Hydrophilic carbon material for removing cs2 in organic solid waste gasification fuel gas, preparation method and application

Abstract

The application discloses a hydrophilic carbon material for removing CS2 in organic solid waste gasification fuel gas, a preparation method and application, and relates to the technical field of organic solid waste gasification fuel gas. 3+ First, sodium alginate solution is added dropwise into a salt solution of Fe The hydrophilic carbon material can adsorb and remove gaseous pollutants CS2 in organic solid waste gasification fuel gas under the condition of room temperature and high air speed, and has high removal efficiency.

Description

Technical Field

[0001] This invention belongs to the field of organic solid waste gasification combustion technology, specifically involving hydrophilic carbon materials for removing CS2 from organic solid waste gasification combustion gas, their preparation methods, and applications. Background Technology

[0002] Organic solid waste mainly includes agricultural organic waste, industrial organic waste, and municipal solid waste. Converting organic solid waste into fuel gas through gasification technology is an important way to achieve energy recovery and resource recycling. However, during the gasification process, certain elements in the waste are converted into gaseous pollutants, with the formation and release of sulfur-containing compounds being particularly prominent. Sulfur mainly originates from the presence of organic sulfur in waste plastics, waste rubber, textiles, and kitchen waste, which is converted into gaseous sulfur pollutants such as H2S, COS, and CS2 in the high-temperature gasification environment. These sulfur-containing substances not only severely corrode metal pipes and equipment, shortening system lifespan, but also bring multiple hazards during subsequent fuel gas utilization.

[0003] Existing technologies utilize adsorbents to remove CS2 from the gasification fuel of organic solid waste. Research reports on the adsorption and removal of CS2 using adsorbents mainly include:

[0004] Application No. CN201210064991.0 discloses a method for preparing a catalyst that simultaneously removes carbonyl sulfide and carbon disulfide. This method involves using microwave-activated carbon as a support, and alkaline substances and metal oxides as active components, to ultrasonically impregnate a salt solution with multiple metals. After drying, an activated carbon-based catalyst capable of simultaneously removing COS and CS2 is obtained. Application No. CN202010679307.4 discloses a method for improving the removal rate of COS and CS2 from natural gas. This method modifies the trays and packing by in-situ deposition of COS and CS2 catalysts on their surfaces and by forming a coating containing COS and CS2 catalysts on the surfaces of the trays and packing. The modified trays or packing replace conventional trays or packing, thereby catalytically hydrolyzing the COS and CS2 catalysts fixed on the trays and packing as natural gas passes through the absorption tower, thus improving the adsorption and removal rate of COS and CS2 from natural gas. Application number CN200910074984.7 discloses an adsorbent for removing thiophene and CS2 from coking benzene. It uses γ-Al2O3 as a support and impregnates it with metal salt solution to load Ag and Ce to obtain the adsorbed active components. The adsorbent is obtained by filtration.

[0005] The adsorbents for removing CS2 in the above-mentioned existing technologies also have the following disadvantages: (1) Limitations in adsorption capacity and efficiency: Most adsorbents have limited adsorption capacity for CS2, and they are prone to rapid saturation when treating medium and high concentration waste gas. In addition, other impurities in the polluted gas will compete with CS2 molecules for adsorption, making it difficult to remove CS2; (2) Difficulty in regeneration: The adsorbed CS2 on the physical adsorption type adsorbent is difficult to completely desorb, and the residue formed will permanently occupy the active site, causing the effective adsorption capacity of the adsorbent to continuously decrease with the increase of regeneration times; (3) Poor anti-interference ability: The actual industrial waste gas has a complex composition and contains other sulfides, dust, etc., which will be preferentially adsorbed or react with the adsorbent, blocking the pores, resulting in a decrease in its adsorption selectivity and adsorption efficiency for CS2; (4) High economic cost: The cost of frequent regeneration or replacement of modified or special adsorbents and the high energy consumption required for regeneration increase the cost of industrial use of adsorbents.

[0006] This shows that the existing technology needs further improvement. Summary of the Invention

[0007] To address the problems in the prior art, this invention discloses a hydrophilic carbon material for removing CS2 from gasification fuel of organic solid waste, its preparation method, and its application.

[0008] One of the objectives of this invention is to provide a method for preparing a hydrophilic carbon material for removing CS2 from gasification fuel of organic solid waste. The hydrophilic carbon material prepared therefrom can remove gaseous pollutant CS2 from gasification fuel of organic solid waste under room temperature and high space velocity conditions, and the removal effect is excellent.

[0009] To achieve the above objectives, the technical solution of the present invention is as follows:

[0010] A method for preparing a hydrophilic carbon material for removing CS2 from gasified fuel gas of organic solid waste includes the following steps:

[0011] a) Dissolve sodium alginate in deionized water to prepare solution one; dissolve Fe(NO3)3•9H2O in deionized water to prepare solution two; dissolve polyvinyl alcohol and sodium dodecylbenzene sulfonate in deionized water, mix and heat to boiling, then cool to room temperature to obtain mixed solution three; mix trimethylolpropane trimethacrylate, acrylonitrile, and benzidine by ultrasonic treatment to obtain mixed solution four.

[0012] b. Add solution one drop to solution two, stir for 6 hours, then filter, freeze, dry, and calcine at high temperature under nitrogen atmosphere to obtain carbon material;

[0013] c. Slowly add the carbon material obtained from solution three and step b to solution four, and stir continuously at 70°C for 12 hours to obtain solution five. After vacuum filtration, wash with distilled water and dry, and then extract with ethanol in a Soxhlet extractor for 12 hours to obtain precursor carbon.

[0014] d. Place the precursor carbon in a round-bottom flask, add anhydrous dichloromethane and red aluminum under ice bath conditions, react overnight, and then dry in an oven to obtain a hydrophilic adsorbent carbon material doped with metal ions.

[0015] Preferably, in step a, the mass ratio of sodium alginate to the total mass of trimethylolpropane trimethacrylate and acrylonitrile is 0.8–1%; the Fe ion loading is 50–80 wt%.

[0016] Preferably, in step a, the amount of sodium dodecylbenzenesulfonate added accounts for 0.5-1% of the total mass of trimethylolpropane trimethacrylate and acrylonitrile; the amount of benzidine added is 30% of the total mass of sodium alginate; and the mass ratio of acrylonitrile to trimethylolpropane trimethacrylate is 3:1 to 1:1.

[0017] Preferably, in step a, acrylonitrile is used as a monomer and trimethylolpropane trimethacrylate is used as a crosslinking agent.

[0018] Preferably, in step b, the carbonization temperature is 600-900 ℃ and the carbonization time is 2 h. After carbonization, the metal ions in the hydrophilic carbon adsorbent material doped with metal ions are transformed into their corresponding metal oxides and metal elements.

[0019] Preferably, in step c, the volume ratio of mixed solution three to mixed solution four is 3:1.

[0020] Preferably, in step d, the amount of anhydrous dichloromethane added is 0.3 times the total amount of solution 5, and the amount of red aluminum added is 30-80% of the total mass of acrylonitrile, wherein red aluminum acts as a reducing agent.

[0021] Another objective of this invention is to provide a method for preparing a hydrophilic carbon material for removing CS2 from gasified fuel gas of organic solid waste, wherein the hydrophilic carbon material prepared by the above-mentioned method has a layered three-dimensional structure.

[0022] Another object of the present invention is to provide the application of the above-mentioned hydrophilic carbon material for removing CS2 from the gasification fuel of organic solid waste, wherein the hydrophilic carbon material is used in a fixed-bed reactor under the condition of passing simulated gas and setting the space velocity to 30,000 h⁻¹. -1At a temperature of 25 ℃, CS2 is removed from the gasification fuel of organic solid waste; the simulated gas consists of 10% CH4, 20% CO, 5% CS2, balanced nitrogen and 30 vol% water vapor by mass percentage, wherein the concentration of CS2 is 100 ppm.

[0023] The beneficial effects of this invention, including the hydrophilic carbon material for removing CS2 from organic solid waste gasification fuel, its preparation method, and its application, are as follows:

[0024] (1) In this invention, sodium alginate is selected as the carrier of hydrophilic carbon material, acrylonitrile is selected as monomer, trimethylolpropane trimethacrylate is selected as crosslinking agent, and polyvinyl alcohol is selected as dispersion medium. This allows the -OH and -COOH hydrophilic groups in the carbon material to be evenly distributed inside the carbon material. At the same time, they can combine with more metal ions to generate more adsorption sites for adsorbing gaseous organic sulfur pollutants, which has greater advantages in terms of cost-effectiveness and removal effect.

[0025] (2) In this invention, red aluminum is selected as a reducing agent. Red aluminum reduces the acrylonitrile monomer in the matrix carbon to cross-linked amino adsorbent carbon, which together with the hydrophilic groups contained in sodium alginate constitutes a hydrophilic carbon adsorbent. This is beneficial for the adsorbent to combine with water in the environment during the adsorption process, and is conducive to the hydrolysis adsorption and removal of CS2. It is suitable for adsorption and removal under high concentration CS2 background conditions.

[0026] (3) The present invention selects to use a mixture of oil phase and water phase to form a heterogeneous system, which is beneficial to improve heat transfer efficiency, ensure the structural integrity of the adsorbent material during high-temperature calcination, prevent pore collapse, effectively improve the adsorbent yield, and can be regenerated in high-temperature environment, with a high number of reuses, making it suitable for industrial-grade adsorption equipment.

[0027] (4) The present invention uses a metal impregnation method to drop the precursor carbon into a solution containing Fe. 3+ In salt solutions, metal impregnation facilitates pore formation in the adsorbent, thereby enhancing the internal support structure of the hydrophilic carbon material. This allows different pore sizes within the hydrophilic carbon material to interconnect, forming a network structure with strong heterogeneity and anisotropy, thus improving the adsorption effect of the adsorbent material.

[0028] (5) In the preparation of mixed solution II, this invention adds trimethylolpropane trimethacrylate as a crosslinking agent to crosslink the nitrogen of benzidine onto the hydrophilic carbon material, thereby achieving nitrogen doping and increasing the number of adsorption active sites. This invention uses Fe metal oxides loaded onto the surface or pores of the hydrophilic carbon material carrier, which can significantly increase the number of active sites of the hydrophilic carbon material. By controlling the interaction force between the carrier and the metal oxide, the electron cloud density of the oxide can be effectively reduced, and local defects and oxygen vacancies can be generated, thereby significantly improving the desulfurization performance of the hydrophilic carbon material.

[0029] (6) The hydrophilic carbon material adsorbent of the present invention is prepared by high-temperature calcination. The Fe element is presented as iron oxide in different forms. Metallic Fe can form directional interactions with gaseous pollutant CS2 in various forms to achieve efficient adsorption of CS2. Attached Figure Description

[0030] Figure 1 This is an electron microscope image of the hydrophilic carbon material prepared in Example 1 of the present invention;

[0031] Figure 2 The image shows the contact angle of the hydrophilic carbon material prepared in Example 1 of this invention, which has a contact angle of 13.4°.

[0032] Figure 3 The amount and efficiency of CS2 removal by hydrophilic carbon materials prepared under different embodiment conditions;

[0033] Figure 4 The amount of CS2 removed and the removal efficiency of three adsorption / regeneration cycles in Example 1 are shown (the three regeneration cycles are represented as R1, R2 and R3 respectively). Detailed Implementation

[0034] The following description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

[0035] The following embodiments can be understood as illustrating a part of the structure or method of the present invention individually, or as combining the embodiments to explain the broader structure or method of the present invention.

[0036] This invention proposes a hydrophilic carbon material for removing CS2 from gasified fuel gas of organic solid waste, its preparation method, and its application. To make the advantages and technical solutions of this invention clearer and more explicit, the invention will be further described below with reference to specific embodiments.

[0037] All the raw materials mentioned in this invention can be purchased through commercial channels.

[0038] The evaluation method for the hydrophilic carbon material prepared by this invention is carried out according to the following steps:

[0039] Detection method: A fixed-bed reactor was used, and the concentration of CS2 at the outlet was detected by gas chromatograph (GC-9720P1us).

[0040] Experimental conditions: air velocity 30,000 h -1 The temperature was 25 ℃. The simulated gas composition was: 10% CH4, 20% CO, 100 ppm CS2, balanced nitrogen, and 30 vol% water vapor. A saturator system was used to supply water, and the water content was expressed as relative humidity (RH).

[0041] Evaluation method: The desulfurization efficiency is obtained by the change in CS2 concentration in the flue gas before and after the process. The calculation method is shown in equation (1).

[0042] (1).

[0043] In equation (1): C in This indicates the concentration of CS2 before the adsorption reaction, in mg / m³. 3 C out This indicates the concentration of CS2 after the adsorption reaction, in mg / m³. 3 .

[0044] Capacity represents the mass of CS2 adsorbed per unit mass of hydrophilic carbon material, and the calculation method is shown in equation (2).

[0045] (2);

[0046] In equation (2), C in This indicates the concentration of CS2 before the adsorption reaction, in mg / m³. 3 C out This indicates the concentration of CS2 after the adsorption reaction, in mg / m³. 3 .

[0047] The main technical concept of this invention is as follows: addressing the technical problem that existing technologies using only carbon material adsorbents have small specific surface area, uneven pore distribution, and low pollutant removal efficiency, this invention uses acrylonitrile as a monomer and trimethylolpropane trimethacrylate as a crosslinking agent to synthesize crosslinked carbon with sodium alginate via suspension polymerization. Using Fe metal as a loading metal for treatment can improve the high-speed and high-pressure resistance of the hydrophilic carbon material adsorbent, promote the generation of surface-active components and oxygen vacancies, and result in a high specific surface area and numerous active sites. Red aluminum reduces nitriles to hydrophilic amino groups, which, together with the -OH and -COOH groups present in sodium alginate, form a hydrophilic carbon adsorbent, facilitating CS2 adsorption. During the adsorbent removal process, organic sulfur is hydrolyzed into inorganic sulfur, further enhancing CS2 removal efficiency. The reduction process also generates cross-linking amino groups (-NH2), making the adsorbent material structure more robust. The use of a mixture of oil and aqueous phases in the hydrophilic carbon adsorbent creates a heterogeneous system with ultra-high heat transfer rates and abundant pores. Nitrogen doping enriches the hydrophilic carbon adsorbent with a pyridine N-Fe-O structure, increasing the CS2 reaction pathway and improving the adsorbent's desulfurization capacity, meeting the requirements for CS2 removal from organic solid waste gasification fuels in environments with varying room temperature and high space velocities. The relevant reaction formulas are as follows:

[0048] ;

[0049] .

[0050] The present invention will be further described below with reference to specific embodiments.

[0051] Example 1:

[0052] The present invention discloses a method for preparing a hydrophilic carbon material for removing CS2 from gasification fuel gas of organic solid waste, comprising the following steps:

[0053] Step 1: Weigh 2g of sodium alginate and dissolve it in 200 mL of deionized water to prepare solution 1; weigh 7.2g of Fe(NO3)3•9H2O and dissolve it in 500 mL of deionized water to prepare a 50 wt% solution 2; weigh 1g of polyvinyl alcohol and 1g of sodium dodecylbenzenesulfonate and dissolve them completely in 200 mL of deionized water by heating to prepare a mixed solution 3; take 10 mL of trimethylolpropane trimethacrylate, 10 mL of acrylonitrile, and 10 mL of benzidine and mix them by ultrasonic treatment to prepare a mixed solution 4.

[0054] The second step is to add solution one drop into solution two and stir for 6 hours. Then, wash the solution repeatedly with deionized water 6 times to remove excess metal ions. After vacuum freeze drying in a freeze dryer at -60 ℃ and 10 Pa, place the solution in a tube furnace and carbonize it at 700 ℃ (heating rate 5 ℃ / min) for 2 hours in a 100% N2 atmosphere to prepare carbon materials.

[0055] Step 3: Under constant stirring speed, solution 3 and carbon material are slowly added to solution 4 and stirred continuously at 70°C for 12 hours to obtain mixed solution 5; solution 5 is filtered under reduced pressure, washed with deionized water and dried; then extracted with ethanol in a Soxhlet extractor for 12 hours to remove solvent and other low molecular weight polymers, washed with deionized water and dried to prepare precursor carbon.

[0056] Step 4: Place the precursor carbon in a round-bottom flask, add 50 mL of anhydrous dichloromethane under ice bath and nitrogen conditions, slowly add 10 mL of 3 mg / mL red aluminum solution and react for 30 min, then heat to 45℃ and react for 12 h; then dry in an oven at 80℃ for 10 h to obtain the hydrophilic adsorbent carbon material.

[0057] The electron microscope image of the hydrophilic carbon material prepared in this embodiment is as follows. Figure 1 As shown, from Figure 1 It can be seen that hydrophilic carbon materials exhibit a layered structure, with particles forming aggregates on the material surface and interspersed in the cross-linked network, exhibiting a layered structure with higher porosity.

[0058] The nitrogen-doped metal oxide-supported hydrophilic carbon material with controllable pore size prepared in this embodiment was tested under high space velocity conditions: space velocity 30,000 h⁻¹. -1 The temperature was 25 ℃. The simulated gas composition was: 10% CH4, 20% CO, 100 ppm CS2, balanced nitrogen, and 30 vol% water vapor. A saturator system was used for water supply, and the water content was expressed as relative humidity (RH). A mass flow controller was used to control the total flow rate at 1 L / min. The desulfurization efficiency was measured to be 96.51%.

[0059] Example 2:

[0060] The difference from Example 1 is that in the first step, 3.2g of sodium alginate, 2g of polyvinyl alcohol, and 2g of sodium dodecylbenzenesulfonate were weighed to prepare mixed solution one; 5mL of trimethylolpropane trimethacrylate, 15mL of acrylonitrile, and 10mL of benzidine were weighed to prepare mixed solution two.

[0061] The desulfurization efficiency was tested and found to be 91.45%.

[0062] Example 3:

[0063] The difference from Example 1 is that in the third step, 10 ml of 8 mg / mL red aluminum solution is added;

[0064] The desulfurization efficiency was found to be 87.94% after testing.

[0065] Example 4:

[0066] The difference from Example 1 is that in the third step, it is added dropwise to an 80% mass fraction Fe(NO3)3•9H2O salt solution;

[0067] The desulfurization efficiency was found to be 95.59% after testing.

[0068] Example 5:

[0069] The difference from Example 1 is that after the adsorption experiment in Example 1, the adsorbent was regenerated in a tube furnace at 900 °C and N2 atmosphere (flow rate of 50 mL / min) at a heating rate of 10 °C / min for 2 hours to desorb and regenerate it, and then the desulfurization experiment was carried out. The above process was repeated 3 times (denoted as R1, R2 and R3 respectively).

[0070] After testing, the desulfurization efficiency of R1 was 91.51%, that of R2 was 88.06%, and that of R3 was 85.26%.

[0071] The removal efficiency and removal amount of CS2 by the hydrophilic carbon materials prepared in Examples 1-4 above are as follows: Figure 2 As shown. The removal efficiency and removal amount of CS2 by the hydrophilic carbon material regenerated multiple times in Example 5 above are as follows. Figure 3 As shown. From Figure 2 As can be seen from the data in Example 1, the adsorbent maintained a high removal rate for CS2 for the longest time and had the largest total adsorption volume, indicating the best removal effect. Figure 3 It can be seen that after the first thermal regeneration treatment, the adsorption capacity of CS2 decreased by only 0.15%, and the adsorption efficiency remained at a high level after three regenerations, showing good regeneration performance.

[0072] Example 6:

[0073] A method for preparing a hydrophilic carbon material for removing CS2 from gasified fuel gas of organic solid waste includes the following steps:

[0074] a) Dissolve sodium alginate in deionized water to prepare solution one; dissolve Fe(NO3)3•9H2O in deionized water to prepare solution two; dissolve polyvinyl alcohol and sodium dodecylbenzene sulfonate in deionized water, mix and heat to boiling, then cool to room temperature to obtain mixed solution three; mix trimethylolpropane trimethacrylate, acrylonitrile, and benzidine by ultrasonic treatment to obtain mixed solution four.

[0075] b. Add solution one drop to solution two, stir for 6 hours, then filter, freeze, dry, and calcine at high temperature under nitrogen atmosphere to obtain carbon material;

[0076] c. Slowly add the carbon material obtained from solution three and step b to solution four, and stir continuously at 70°C for 12 hours to obtain solution five. After vacuum filtration, wash with distilled water and dry, and then extract with ethanol in a Soxhlet extractor for 12 hours to obtain precursor carbon.

[0077] d. Place the precursor carbon in a round-bottom flask, add anhydrous dichloromethane and red aluminum under ice bath conditions, react overnight, and then dry in an oven to obtain a hydrophilic adsorbent carbon material doped with metal ions.

[0078] In step a, the mass ratio of sodium alginate to the total mass of trimethylolpropane trimethacrylate and acrylonitrile is 0.8%; the Fe ion loading is 50 wt%.

[0079] In step a, the amount of sodium dodecylbenzenesulfonate added accounts for 0.5% of the total mass of trimethylolpropane trimethacrylate and acrylonitrile; the amount of benzidine added is 30% of the total mass of sodium alginate; and the mass ratio of acrylonitrile to trimethylolpropane trimethacrylate is 3:1.

[0080] In step a, acrylonitrile is used as a monomer and trimethylolpropane trimethacrylate is used as a crosslinking agent.

[0081] In step b, the carbonization temperature is 600℃ and the carbonization time is 2h. After carbonization, the metal ions in the hydrophilic carbon adsorbent material doped with metal ions are oxidized to their corresponding oxides to adsorb CS2 in the gasification fuel of organic solid waste.

[0082] In step c, the volume ratio of mixed solution three to mixed solution four is 3:1;

[0083] In step d, the amount of anhydrous dichloromethane added is 0.3 times the total amount of solution V, and the amount of red aluminum added is 30% of the total mass of acrylonitrile. Red aluminum acts as a reducing agent to enhance hydrophilicity, which is beneficial for the hydrolysis removal of CS2.

[0084] Example 7:

[0085] The difference from Example 6 is:

[0086] In step a, the mass ratio of sodium alginate to the total mass of trimethylolpropane trimethacrylate and acrylonitrile is 1%; Fe 3+ The salt solution is Fe(NO3)3•9H2O, in which the loading of Fe ions is 80wt%;

[0087] In step a, the amount of sodium dodecylbenzenesulfonate added accounts for 1% of the total mass of trimethylolpropane trimethacrylate and acrylonitrile; the mass ratio of acrylonitrile to trimethylolpropane trimethacrylate is 1:1.

[0088] In step b, the carbonization temperature is 900 ℃;

[0089] In step d, the amount of red aluminum added is 80% of the total mass of acrylonitrile.

[0090] Example 8:

[0091] This example provides a method for preparing a hydrophilic carbon material for removing CS2 from gasified fuel gas of organic solid waste, as described above. The hydrophilic carbon material prepared by this method has a layered three-dimensional structure.

[0092] Example 9:

[0093] This embodiment provides the application of the hydrophilic carbon material described above for removing CS2 from gasified fuel gas of organic solid waste. The hydrophilic carbon material is used in a fixed-bed reactor with simulated gas introduced, and the space velocity is set to 30,000 h⁻¹. -1 At a temperature of 25°C, CS2 is removed from the gasification fuel of organic solid waste; the simulated gas consists of 10% CH4, 20% CO, 5% CS2, balanced nitrogen, and 30 vol% water vapor by mass percentage, wherein the concentration of CS2 is 100 ppm.

[0094] Comparative Example 1:

[0095] The difference from Example 1 is that sodium alginate is replaced with carrageenan.

[0096] The specific preparation steps are as follows:

[0097] Step 1: Weigh 2g of carrageenan and dissolve it in 200mL of deionized water to prepare solution 1; weigh 7.2g of Fe(NO3)3•9H2O and dissolve it in 500mL of deionized water to prepare a 50wt% solution 2; weigh 1g of polyvinyl alcohol and 1g of sodium dodecylbenzenesulfonate and dissolve them completely in 200mL of deionized water by heating to prepare a mixed solution 3; take 10mL of trimethylolpropane trimethacrylate, 10mL of acrylonitrile, and 10mL of benzidine and prepare a mixed solution 4 by ultrasonic treatment.

[0098] The second step is to add solution one drop into solution two and stir for 6 hours. Then, wash the solution repeatedly with deionized water 6 times to remove excess metal ions. After vacuum freeze drying in a freeze dryer at -60 ℃ and 10 Pa, place the solution in a tube furnace and carbonize it at 100% N2 atmosphere and 700 ℃ (heating rate 5 ℃ / min) for 2 hours to prepare carbon materials.

[0099] Step 3: Under constant stirring speed, solution 3 and carbon material are slowly added to solution 4 and stirred continuously at 70°C for 12 hours to obtain mixed solution 5; solution 5 is filtered under reduced pressure, washed with deionized water and dried; then extracted with ethanol in a Soxhlet extractor for 12 hours to remove solvent and other low molecular weight polymers, washed with deionized water and dried to prepare precursor carbon.

[0100] Step 4: Place the precursor carbon in a round-bottom flask, add 50 mL of anhydrous dichloromethane under ice bath and nitrogen conditions, slowly add 10 mL of 3 mg / mL red aluminum solution and react for 30 min, then heat to 45℃ and react for 12 h; then dry in an oven at 80℃ for 10 h to obtain the hydrophilic adsorbent carbon material.

[0101] The adsorbent material prepared in this comparative example was tested under high air velocity conditions, with specific steps following those in Example 1. The results showed that the pollutant removal efficiency decreased, with a desulfurization efficiency of 81.70%.

[0102] Comparative Example 2:

[0103] The difference from Example 1 is that no red aluminum solution is added.

[0104] Step 1: Weigh 2g of sodium alginate and dissolve it in 200 mL of deionized water to prepare solution 1; weigh 7.2g of Fe(NO3)3•9H2O and dissolve it in 500 mL of deionized water to prepare a 50 wt% solution 2; weigh 1g of polyvinyl alcohol and 1g of sodium dodecylbenzenesulfonate and dissolve them completely in 200 mL of deionized water by heating to prepare a mixed solution 3; take 10 mL of trimethylolpropane trimethacrylate, 10 mL of acrylonitrile, and 10 mL of benzidine and prepare a mixed solution 4 by ultrasonic treatment.

[0105] The second step is to add solution one drop into solution two and stir for 6 hours. Then, wash the solution repeatedly with deionized water 6 times to remove excess metal ions. After vacuum freeze drying in a freeze dryer at -60 ℃ and 10 Pa, place the solution in a tube furnace and carbonize it at 100% N2 atmosphere and 700 ℃ (heating rate 5 ℃ / min) for 2 hours to prepare carbon materials.

[0106] Step 3: Under constant stirring speed, solution 3 and carbon material are slowly added to solution 4 and stirred continuously at 70°C for 12 hours to obtain mixed solution 5; solution 5 is filtered under reduced pressure, washed with deionized water and dried; then extracted with ethanol in a Soxhlet extractor for 12 hours to remove solvent and other low molecular weight polymers, washed with deionized water and dried to prepare precursor carbon.

[0107] Step 4: Place the precursor carbon in a round-bottom flask, add 50 mL of anhydrous dichloromethane under ice bath and nitrogen conditions, heat to 45℃ and react for 12 h; then dry in an oven at 80℃ for 10 h to obtain hydrophilic adsorbent carbon material.

[0108] The adsorbent material prepared in this comparative example was tested under high space velocity conditions, with specific steps referring to Example 1. The results showed that the pollutant removal efficiency decreased, and the desulfurization efficiency was 79.86%.

[0109] Comparative Example 3:

[0110] The difference from Example 1 is that no acrylonitrile is added.

[0111] Step 1: Weigh 2g of sodium alginate and dissolve it in 200mL of deionized water to prepare solution 1; weigh 7.2g of Fe(NO3)3•9H2O and dissolve it in 500mL of deionized water to prepare a 50wt% solution 2; weigh 1g of polyvinyl alcohol and 1g of sodium dodecylbenzenesulfonate and dissolve them completely in 200mL of deionized water by heating to prepare a mixed solution 3; take 10mL of trimethylolpropane trimethacrylate and 10mL of benzidine and prepare a mixed solution 4 by ultrasonic treatment.

[0112] The second step is to add solution one drop into solution two and stir for 6 hours. Then, wash the solution repeatedly with deionized water 6 times to remove excess metal ions. After vacuum freeze drying in a freeze dryer at -60 ℃ and 10 Pa, place the solution in a tube furnace and carbonize it at 100% N2 atmosphere and 700 ℃ (heating rate 5 ℃ / min) for 2 hours to prepare carbon materials.

[0113] Step 3: Under constant stirring speed, solution 3 and carbon material are slowly added to solution 4 and stirred continuously at 70°C for 12 hours to obtain mixed solution 5; solution 5 is filtered under reduced pressure, washed with deionized water and dried; then extracted with ethanol in a Soxhlet extractor for 12 hours to remove solvent and other low molecular weight polymers, washed with deionized water and dried to prepare precursor carbon.

[0114] Step 4: Place the precursor carbon in a round-bottom flask, add 50 mL of anhydrous dichloromethane under ice bath and nitrogen conditions, slowly add 10 mL of 3 mg / mL red aluminum solution and react for 30 min, then heat to 45℃ and react for 12 h; then dry in an oven at 80℃ for 10 h to obtain the hydrophilic adsorbent carbon material.

[0115] The adsorbent material prepared in this comparative example was tested under high air velocity conditions, with specific steps following those in Example 1. The results showed that the pollutant removal efficiency decreased, with a desulfurization efficiency of 78.94%.

[0116] Comparative Example 4:

[0117] The difference from Example 1 is that the metal salt solution used in this comparative example is a 50% mass fraction AlCl3•6 H2O solution.

[0118] The specific steps are as follows:

[0119] Step 1: Weigh 2g of sodium alginate and dissolve it in 200mL of deionized water to prepare solution 1; weigh 8.9g of AlCl3•6H2O and dissolve it in 500mL of deionized water to prepare a 50wt% solution 2; weigh 1g of polyvinyl alcohol and 1g of sodium dodecylbenzenesulfonate and dissolve them completely in 200mL of deionized water by heating to prepare a mixed solution 3; take 10mL of trimethylolpropane trimethacrylate, 10mL of acrylonitrile, and 10mL of benzidine and prepare a mixed solution 4 by ultrasonic treatment.

[0120] The second step is to add solution one drop into solution two and stir for 6 hours. Then, wash the solution repeatedly with deionized water 6 times to remove excess metal ions. After vacuum freeze drying in a freeze dryer at -60 ℃ and 10 Pa, place the solution in a tube furnace and carbonize it at 100% N2 atmosphere and 700 ℃ (heating rate 5 ℃ / min) for 2 hours to prepare carbon materials.

[0121] Step 3: Under constant stirring speed, solution 3 and carbon material are slowly added to solution 4 and stirred continuously at 70°C for 12 hours to obtain mixed solution 5; solution 5 is filtered under reduced pressure, washed with deionized water and dried; then extracted with ethanol in a Soxhlet extractor for 12 hours to remove solvent and other low molecular weight polymers, washed with deionized water and dried to prepare precursor carbon.

[0122] Step 4: Place the precursor carbon in a round-bottom flask, add 50 mL of anhydrous dichloromethane under ice bath and nitrogen conditions, slowly add 10 mL of 3 mg / mL red aluminum solution and react for 30 min, then heat to 45℃ and react for 12 h; then dry in an oven at 80℃ for 10 h to obtain the hydrophilic adsorbent carbon material.

[0123] The adsorbent material prepared in this comparative example was tested under high air velocity conditions, with specific steps following those in Example 1. The results showed that the pollutant removal efficiency decreased, with a desulfurization efficiency of 92.38%.

[0124] The removal efficiency and removal amount of CS2 by the adsorbent materials prepared in Comparative Examples 1-4 are shown in Table 1. Table 1 shows that the adsorption efficiency and adsorption capacity of the adsorbents prepared in the comparative examples are not high. Compared with the adsorption efficiency of Example 1, the experimental conditions of Example 1 are optimal, resulting in the best CS2 removal efficiency.

[0125] Table 1:

[0126] Adsorption efficiency (%) <![CDATA[Adsorption capacity (mg / m 3 )]]> Comparative Example 1 81.70 197.36 Comparative Example 2 79.86 193.72 Comparative Example 3 78.94 188.23 Comparative Example 4 92.38 223.97

[0127] Those skilled in the art should recognize that the above embodiments are only used to illustrate this application and are not intended to limit this application. Any appropriate changes and variations made to the above embodiments within the essential spirit and scope of this application fall within the scope of protection claimed in this application.

Claims

1. A method for preparing a hydrophilic carbon material for removing CS2 from gasified fuel gas of organic solid waste, characterized in that, Includes the following steps: a) Dissolve sodium alginate in deionized water to prepare solution one; dissolve Fe(NO3)3•9H2O in deionized water to prepare solution two; dissolve polyvinyl alcohol and sodium dodecylbenzene sulfonate in deionized water, mix and heat to boiling, then cool to room temperature to obtain mixed solution three; mix trimethylolpropane trimethacrylate, acrylonitrile, and benzidine by ultrasonic treatment to obtain mixed solution four. b. Add solution one drop to solution two, stir for 6 hours, then filter, freeze, dry, and calcine at high temperature under nitrogen atmosphere to obtain carbon material; c. Slowly add the carbon material obtained from solution three and step b to solution four, and stir continuously at 70°C for 12 h to obtain solution five. After vacuum filtration, wash with distilled water and dry, and then extract with ethanol in a Soxhlet extractor for 12 h to obtain precursor carbon. d. Place the precursor carbon in a round-bottom flask, add anhydrous dichloromethane and red aluminum under ice bath conditions, react overnight, and then dry in an oven to obtain a hydrophilic adsorbent carbon material doped with metal ions. In step a, the mass ratio of sodium alginate to the total mass of trimethylolpropane trimethacrylate and acrylonitrile is 0.8–1%; the Fe ion loading is 50–80 wt%. In step a, the amount of sodium dodecylbenzenesulfonate added accounts for 0.5-1% of the total mass of trimethylolpropane trimethacrylate and acrylonitrile; the amount of benzidine added is 30% of the total mass of sodium alginate; and the mass ratio of acrylonitrile to trimethylolpropane trimethacrylate is 3:1 to 1:

1.

2. The method for preparing a hydrophilic carbon material for removing CS2 from gasified fuel gas of organic solid waste as described in claim 1, characterized in that, In step a, acrylonitrile is used as a monomer and trimethylolpropane trimethacrylate is used as a crosslinking agent.

3. The method for preparing a hydrophilic carbon material for removing CS2 from gasified fuel gas of organic solid waste as described in claim 1, characterized in that, In step b, the carbonization temperature is 600–900 °C and the carbonization time is 2 h. After carbonization, the metal ions in the hydrophilic carbon adsorbent material doped with metal ions are transformed into their corresponding metal oxides and metal elements.

4. The method for preparing a hydrophilic carbon material for removing CS2 from gasified fuel gas of organic solid waste as described in claim 1, characterized in that, In step c, the volume ratio of mixed solution three to mixed solution four is 3:

1.

5. The method for preparing a hydrophilic carbon material for removing CS2 from gasified fuel gas of organic solid waste as described in claim 1, characterized in that, In step d, the amount of anhydrous dichloromethane added is 0.3 times the total amount of solution V, and the amount of red aluminum added is 30-80% of the total mass of acrylonitrile, wherein red aluminum acts as a reducing agent.

6. The hydrophilic carbon material prepared by the method for preparing hydrophilic carbon material for removing CS2 from gasification fuel gas of organic solid waste as described in claim 1, is characterized in that: It has a layered three-dimensional structure.

7. The application of the hydrophilic carbon material as described in claim 6, characterized in that: Hydrophilic carbon materials were tested in a fixed-bed reactor with simulated gas introduced, and the space velocity was set to 30,000 h⁻¹. -1 At a temperature of 25 ℃, CS2 is removed from the gasification fuel of organic solid waste; the simulated gas consists of 10% CH4, 20% CO, 5% CS2, balanced nitrogen and 30 vol% water vapor by mass percentage, wherein the concentration of CS2 is 100 ppm.

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