An ordered porous carbon fiber and a preparation method and application thereof

Abstract

The application provides an ordered porous carbon fiber and a preparation method and application thereof, and relates to the technical field of adsorbing materials. Traditional carbon fibers have a large pore size distribution, and the pore structure cannot be fully utilized in purifying gas pollutants. In the application, a template agent is used to form a fixed skeleton in a polymer organic substance, and an ordered porous carbon fiber material with a large specific surface area is synthesized. The ordered porous carbon fiber material has a regular pore structure. The ordered porous carbon fiber material provides sufficient adsorption space and sufficient active sites, so that organic sulfur molecules such as COS and CH3SH are intercepted on the material surface and in the pore channel, and the adsorption and removal of organic sulfur are achieved. Compared with existing disordered carbon-based materials, the ordered porous carbon fiber prepared by the application has more effective adsorption sites, and has a more extensive application prospect in the field of purifying organic sulfur and the like.

Description

Technical Field

[0001] This invention relates to the field of adsorption materials technology, and in particular to an ordered porous carbon fiber, its preparation method, and its application. Background Technology

[0002] Organic sulfur compounds, typical sulfur-containing pollutants, are commonly found in coke oven gas, water gas, natural gas, and petroleum gas. Examples include carbonyl sulfide (COS) and methanethiol (CH3SH). As organic sulfur pollutants present in high concentrations, COS and CH3SH not only cause catalyst poisoning and deactivation and corrosion of pipelines and equipment during the utilization of resource gases, but also harm the environment and human health. Therefore, the deep purification of COS and CH3SH in resource gases is essential.

[0003] Currently, the purification of COS and CH3SH mainly relies on dry methods. Among these, adsorption is particularly effective for low-concentration organic sulfur gases, offering advantages such as low cost, simple operation, and no secondary pollution. Activated carbon is widely used in organic sulfur purification due to its large specific surface area, low price, good hydrothermal stability, and sulfur resistance. Chinese patent CN113070039A discloses an adsorption material for removing organic sulfur from coke oven gas and its application. Using activated carbon as a carrier, a 1-ethyl-3-methylimidazolium acetate ionic liquid synthesis catalyst is in-situ supported for COS removal from coke oven gas. This method can achieve effective COS adsorption at low temperatures (20–50℃), but activated carbon has an amorphous structure, and the irregular mesopores formed by the stacking of micropores reduce its adsorption capacity. In comparison, activated carbon fibers can effectively address the problems associated with activated carbon. Chinese patent CN110102302A discloses a catalyst for carbonyl sulfur purification, its preparation method, and its application. This patent uses activated carbon fiber as a carrier and treats the porous carrier through methods such as strong alkali impregnation and heat treatment. This method can effectively improve the surface properties of carbon-based materials, thereby enhancing their ability to adsorb COS at low temperatures. However, the disordered microporous structure of activated carbon fibers is not conducive to fully utilizing their adsorption sites, reducing the binding of active sites to organic sulfur molecules. Current research mainly focuses on the removal of organic sulfur from disordered carbon-based materials; there is currently no research on the use of ordered carbon fiber materials for the simultaneous purification of COS and CH3SH. Summary of the Invention

[0004] The purpose of this invention is to provide an ordered porous carbon fiber, its preparation method and application. The ordered porous carbon fiber provided by this invention can achieve efficient and simultaneous removal of organic sulfur as a desulfurizing agent.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a method for preparing ordered porous carbon fibers, comprising the following steps:

[0007] The template agent is dissolved in a first polar organic solvent to obtain solution A;

[0008] A high molecular weight organic compound is dissolved in a second polar organic solvent to obtain solution B;

[0009] Solution A is mixed with solution B to obtain solution C;

[0010] The pH of solution C is adjusted to acidic, and the acidified solution is crystallized to obtain polymeric organic crystals embedded with template agents;

[0011] The template-embedded polymeric organic crystals are dispersed in a third polar organic solvent, and the resulting spinning solution is electrospun to obtain nanofibers.

[0012] The nanofibers were calcined under a protective atmosphere to obtain the ordered porous carbon fibers.

[0013] Preferably, the template agent is hexadecyltrimethylammonium bromide, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, or tetrapropylammonium hydroxide; the first polar organic solvent is dimethylformamide, methanol, ethanol, or acetone; and the content of the template agent in solution A is 5–20 g / 100 mL.

[0014] Preferably, the high molecular weight organic compound is polyvinylidene fluoride, polyacrylonitrile, polyvinylpyrrolidone, or polymethyl methacrylate; the second polar organic solvent is dimethylformamide, methanol, ethanol, or acetone; and the content of the high molecular weight organic compound in solution B is 10–30 g / 100 mL.

[0015] Preferably, the mass ratio of template agent to high molecular weight organic matter in solution C is (1-4):(2-6).

[0016] Preferably, the pH value of the acidified solution is 1 to 5.

[0017] Preferably, the crystallization temperature is 100-150°C and the time is 24-72 hours.

[0018] Preferably, the content of the template agent-embedded polymeric organic crystals in the spinning solution is 6-15 g / 100 mL.

[0019] Preferably, the roasting includes sequentially performing a first roasting, heating, and a second roasting; the temperature of the first roasting is 150–300°C; and the temperature of the second roasting is 500–700°C.

[0020] The present invention provides ordered porous carbon fibers prepared by the preparation method described above.

[0021] This invention provides the application of the ordered porous carbon fiber described above as a desulfurizing agent in the simultaneous removal of COS and CH3SH.

[0022] Traditional carbon fibers have a large pore size distribution, which cannot fully utilize the pore structure for purifying gaseous pollutants. This invention synthesizes ordered porous carbon fiber materials with a large specific surface area by forming a fixed framework within the polymer organic material using a template agent. These ordered porous carbon fiber materials possess a regular pore structure. By utilizing the sufficient adsorption space and active sites provided by the ordered porous carbon fiber material, organic sulfur molecules such as COS and CH3SH are trapped on the material surface and within the pores, achieving the goal of adsorption and removal of organic sulfur. Compared with existing disordered carbon-based materials, the ordered porous carbon fibers prepared in this invention have more effective adsorption sites and have broader application prospects in the purification of organic sulfur and other fields.

[0023] COS and CH3SH exhibit competitive adsorption on catalysts. Traditional desulfurizers primarily target one type of organic sulfur, failing to achieve simultaneous purification of multiple organic sulfur components. The ordered porous carbon fiber desulfurizer developed in this invention can be used for the simultaneous and efficient purification and removal of COS and CH3SH. Its excellent water resistance and sulfur poisoning resistance improve the hydrothermal stability and service life of the desulfurizer, achieving a 100% desulfurization rate even at low temperatures (≤100℃). Attached Figure Description

[0024] Figure 1 This is an electron microscope image of the morphology of the ordered porous carbon fiber desulfurizer of Example 1 of the present invention;

[0025] Figure 2 The nitrogen isothermal adsorption curve of the ordered porous carbon fiber desulfurizer in Example 1;

[0026] Figure 3 The image shows the pore size distribution of the ordered porous carbon fiber desulfurizer in Example 1.

[0027] Figure 4 The graph shows the removal efficiency of COS and CH3SH by the desulfurizing agents prepared in Examples 1-4 and Comparative Examples 1-3 of this invention. Detailed Implementation

[0028] This invention provides a method for preparing ordered porous carbon fibers, comprising the following steps: dissolving a template agent in a first polar organic solvent to obtain solution A; dissolving a polymeric organic compound in a second polar organic solvent to obtain solution B; mixing solution A and solution B to obtain solution C; adjusting the pH of solution C to acidic, and crystallizing the acidified solution to obtain polymeric organic compound crystals embedded with the template agent; dispersing the polymeric organic compound crystals embedded with the template agent in a third polar organic solvent, and electrospinning the resulting spinning solution to obtain nanofibers; calcining the nanofibers under a protective atmosphere to obtain the ordered porous carbon fibers.

[0029] Unless otherwise specified, all raw materials used in this invention are commercially available products well known in the art.

[0030] In this invention, the template agent is dissolved in a first polar organic solvent to obtain solution A.

[0031] In this invention, the template agent is preferably hexadecyltrimethylammonium bromide (CTAB), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), or tetrapropylammonium hydroxide (TPAOH); the first polar organic solvent is preferably dimethylformamide, methanol, ethanol, or acetone; the content of the template agent in solution A is preferably 5–20 g / 100 mL, more preferably 10–15 g / 100 mL. In this invention, the dissolution of the template agent in the first polar organic solvent is preferably carried out under the first stirring conditions, the temperature of the first stirring is preferably 20–40 °C, and the stirring time is preferably 1–5 h.

[0032] This invention involves dissolving a high molecular weight organic compound in a second polar organic solvent to obtain solution B.

[0033] In this invention, the polymeric organic compound is preferably polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), or polymethyl methacrylate (PMMA); the second polar organic solvent is preferably dimethylformamide, methanol, ethanol, or acetone; the content of the polymeric organic compound in solution B is preferably 10–30 g / 100 mL, more preferably 15–25 g / 100 mL, and even more preferably 18–22 g / 100 mL. In this invention, the dissolution of the polymeric organic compound in the second polar organic solvent is preferably carried out under the second stirring conditions, the temperature of the second stirring is preferably 20–40 °C, and the stirring time is preferably 1–5 h.

[0034] After obtaining solution A and solution B, the present invention mixes solution A and solution B to obtain solution C.

[0035] In this invention, the mass ratio of template agent to high molecular weight organic matter in solution C is preferably (1-4):(2-6), more preferably (1-4):(2-3).

[0036] In this invention, the mixing is preferably performed by adding solution B dropwise to solution A under a third stirring condition; the dropping rate is preferably 1–10 mL / min, more preferably 3–7 mL / min; the temperature of the third stirring is preferably 30–50°C, and stirring is preferably continued for 6–36 hours after the dropping is completed. This invention uses a dropwise addition method to better mix the polymeric organic compound with the template agent.

[0037] After obtaining solution C, the present invention adjusts the pH value of solution C to acidic, and crystallizes the acidified solution to obtain high molecular organic crystals embedded with template agents.

[0038] In this invention, the acid used to adjust the pH of solution C to acidic is preferably one of hydrochloric acid, sulfuric acid, phosphoric acid, and acetic acid, and the molar concentration of the acid is preferably 0.1–2 mol / L, more preferably 0.5–1.5 mol / L. In this invention, the pH of the acidified solution is preferably 1–5, more preferably 2–4, and even more preferably 2.5–3.5. By adjusting the pH of solution C to the above range, this invention facilitates crystallization and promotes the formation of crystal structures with suitable particle sizes.

[0039] In this invention, the crystallization temperature is preferably 100–150°C, more preferably 110–140°C, and even more preferably 120–130°C; the crystallization time is preferably 24–72 h, more preferably 30–60 h, and even more preferably 40–50 h. During the crystallization process, the template agent is orderly and stably embedded into the polymeric organic compound, forming polymeric organic compound crystals embedded with the template agent.

[0040] After crystallization, the present invention preferably filters the resulting mixture to obtain a solid, washes it repeatedly with an organic solvent until the filtrate is neutral, and then dries it to obtain polymeric organic crystals embedded with a template agent. In the present invention, the organic solvent is preferably dimethylformamide, methanol, ethanol, or acetone; the drying temperature is preferably 60–100°C, more preferably 70–90°C; and the drying time is preferably 12–48 hours.

[0041] After obtaining the template-embedded polymeric organic crystals, the present invention disperses the template-embedded polymeric organic crystals in a third polar organic solvent, and performs electrospinning on the resulting spinning solution to obtain nanofibers.

[0042] In this invention, the third polar organic solvent is preferably dimethylformamide, methanol, ethanol, or acetone; the dispersion method is not particularly required and can be any method well known in the art. In this invention, the content of the template agent-embedded polymeric organic crystals in the spinning solution is preferably 6–15 g / 100 mL, more preferably 8–13 g / 100 mL, and even more preferably 10–12 g / 100 mL.

[0043] The present invention does not impose any special limitations on the electrospinning conditions, and electrospinning conditions well known in the art can be used.

[0044] After obtaining the nanofibers, the present invention calcines the nanofibers under a protective atmosphere to obtain the ordered porous carbon fibers.

[0045] In this invention, the protective atmosphere is preferably a nitrogen atmosphere; the calcination preferably includes sequentially performing a first calcination, heating, and a second calcination; the temperature of the first calcination is preferably 150–300°C, more preferably 200–250°C; the temperature of the second calcination is preferably 500–700°C, more preferably 550–650°C, and even more preferably 580–620°C; the heating rate is preferably 5–10°C / min, more preferably 6–8°C / min; and the rate of heating to the temperature of the first calcination is preferably 1–2°C / min.

[0046] In the first calcination stage of this invention, organic solvents are removed, and in the second calcination stage, template agents are removed, while the high molecular organic matter is carbonized to form ordered porous carbon fibers.

[0047] The present invention provides ordered porous carbon fibers prepared by the preparation method described above.

[0048] In this invention, the specific surface area of ​​the ordered porous carbon fiber is preferably >400 m². 2 / g, preferably a mesoporous structure.

[0049] Traditional carbon fibers have a large pore size distribution, which cannot fully utilize the pore structure for purifying gaseous pollutants. This invention synthesizes ordered porous carbon fiber materials with a large specific surface area by forming a fixed framework within the polymer organic material using a template agent. These ordered porous carbon fiber materials possess a regular pore structure. By utilizing the sufficient adsorption space and active sites provided by the ordered porous carbon fiber material, organic sulfur molecules such as COS and CH3SH are trapped on the material surface and within the pores, achieving the goal of adsorption and removal of organic sulfur. Compared with existing disordered carbon-based materials, the ordered porous carbon fibers prepared in this invention have more effective adsorption sites and have broader application prospects in the purification of organic sulfur and other fields.

[0050] This invention provides the application of the ordered porous carbon fiber described above as a desulfurizing agent in the simultaneous removal of COS and CH3SH.

[0051] This invention does not impose specific limitations on the conditions for the removal of COS and CH3SH. In an embodiment of this invention, the simultaneous removal of COS and CH3SH is carried out in a fixed-bed quartz reactor under the following reaction conditions: COS concentration 400 ppm, CH3SH concentration 200 ppm, and space velocity 20000 h⁻¹. -1 The reaction temperature is 40℃.

[0052] COS and CH3SH exhibit competitive adsorption on catalysts. Traditional desulfurizers primarily target one type of organic sulfur, failing to achieve simultaneous purification of multiple organic sulfur components. The ordered porous carbon fiber desulfurizer developed in this invention can be used for the simultaneous and efficient purification and removal of COS and CH3SH. Its excellent water resistance and sulfur poisoning resistance improve the hydrothermal stability and service life of the desulfurizer, achieving a 100% desulfurization rate even at low temperatures (≤100℃).

[0053] The following detailed description of the ordered porous carbon fiber desulfurizer and its preparation method provided by the present invention, with reference to specific embodiments, should not be construed as limiting the scope of protection of the present invention.

[0054] Example 1

[0055] 15g of CTAB was added to 100mL of dimethylformamide and stirred at 20℃ for 5h to form solution A. 30g of PAN was added to 100mL of dimethylformamide and stirred at 35℃ for 4h to form solution B. Solution B was added dropwise to solution A at a rate of 1mL / min and stirred at 30℃ for 12h to form a mixed solution C. 0.5mol / L hydrochloric acid solution was added to the mixed solution to adjust the pH to 4. The acidified solution was then transferred to a reaction vessel and crystallized at 100℃ for 72h. The crystallized mixture was filtered to obtain a solid, which was repeatedly washed with dimethylformamide until the filtrate was neutral. The solid was then dried at 80℃ for 12h to obtain high-molecular-weight organic crystals embedded with a template agent. Six g of polymeric organic crystals embedded with template agents were dispersed in 100 mL of dimethylformamide and nanofiber structures were synthesized by electrospinning. The resulting nanofibers were then calcined in a nitrogen atmosphere in two stages. The first stage calcination temperature was 200℃, the heating rate was 1℃ / min, and the holding time was 2 h. The second stage calcination temperature was 700℃, the heating rate was 5℃ / min, and the holding time was 5 h. Finally, ordered porous carbon fiber desulfurizer A was obtained.

[0056] The morphology of ordered porous carbon fiber desulfurizer A was characterized, and the results are as follows: Figure 1As shown, by Figure 1 It can be seen that the desulfurizing agent prepared by the present invention has a porous structure and the pores are distributed in an orderly manner.

[0057] BET testing was performed on ordered porous carbon fiber desulfurizer A, and the resulting nitrogen adsorption isotherm is as follows: Figure 2 As shown, the aperture distribution is as follows Figure 3 As shown, by Figure 2 It can be seen that the nitrogen adsorption-desorption curve is an H4 type curve, belonging to a micro-mesoporous structure material, which is composed of... Figure 3 It can be seen that the desulfurizing agent has a uniform pore size, all concentrated at 4.6 nm, belonging to an ordered mesoporous structure material. Specific analytical results are shown in Table 1.

[0058] Table 1. BET analysis results of desulfurizing agent A in Example 1

[0059] sample Specific surface area Pore ​​volume Average aperture Example 1 <![CDATA[444.62m 2 / g]]> <![CDATA[0.3959cm 3 / g]]> 4.625nm

[0060] As shown in Table 1, the ordered porous carbon fiber material prepared by this invention has a large specific surface area and is mainly mesoporous.

[0061] Example 2

[0062] 5g of P123 was added to 100mL of methanol and stirred at 40℃ for 4h to form solution A. 10g of PVDF was added to 100mL of methanol and stirred at 40℃ for 3h to form solution B. Solution B was added dropwise to solution A at a rate of 5mL / min and stirred at 50℃ for 36h to form a mixed solution C. 2mol / L acetic acid solution was added to the mixed solution to adjust the pH to 1. The acidified solution was then transferred to a reaction vessel and crystallized at 150℃ for 36h. The crystallized mixture was filtered to obtain a solid, which was repeatedly washed with methanol until the filtrate was neutral. The solid was then dried at 100℃ for 48h to obtain high molecular weight organic crystals embedded with a template agent. Nine g of polymeric organic crystals embedded with template agents were dispersed in 100 mL of methanol, and nanofiber structures were synthesized by electrospinning. The resulting nanofibers were then calcined in a nitrogen atmosphere in two stages. The first stage calcination temperature was 150℃, the heating rate was 2℃ / min, and the holding time was 3 h. The second stage calcination temperature was 650℃, the heating rate was 8℃ / min, and the holding time was 3 h. Finally, ordered porous carbon fiber desulfurizer B was obtained.

[0063] Example 3

[0064] 20 g of TPAOH was added to 100 mL of ethanol and stirred at 30 °C for 1 h to form solution A. 15 g of PVP was added to 100 mL of ethanol and stirred at 25 °C for 5 h to form solution B. Solution B was added dropwise to solution A at a rate of 2 mL / min and stirred at 40 °C for 24 h to form a mixed solution C. 0.1 mol / L sulfuric acid solution was added to the mixed solution to adjust the pH to 3. The acidified solution was then transferred to a reaction vessel and crystallized at 120 °C for 48 h. The crystallized mixture was filtered to obtain a solid, which was repeatedly washed with ethanol until the filtrate was neutral. The solid was then dried at 75 °C for 36 h to obtain high molecular weight organic crystals embedded with a template agent. 15g of template-embedded polymeric organic crystals were dispersed in 100mL of ethanol, and nanofiber structures were synthesized by electrospinning. The resulting nanofibers were then subjected to multi-stage calcination under a nitrogen atmosphere. The calcination process was divided into two stages: the first stage calcination temperature was 300℃, the heating rate was 1.5℃ / min, and the holding time was 4h; the second stage calcination temperature was 600℃, the heating rate was 10℃ / min, and the holding time was 4h. The resulting ordered porous carbon fiber desulfurizer C was obtained. The removal efficiencies of desulfurizer C for COS and CH3SH are shown in [reference needed]. Figure 2 .

[0065] Example 4

[0066] 10g of CTAB was added to 100mL of acetone and stirred at 25℃ for 2h to form solution A. 20g of PMMA was added to 100mL of acetone and stirred at 20℃ for 5h to form solution B. Solution B was added dropwise to solution A at a rate of 10mL / min and stirred at 45℃ for 6h to form a mixed solution C. A 1mol / L phosphoric acid solution was added to the mixed solution to adjust the pH to 5. The acidified solution was then transferred to a reaction vessel and crystallized at 125℃ for 24h. The crystallized mixture was filtered to obtain a solid, which was repeatedly washed with acetone until the filtrate was neutral. The solid was then dried at 60℃ for 24h to obtain template-embedded high-molecular-weight organic crystals. 12g of polymeric organic crystals embedded with template agents were dispersed in 100mL of acetone and nanofiber structures were synthesized by electrospinning. The resulting nanofibers were then calcined in a nitrogen atmosphere in two stages. The first stage calcination temperature was 250℃, the heating rate was 2℃ / min, and the holding time was 2.5h. The second stage calcination temperature was 500℃, the heating rate was 6℃ / min, and the holding time was 6h. The ordered porous carbon fiber desulfurizer D was finally obtained.

[0067] Comparative Example 1 (without template agent)

[0068] 20g of PAN was added to 100mL of dimethylformamide and stirred at 20℃ for 25h to form solution A. A 1.5mol / L acetic acid solution was added to solution A to adjust the pH to 4.5. The acidified solution was then transferred to a reaction vessel and crystallized at 140℃ for 55h. The crystallized mixture was filtered to obtain a solid, which was repeatedly washed with dimethylformamide until the filtrate was neutral. The solid was then dried at 80℃ for 40h to obtain desulfurizer precursor B. 12g of desulfurizing agent precursor B was dissolved in 100mL of dimethylformamide, and nanofiber structures were synthesized by electrospinning. The obtained nanofibers were then calcined in a nitrogen atmosphere in two stages. The first stage calcination temperature was 270℃, the heating rate was 1℃ / min, and the calcination time was 2h. The second stage calcination temperature was 650℃, the heating rate was 10℃ / min, and the holding time was 5h. Finally, desulfurizing agent DB-1 was obtained.

[0069] Comparative Example 2 (without crystallization process)

[0070] 10 g of P123 was added to 100 mL of ethanol and stirred at 35 °C for 4 h to form solution A. 30 g of PMMA was added to 100 mL of ethanol and stirred at 40 °C for 5 h to form solution B. Solution B was added dropwise to solution A at a rate of 5 mL / min, and the mixture was stirred at 50 °C for 20 h to form a mixed solution C. 0.2 mol / L hydrochloric acid solution was added to the mixed solution to adjust the pH to 3.5. The pH-adjusted mixture was dried at 100 °C for 12 h to obtain polymeric organic crystals embedded with the template agent. 13g of polymeric organic crystals embedded with template agents were dispersed in 100mL of ethanol and nanofiber structures were synthesized by electrospinning. The obtained nanofibers were then calcined in a nitrogen atmosphere in two stages. The first stage calcination temperature was 250℃, the heating rate was 2℃ / min, and the calcination time was 3h. The second stage calcination temperature was 500℃, the heating rate was 5℃ / min, and the calcination time was 4h. Finally, desulfurizer DB-2 was obtained.

[0071] Comparative Example 3 (without acidification process)

[0072] 20 g of TPAOH was added to 100 mL of methanol and stirred at 30 °C for 2 h to form solution A. 15 g of PAN was added to 100 mL of methanol and stirred at 30 °C for 4 h to form solution B. Solution B was added dropwise to solution A at a rate of 3 mL / min and stirred at 45 °C for 12 h to form a mixed solution C. Mixed solution C was then transferred to a reaction vessel and crystallized at 120 °C for 40 h. The crystallized mixture was filtered to obtain a solid, which was repeatedly washed with methanol until the filtrate was neutral. The solid was then dried at 70 °C for 12 h to obtain high molecular weight organic crystals embedded with a template agent. Nine g of polymeric organic crystals embedded with template agents were dispersed in 100 mL of methanol, and nanofiber structures were synthesized by electrospinning. The resulting nanofibers were then calcined in a nitrogen atmosphere in two stages. The first stage calcination temperature was 220℃, the heating rate was 1.5℃ / min, and the calcination time was 3 h. The second stage calcination temperature was 550℃, the heating rate was 8℃ / min, and the calcination time was 3 h. Finally, desulfurizer DB-3 was obtained.

[0073] The desulfurization performance of the desulfurizing agents in the examples and comparative examples was tested. The activity test of the desulfurizing agents was carried out in a fixed-bed quartz reactor under the following reaction conditions: COS concentration 400 ppm, CH3SH concentration 200 ppm, and space velocity 20000 h⁻¹. -1 The reaction temperature was 40℃. The removal rates of COS and CH3SH in Examples 1-4 and Comparative Examples 1-3 are shown in the table below. Figure 4 , Figure 4 The specific data are shown in Tables 2 and 3.

[0074] Table 2. COS Removal Rates of Examples and Comparative Examples

[0075]

[0076] Table 3. CH3SH Removal Rate of Examples and Comparative Examples

[0077]

[0078]

[0079] from Figure 4 As can be seen from Tables 2 and 3, the desulfurization performance of the desulfurizers prepared in Examples 1 to 4 is far superior to that of Comparative Examples 1 to 3. Under the above reaction conditions, they can achieve 100% desulfurization efficiency, which indicates that the ordered porous carbon fiber desulfurizer has a significant effect on the removal of COS and CH3SH.

[0080] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. The application of ordered porous carbon fiber as a desulfurizing agent in the simultaneous removal of COS and CH3SH, characterized in that, The method for preparing the ordered porous carbon fiber includes the following steps: The template agent is dissolved in a first polar organic solvent to obtain solution A; the template agent is hexadecyltrimethylammonium bromide, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, or tetrapropylammonium hydroxide; A high-molecular-weight organic compound is dissolved in a second polar organic solvent to obtain solution B; the high-molecular-weight organic compound is polyvinylidene fluoride, polyacrylonitrile, polyvinylpyrrolidone, or polymethyl methacrylate. Solution A is mixed with solution B to obtain solution C; The pH of solution C is adjusted to acidic, and the acidified solution is crystallized to obtain polymeric organic crystals embedded with template agents; The template-embedded polymeric organic crystals are dispersed in a third polar organic solvent, and the resulting spinning solution is electrospun to obtain nanofibers. The nanofibers were calcined under a protective atmosphere to obtain the ordered porous carbon fibers.

2. The application according to claim 1, characterized in that, The first polar organic solvent is dimethylformamide, methanol, ethanol or acetone; the content of the template agent in solution A is 5~20g / 100mL.

3. The application according to claim 1, characterized in that, The second polar organic solvent is dimethylformamide, methanol, ethanol or acetone; the content of high molecular weight organic matter in solution B is 10~30g / 100mL.

4. The application according to any one of claims 1 to 3, characterized in that, The mass ratio of template agent to high molecular weight organic matter in solution C is (1~4):(2~6).

5. The application according to claim 1, characterized in that, The pH value of the acidified solution is 1~5.

6. The application according to claim 1, characterized in that, The crystallization temperature is 100~150℃ and the time is 24~72h.

7. The application according to claim 1, characterized in that, The content of high molecular weight organic crystals with template agent embedded in the spinning solution is 6~15g / 100mL.

8. The application according to claim 1, characterized in that, The roasting process includes sequentially performing a first roasting, heating, and a second roasting; the temperature of the first roasting is 150~300℃; and the temperature of the second roasting is 500~700℃.

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