed Description
In order to make the present invention more comprehensible, the present invention is described in further detail with reference to specific examples, but the present invention is not limited thereto.
Example 1
Putting 1 mL of pyrrole and 2.5 g of anhydrous ferric trichloride into an agate mortar, uniformly mixing, and grinding for 7 min to obtain polypyrrole powder; putting polypyrrole powder into a crucible, carbonizing at high temperature in nitrogen atmosphere, heating from room temperature to 800 ℃ at the heating rate of 2 ℃/min, and keeping at 800 ℃ for 60 min; 0.4 g of the carbonized sample was washed with 30 mL of 0.5 mol/L H2SO4And washing the solution to remove inorganic salts, washing the solution to be neutral by using deionized water, then drying the solution in an oven at 110 ℃ for 18 h, and naturally cooling the solution to room temperature to obtain the nitrogen-doped porous carbon material which can be used for selective catalytic oxidation of hydrogen sulfide and is marked as a catalyst A (adsorbent A).
Example 2
Putting 1 mL of pyrrole and 3 g of anhydrous ferric chloride into an agate mortar, uniformly mixing, and grinding for 6 min to obtain polypyrrole powder; putting polypyrrole powder into a crucible, carbonizing at high temperature in nitrogen atmosphere, heating from room temperature to 700 ℃ at the heating rate of 2 ℃/min, and keeping at 700 ℃ for 70 min; and (3) washing 0.3 g of carbonized sample by using 20 mL of 1 mol/L HCl solution to remove inorganic salts, washing the sample by using deionized water to be neutral, then putting the sample into an oven, drying the sample for 14 h at 100 ℃, and naturally cooling the sample to room temperature to obtain the nitrogen-doped porous carbon material which can be used for selective catalytic oxidation of hydrogen sulfide and is marked as a catalyst B (adsorbent B).
Example 3
Putting 1 mL of pyrrole and 4 g of anhydrous ferric trichloride into an agate mortar, uniformly mixing, and grinding for 4 min to obtain polypyrrole powder; putting polypyrrole powder into a crucible, and carbonizing at high temperature in nitrogen atmosphereHeating from room temperature to 900 ℃ at a heating rate of 3 ℃/min, and keeping at 900 ℃ for 80 min; 0.3 g of the carbonized sample was washed with 15 mL of 1.5 mol/L H2SO4And washing the solution to remove inorganic salts, washing the solution to be neutral by using deionized water, then drying the solution in an oven at 90 ℃ for 20 hours, and naturally cooling the solution to room temperature to obtain the nitrogen-doped porous carbon material which can be used for selective catalytic oxidation of hydrogen sulfide and is marked as a catalyst C (adsorbent B).
Example 4
Putting 1 mL of pyrrole and 3.5g of ammonium persulfate into an agate mortar, uniformly mixing, and grinding for 3min to obtain polypyrrole powder; putting polypyrrole powder into a crucible, carbonizing at high temperature in nitrogen atmosphere, heating from room temperature to 600 ℃ at the heating rate of 2.5 ℃/min, and keeping at 600 ℃ for 90 min; and (3) washing 0.2 g of carbonized sample by using 10mL of 2 mol/L HCl solution to remove inorganic salts, washing the sample by using deionized water to be neutral, then placing the sample into an oven to be dried for 24 hours at the temperature of 80 ℃, and naturally cooling the sample to room temperature to obtain the nitrogen-doped porous carbon material which can be used for selective catalytic oxidation of hydrogen sulfide and is marked as a catalyst D (adsorbent D).
Comparative example 1
Putting 1 mL of pyrrole and 3.5g of anhydrous ferric trichloride into an agate mortar, uniformly mixing, and grinding for 10 min to obtain polypyrrole powder; 4 g of polypyrrole powder was mixed with 30 mL of 1 mol/L H2SO4And washing the solution to remove inorganic salts, washing the solution to be neutral by using deionized water, then putting the solution into an oven to dry the solution at 900 ℃ for 18 hours, and naturally cooling the solution to room temperature to obtain a product, namely the catalyst E (adsorbent E).
Comparative example 2
And pouring 20g of anhydrous ethanol and 250mg of alkaline modifier ethylenediamine into the same beaker, uniformly mixing, standing for 30min, then filling the mixed solution into a three-neck flask, adding 5g of alkaline-washed activated carbon into the three-neck flask, then placing the three-neck flask into a constant-temperature water bath kettle, sealing and stirring for 24h at 80 ℃, taking out the activated carbon after the reaction is finished, drying for 12 h at 120 ℃, and marking the obtained product as catalyst F (adsorbent F). The preparation method of the alkali-washed active carbon comprises the following steps: pouring the commercial fruit shell activated carbon into a sodium hydroxide solution with the mass fraction of 14%, stirring for 8h to soften, loosen, emulsify and disperse sediments, washing the sediments to be neutral by using deionized water, and drying the sediments for 24h at 100 ℃ to obtain the alkali-washed activated carbon.
The catalysts (adsorbents) obtained in examples 1 to 4, i.e., comparative examples 1 to 2 were analyzed and tested accordingly.
FIG. 1 is an XRD pattern of nitrogen-doped porous carbon materials prepared in examples 1 to 4. For the catalyst A, B, C, D sample, a broad peak was observed around 2 θ =26 °, corresponding to the (002) crystal plane of the graphite structure; the peak intensity of catalyst B, D was weaker, indicating that it was predominantly amorphous carbon; the peak intensity of the catalyst A, C is stronger, which shows that the material has high crystallinity; on the other hand, the catalyst A, C showed a diffraction peak around 2 θ =44 °, which corresponds to the (100) crystal plane of the graphite structure.
FIG. 2 is a Raman spectrum of the nitrogen-doped porous carbon material obtained in examples 1 to 4. All samples showed two broad peaks associated with the D and G bands, at 1350 and 1580 cm respectively-1Left and right, which represent the disordered and ordered structure of the carbon material, respectively; on the other hand, peak intensity ratio (I)D/IG) Indicating the defect degree of the carbon material and further reflecting the graphitization degree, by comparison ID/IGIt shows that the catalyst A, B, C, D has a large amount of micro-nano defects and nitrogen sites.
FIG. 3 is an SEM spectrum of nitrogen-doped porous carbon materials prepared in examples 1-4. As can be seen from the figure, the material synthesized by the invention is composed of the carbon nano sheet-shaped structures, the structures are loose to form rich pores, and the sheet-shaped structures are mutually connected to form a meso-macroporous structure, which is beneficial to H2And mass transfer and diffusion of S gas molecules improve the specific surface area of the material and the utilization efficiency of nitrogen active sites.
FIG. 4 shows N in the nitrogen-doped porous carbon materials prepared in examples 1 to 42Adsorption-desorption isotherms and pore size distributions. The results show that each nitrogen-doped porous carbon material sample shows similar isotherms at the relative pressure P/P0Not more than 0.15, having a significant adsorption amount, corresponding to a typical microporous structure. Capillary condensation occurs at a relatively high relative pressure (P/P)0= 0.9-1.0) due to mesopores and macropores in the hierarchical porous material. In addition, the structural parameters of the synthesized samples are summarized in table 1. The BET surface area and the pore volume of the porous carbon material sample are respectively 196-931m2G and 0.27-0.43cm3In the range of/g, it was found that the BET surface area of the synthesized sample decreased and the pore volume and average pore size increased with increasing pyrolysis temperature, which can be explained by the increase in graphitization at high temperatures and the partial destruction of microporosity. In addition, nitrogen-doped porous carbon materials exhibit hierarchical nanopores distributed with micro-mesopore sizes (0.5-10 nm) and macropore sizes (20-150 nm). The presence of abundant bimodal nanopores increases the degree of internal connectivity in the samples, which facilitates rapid diffusion of the reaction medium in these samples.
TABLE 1 structural parameters of Nitrogen-doped porous carbon materials prepared in examples 1-4
FIG. 5 is a graph showing the H values at different temperatures of the catalysts prepared in examples 1 to 4 and comparative examples 1 to 22S catalytic conversion performance. The result shows that the catalytic activity of the hydrogen sulfide shows a rising trend along with the rise of the reaction temperature, and the performance of the nitrogen-doped porous carbon material in the whole active temperature region of the embodiment is obviously superior to that of the comparative example. During the test, the H of catalyst B was measured at a catalytic reaction temperature of 60 deg.C2The S conversion rate can approach 100 percent and is better than H of catalyst A, C, D under the same condition2And (4) S conversion rate. When the reaction temperature reached 120 ℃, catalyst A, B, C exhibited near 100% conversion; when the reaction temperature reached 150 ℃, the catalyst A, B, C, D showed nearly 100% conversion, which was far superior to the comparative example under the same test conditions. The structural characteristics of the combined material show that the nitrogen-doped porous carbon material prepared by the embodiment of the invention has excellent catalytic activity in a hydrogen sulfide catalytic conversion test due to the characteristics of high specific surface area, rich pyrrole, pyridine nitrogen sites, hierarchical pores and the like.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method for synthesizing a nitrogen-doped porous carbon material without a solvent is characterized by comprising the following steps:
1) putting pyrrole and an oxidant in a mortar with agate according to a certain proportion, uniformly mixing and grinding to obtain powdery polypyrrole;
2) putting the polypyrrole powder prepared in the step 1) into a crucible, and putting the crucible into a tubular furnace for high-temperature carbonization in a nitrogen atmosphere;
3) washing the sample carbonized in the step 2) with acid liquor to remove inorganic salts, washing with deionized water to be neutral, and drying to obtain the nitrogen-doped porous carbon material.
2. The method of claim 1, wherein: in the step 1), the oxidant is any one of anhydrous ferric trichloride and ammonium persulfate.
3. The method of claim 1, wherein: in the step 1), the molar ratio of the pyrrole to the oxidant is 1:1-1: 2.
4. The method of claim 1, wherein: in the step 1), the grinding time is 2-10 min.
5. The method of claim 1, wherein: in the step 2), the high-temperature carbonization condition is to heat the mixture from room temperature to 900 ℃ at the heating rate of 1-3 ℃/min and keep the mixture for 30-90 min.
6. The method of claim 1, wherein: in the step 3), the acid liquor is 0.2-2M H2SO4Solution, 0.2-2M HCl solution.
7. The method of claim 1, wherein: in the step 3), the mass volume ratio of the carbonized sample to the acid solution is 1-3: 100 g/ml.
8. The method of claim 1, wherein: in the step 3), the drying temperature is 60-120 ℃, and the drying time is 12-48 h.
9. A nitrogen-doped porous carbon material produced by the production method according to claim 1.
10. Use of the nitrogen-doped porous carbon material of claim 9 for the selective catalytic oxidation of hydrogen sulfide gas.
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