Carbon-based pi complexing material for removing CS2 in organic solid waste gasified fuel gas as well as preparation method and application of carbon-based pi complexing material

Abstract

The invention discloses a carbon-based pi complexing material for removing CS2 in organic solid waste gasified fuel gas as well as a preparation method and application thereof, and relates to the technical field of organic solid waste gasified fuel gas. The method comprises the following steps: mixing sodium hyaluronate, mannitol and dried sodium alginate to prepare a mixed solution I; dimethylformamide and methyl acrylate are mixed, polystyrene microspheres and a surfactant are mixed, phenylboronic acid is added into the mixture, the polystyrene microspheres and the phenylboronic acid are chemically bonded and then mixed with the first mixed solution, a cross-linking agent is added, and a third mixed solution is obtained; dropwise adding the mixed solution III into a salt solution containing Sr < 2 + > and Gd < 3 + >; and drying and freezing the obtained metal ion doped hydrogel, and calcining and carbonizing at a high temperature in a nitrogen atmosphere to obtain the metal ion doped hydrogel. The carbon-based pi complexing material prepared by the invention can remove gaseous pollutant CS2 in organic solid waste gasified fuel gas through pi complexing adsorption under the conditions of room temperature and high space velocity, and the removal efficiency is excellent.

Description

Technical Field

[0001] The present invention relates to the technical field of organic solid waste gasification gas, and particularly relates to a carbon-based π complex material for removing CS2 from organic solid waste gasification gas, a preparation method and an application thereof. Background Art

[0002] In China, the annual output of organic solid waste is as high as 6 billion tons, which is characterized by decentralized generation sources, large output, complex composition, etc., and has both resource and pollution attributes. Organic solid waste mainly includes agricultural organic waste, industrial organic waste, municipal domestic waste, etc. Among them, organic sulfur mainly exists in waste plastics, waste rubbers, fabrics and kitchen waste. In the production of organic solid waste gasification gas, sulfur elements will enter the gas in the form of gaseous sulfur pollutants. The presence of gaseous sulfur will accelerate the corrosion of metal pipeline equipment, shorten the service life of the equipment, and the CS2 and dioxin pollutants generated during the combustion process are prone to catalyst poisoning during catalytic processing, and will enter the atmosphere during the combustion process, causing great harm to human life and safety.

[0003] In the prior art, CS2 in organic solid waste gasification gas is adsorbed by sodium alginate aerosol. For example, the research reports on sodium alginate aerosol mainly include:

[0004] Application No. 202111409037.6 discloses a preparation method of a highly catalytically active copper alginate aerosol catalyst, which uses the biomass polymer sodium alginate as a raw material. Iminodiacetic acid and sodium alginate undergo an amidation reaction to convert the monocarboxyl group in the sodium alginate structural unit into a dicarboxyl group, and then crosslink with divalent metal copper ions. After freeze-drying, a highly catalytically active copper alginate aerosol catalyst is obtained. Application No. 202411982606.X discloses a preparation method of a floating copper-loaded sodium alginate hydrogel sphere. By preparing Solution A: composed of sodium alginate, citrate, acidic pH regulator, hydrogen peroxide and water; Solution B: copper sulfate pentahydrate, citrate, pH regulator and water; dropping Solution A into Solution B to obtain hydrogel spheres. Application No. 202310832697.8 discloses a three-dimensional silver-based composite aerogel, a preparation method and an application thereof. A poly(acrylamide-co-acrylic acid) / sodium alginate carbon aerogel is prepared by a sintering method, and then a three-dimensional silver-based composite aerogel with a high specific surface area and high catalytic activity is prepared by an in-situ deposition method using a silver nitrate precursor solution.

[0005] The single-component sodium alginate aerogel used in the above prior art also has the following disadvantages: (1) Low mechanical strength: It is prone to collapse or deformation during use; (2) Limited porosity and adsorption performance: Although it has a high porosity, the internal structure is uneven, resulting in unstable adsorption performance. Its adsorption capacity and adsorption rate are relatively low, making it difficult to meet the requirements of efficient adsorption; (3) Poor thermal stability: It is prone to structural damage under high-temperature conditions, limiting its application in high-temperature environments; (4) Poor resistance to air velocity: Under high air velocity conditions, the pore structure in the adsorbent material is prone to collapse, making it impossible to achieve adsorption at high air velocity; (5) Poor reusability: During the reuse process, it cannot be completely desorbed, resulting in a reduction in adsorption sites and thus affecting its reuse efficiency.

[0006] It can be seen from this that the prior art needs to be further improved. Summary of the Invention

[0007] One of the objectives of the present invention is to provide a preparation method of a carbon-based π complex material for removing CS2 from the gasified gas of organic solid waste. The prepared carbon-based π complex material can remove gaseous pollutant CS2 from the gasified gas of organic solid waste at room temperature and high air velocity, and has excellent removal efficiency.

[0008] To achieve the above objective, the present invention adopts the following technical solutions:

[0009] A preparation method of a carbon-based π complex material for removing CS2 from the gasified gas of organic solid waste, comprising the following steps:

[0010] a. Mix sodium hyaluronate, mannitol, and dried sodium alginate according to a certain ratio to prepare a first mixed solution;

[0011] b. Prepare solution A: Mix dimethylformamide and methyl acrylate;

[0012] Prepare solution B: Mix polystyrene microspheres with a surfactant, add phenylboronic acid thereto, and the polystyrene microspheres react with phenylboronic acid to form a chemical bond;

[0013] Mix solution A and solution B to form a second mixed solution;

[0014] Add the second mixed solution to the first mixed solution, then add sodium tripolyphosphate as a crosslinking agent thereto, control the reaction temperature at 40-60°C and stir to obtain a third mixed solution;

[0015] c. Using the microwave impregnation method, drop the third mixed solution into a salt solution containing Sr 2+ , Gd 3+ to obtain a hydrogel doped with metal ions;

[0016] d. The hydrogel doped with metal ions is dried, frozen, and calcined and carbonized at high temperature under a nitrogen atmosphere to obtain the carbon-based π complex material.

[0017] In the preparation method of the carbon-based π complex material for removing CS2 from the gasified gas of organic solid waste mentioned above, in step a, the mass ratio of sodium alginate, sodium hyaluronate, and mannitol is 1-2:1-4:1-4. The solvent of the first mixed solution is water, and the total mass ratio of sodium alginate, sodium hyaluronate, and mannitol in the first mixed solution is 6-8%. The drying temperature of sodium alginate is 600 °C.

[0018] In the preparation method of the carbon-based π complex material for removing CS2 from the gasified gas of organic solid waste mentioned above, in step b, the total addition amount of dimethylformamide and methyl acrylate is 15-35% of the total mass of sodium hyaluronate, mannitol, and sodium alginate. The addition amounts of the polystyrene microspheres and the surfactant are 3-5% of the total mass of sodium hyaluronate, mannitol, and sodium alginate. The surfactant is cetyltrimethylammonium chloride. The addition amount of the cross-linking agent is 60% of the total mass of sodium hyaluronate, mannitol, and sodium alginate. The addition amount of phenylboronic acid is 0.3 times the addition amount of the polystyrene microspheres.

[0019] In the preparation method of the carbon-based π complex material for removing CS2 from the gasified gas of organic solid waste mentioned above, in step c, Sr 2+ 、Gd 3+ The mass ratio of the two metals in the salt solution of is 1:1. The salt solutions of Sr 2+ 、Gd 3+ are Sr(NO3)2 and Gd(NO3)3·6H2O.

[0020] In the preparation method of the carbon-based π complex material for removing CS2 from the gasified gas of organic solid waste mentioned above, in step c, the microwave impregnation time is 20-40 min, the impregnation temperature is 40-50 °C, and the microwave frequency is 200 GHz.

[0021] In the preparation method of the carbon-based π complex material for removing CS2 from the gasified gas of organic solid waste mentioned above, in step d, the carbonization temperature is 300-900 °C, the carbonization time is 1-3 h. After carbonization, the metal ions in the hydrogel doped with metal ions are oxidized to their corresponding oxides to adsorb CS2 in the gasified gas of organic solid waste.

[0022] In the preparation method of the carbon-based π complex material for removing CS2 from the gasified gas of organic solid waste mentioned above, in step a, sodium alginate is used as a carrier, mannitol is used as a shaping agent for the sodium alginate carrier, and sodium hyaluronate is used as a water retention agent to facilitate the removal of CS2.

[0023] Another object of the present invention is to provide a carbon-based π-complex material prepared by the preparation method of a carbon-based π-complex material for removing CS2 from the gasified gas of organic solid waste, which has a lamellar structure.

[0024] Another object of the present invention is to provide the application of a carbon-based π-complex material for removing CS2 from the gasified gas of organic solid waste. Under the condition of introducing simulated gas into a fixed-bed reactor, the space velocity is set to 60000 h -1 , and when the temperature is 25°C, CS2 in the gasified gas of organic solid waste is removed; the components of the simulated gas include 40% CH4, 20% CO, 35% H2 and 5% CS2 by mass percentage, and the concentration of CS2 is 200 ppm.

[0025] Compared with the prior art, the present invention brings the following beneficial technical effects:

[0026] (1) The present invention selects a carbon carrier hydrogel mixed with sodium hyaluronate, mannitol and dried sodium alginate as the carrier of the carbon-based π-complex material. During the drying process of sodium alginate, the polysaccharide chains are pyrolyzed, oxygen-containing functional groups are removed, and the remaining carbon atoms are rearranged. The carbon atoms are SP 2 hybridized to form an aromatic carbon skeleton, which can combine with more metal ions and generate more adsorption sites for adsorbing organic sulfur and inorganic sulfur gaseous pollutants, having greater advantages in terms of cost-effectiveness and removal effect.

[0027] (2) The present invention selects polystyrene microspheres as the template agent. Polystyrene generates a graphitized carbon-like structure at high temperature and undergoes π-π complexation with the aromatic region of the porous carbon structure of sodium alginate to form a lamellar carbon-based π-complex adsorbent material. The lamellar adsorbent structure has high thermal stability and chemical stability, can be regenerated in a high-temperature environment, has a high number of repeated uses, reduces the long-term application cost, and is suitable for industrial-level adsorption equipment.

[0028] (3) The present invention selects dimethylformamide and methyl acrylate to jointly adjust the solubility and control the film-forming performance of the hydrogel, which is convenient for subsequent loading of metal ions and doping of phosphorus elements. At the same time, both are suitable for high-temperature polymerization systems, ensuring the integrity of the structure of the adsorbent material during high-temperature calcination and preventing pore collapse, which can effectively improve the yield of the adsorbent.

[0029] (4) The present invention adopts the microwave impregnation method, and three drops of the mixed solution are added dropwise to a solution containing Sr 2+ , Gd 3+In the salt solution, the microwave process runs through the chelation cross-linking process of the hydrogel and metal ions; the microwave impregnation method is conducive to pore formation by the cross-linking agent. By controlling the microwave frequency, the pore size of the carbon-based π complex material can be controlled, the proportion of different pore sizes of the carbon-based π complex material can be increased, the internal support structure of the carbon-based π complex material can be enhanced, and a network structure can be formed by the interconnection of different pore sizes inside the carbon-based π complex material, which has strong heterogeneity and anisotropy, and improves the adsorption effect of the carbon-based π complex material.

[0030] (5) In the first mixed solution formed by sodium alginate, sodium hyaluronate and mannitol, polystyrene microspheres and cetyltrimethylammonium chloride are added in the present invention. After high-temperature calcination and carbonization, oxygen-containing groups such as hydroxyl groups (-OH) appear on the polystyrene microspheres, which are chemically bonded to the boric acid groups (B(OH)2) in phenylboronic acid to form borate bonds (B-O), thereby forming a cross-linked structure between the polystyrene chains, making the structure of the adsorbent material more firm, and forming a carbon-based π complex material with a large specific surface area and a porous structure; cetyltrimethylammonium chloride is used as a surfactant to reduce the surface tension of the polystyrene microspheres during the production of the carbon-based π complex material, so that subsequent sodium alginate and metal ions can better chelate with the polystyrene microspheres; the combination of polystyrene microspheres and cetyltrimethylammonium chloride results in a carbon-based π complex material with a more complete internal structure.

[0031] (6) During the preparation of the third mixed solution in the present invention, sodium tripolyphosphate is added as a cross-linking agent for cross-linking, and at the same time, phosphorus element doping is realized, which increases the number of adsorption active sites. In the present invention, two metal oxides of Sr and Gd are doped and loaded on the surface or pores of the carrier of the carbon-based π complex material, which can greatly increase the number of active sites of the carbon-based π complex 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 carbon-based π complex material.

[0032] (7) The adsorption of organic sulfur CS2 by the carbon-based π complex material adsorbent in the present invention is a π complex adsorption process. The central carbon atom of CS2 is SP hybridized to form two delocalized π bonds, and the metal Sr doped in the adsorbent 2+ has 5S empty orbitals. Electrons transfer from the π orbit of the organic sulfide CS2 to the empty S orbit of the metal atom of the adsorbent, which is π complex adsorption. The π electron system of the π complex adsorbent can form a directional interaction with the gaseous pollutant containing π bonds, and high-efficiency adsorption can be achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The present invention will be further described below with reference to the drawings:

[0034] Figure 1 is the electron microscope image of the carbon-based π complex material prepared in Example 1 of the present invention;

[0035] Figure 2 The CS2 removal amount and removal efficiency of the carbon-based π complex materials prepared under the conditions of different embodiments.

[0036] Figure 3 The CS2 removal amount and removal efficiency of Example 1 for three adsorption / regeneration cycles (the three-cycle regenerations are respectively denoted as R1, R2, and R3). Specific Embodiments

[0037] The present invention provides a carbon-based π complex material, a preparation method and an application for removing CS2 from the gasified gas of organic solid waste. In order to make the advantages and technical solutions of the present invention clearer and more definite, the present invention will be further described below with specific embodiments.

[0038] The raw materials mentioned in the present invention can all be obtained through commercial channels.

[0039] The evaluation method of the carbon-based π complex material prepared in the present invention is carried out according to the following steps:

[0040] Detection method: A fixed-bed reactor is used, and a gas chromatograph (GC-9720P1us) is used to detect the concentration of CS2 at the outlet.

[0041] Experimental conditions: Space velocity 60000 h -1 , temperature is 25 °C. The simulated gas composition is: 40% CH4, 20% CO, 35% H2, 500 ppm CS2 and balance nitrogen. A saturator system is used to supply water and the water content is expressed by relative humidity (RH).

[0042] Evaluation method: The desulfurization efficiency is obtained by the change in the concentration of CS2 in the flue gas before and after, and the calculation method is shown in Equation (1).

[0043]

[0044] In Equation (1): C in represents the concentration of CS2 before the adsorption reaction, mg / m 3 ; C out represents the concentration of CS2 after the adsorption reaction, mg / m 3 .

[0045] The capacity represents the mass of CS2 adsorbed per unit mass of the carbon-based π complex material, and the calculation method is shown in Equation (2).

[0046]

[0047] In Equation (2), C in represents the concentration of CS2 before the adsorption reaction, mg / m 3 ; Cout represents the concentration of CS2 after the adsorption reaction, mg / m 3 .

[0048] The main technical concept of the present invention lies in: surrounding the technical problem that the adsorption material caused by only using sodium alginate as the carbon source without metal loading sites in the prior art has a small specific surface area, uneven pore distribution, and low removal efficiency of pollutants. The present invention uses mannitol as a shaping agent, sodium hyaluronate as a water retention agent, and mixes them with dried sodium alginate to obtain a first mixed solution. Using metals Sr and Gd as loading metals for synergistic treatment can improve the high-speed and high-pressure resistance of the carbon-based π complex material adsorbent, promote the generation of surface active components and oxygen vacancies. Doping with phosphorus elements and adding polystyrene microspheres and cetyltrimethylammonium chloride make the adsorbent have the characteristics of adjustable pore size, rich pore channels, high specific surface area and many active sites; obtaining hydrogel balls with more regular shapes and stronger internal structure support. Dimethylformamide and methyl acrylate jointly regulate the film-forming performance of the hydrogel, which is convenient for subsequent loading of metal ions and doping of phosphorus elements. The polystyrene microspheres crosslink with phenylboronic acid to form borate bonds (B-O), making the structure of the adsorbent material more firm. Using cetyltrimethylammonium chloride as a surfactant during the production of hydrogel balls, micelles can be formed to reduce the surface tension of the metal ion solution, and it has the characteristics of amphiphilicity, which can meet the removal of CS2 in organic solid waste gasification gas in different dry and wet environments.

[0049] C6H5B(OH)2 + 2ROH → C6H5B(OR)2 + 2H2O

[0050] The following further illustrates the present invention with specific embodiments.

[0051] Example 1:

[0052] A carbon-based π complex material for removing CS2 from organic solid waste gasification gas according to the present invention, the preparation method comprising the following steps:

[0053] First step, weigh 2 g of sodium hyaluronate, 2 g of mannitol, and 1 g of sodium alginate dried at 600 °C for 2 h and completely dissolve them in 600 mL of deionized water to prepare a first mixed solution; the total mass ratio of sodium hyaluronate, mannitol and sodium alginate in the first mixed solution is 8%.

[0054] Step 2: Prepare Solution A: Take 1 mL of dimethylformamide and 0.05 mL of methyl acrylate to form a mixed solution. Slowly add 1 mL of deionized water to the mixed solution to cause micelle aggregation, and then add the solution to 7 mL of deionized water to inhibit aggregation. Add distilled water to the total volume of the solution to 500 mL, heat to 60 °C, and stir at this temperature for 1 h; Prepare Solution B: 1 g of polystyrene microspheres and 1 g of cetyltrimethylammonium chloride, add 0.3 g of phenylboronic acid to carry out chemical bonding with the polystyrene microspheres; Mix Solution A and Solution B to form Mixed Solution II; Add Mixed Solution II to Mixed Solution I, and then add 3 g of sodium tripolyphosphate as a crosslinking agent, control the reaction temperature at 60 °C and stir for 3 h to obtain Mixed Solution III;

[0055] Step 3: Weigh 1 g of Sr(NO3)2 and 1 g of Gd(NO3)3·6H2O, dissolve them in distilled water to make the mass ratio of Sr:Gd 1:1, and prepare a mixed salt solution. Using the microwave impregnation method, drip the well-stirred Mixed Solution III into the mixed salt solution with the same mass fraction through a peristaltic pump. Use a microwave hydrothermal synthesizer, the microwave impregnation time is 30 min, the temperature is 45 °C, and the microwave frequency is 200 GHz to prepare a hydrogel doped with metal ions;

[0056] Step 4: Wash the hydrogel doped with metal ions with deionized water repeatedly for 6 times to remove excess metal ions. After placing the hydrogel doped with metal ions in a freeze dryer and freeze-drying for 24 h, carry out vacuum freeze-drying under the conditions of -60 °C and 10 Pa, and place it in a tubular furnace to carbonize for 2 h under the conditions of 100% N2 atmosphere and 900 °C (heating rate 5 °C / min) to prepare a carbon-based π complex material with adjustable pore size loaded with metal oxides.

[0057] The electron micrograph of the carbon-based π complex material prepared in this example is as Figure 1 shown. It can be seen from Figure 1 that: The carbon-based π complex material presents a lamellar structure. The polystyrene microspheres are transformed into a graphitized carbon-like structure under high-temperature conditions to form a more stable π-π complex stacking π complex structure with the aromatic carbon skeleton of sodium alginate. At the same time, the surface of the adsorbent is smooth, visible nanoparticle aggregation, showing a lamellar structure with higher void abundance.

[0058] Experiment on the carbon-based π complex material with controllable pore size loaded with doped phosphorus metal oxides prepared in this example under high space velocity conditions: Space velocity 60000 h -1, Temperature: 25°C. The simulated gas, by mass percentage, includes: 40% CH4, 20% CO, 35% H2, and 5% CS2, where the concentration of CS2 is 200 ppm and the balance gas is N2. A saturator system is used for water supply, and the water content is represented by relative humidity (RH). A mass flow controller is used to control the total flow rate at 1 L / min. After detection, the desulfurization efficiency is 97.36%.

[0059] Example 2:

[0060] The difference from Example 1 is that in the first step, the mass ratio of sodium hyaluronate, mannitol, and sodium alginate is 1:1:1; the total mass ratio of sodium alginate, sodium hyaluronate, and mannitol in the first mixed solution is 8%;

[0061] After detection, the desulfurization efficiency is 91.04%.

[0062] Example 3:

[0063] The difference from Example 1 is that in the first step, the mass ratio of sodium hyaluronate, mannitol, and sodium alginate is 1:4:2; the total mass ratio of sodium hyaluronate, mannitol, and sodium alginate in the first mixed solution is 8%;

[0064] After detection, the desulfurization efficiency is 93.42%.

[0065] Example 4:

[0066] The difference from Example 1 is that in the first step, the mass ratio of sodium hyaluronate, mannitol, and sodium alginate is 4:1:2, and the total mass ratio of sodium hyaluronate, mannitol, and sodium alginate in the first mixed solution is 8%;

[0067] After detection, the desulfurization efficiency is 95.59%.

[0068] Example 5:

[0069] The difference from Example 1 is that in the first step, the mass ratio of sodium hyaluronate, mannitol, and sodium alginate is 2:1:2, and the total mass ratio of sodium hyaluronate, mannitol, and sodium alginate in the first mixed solution is 8%;

[0070] After detection, the desulfurization efficiency is 89.95%.

[0071] Example 6:

[0072] The difference from Example 1 is that in the first step, the total mass ratio of sodium hyaluronate, mannitol, and sodium alginate is 6%.

[0073] After detection, the desulfurization efficiency is 92.75%.

[0074] Example 7:

[0075] The difference from Example 1 is that: the reaction temperature in the second step is 40 °C, and the carbonization temperature in the third step is 500 °C.

[0076] After testing, the desulfurization efficiency is 88.46%.

[0077] Example 8:

[0078] The difference from Example 1 is that: in the third step, the microwave impregnation time is 15 min, the temperature is 40 °C, and the microwave frequency is 50 GHz.

[0079] After testing, the desulfurization efficiency is 92.80%.

[0080] Example 9:

[0081] The difference from Example 1 is that: after the adsorption experiment in Example 1, the adsorbent is regenerated by desorption at a heating rate of 10 °C / min for 2 hours at 400 °C in a tubular furnace under a N2 atmosphere (flow rate of 50 mL / min), and then the desulfurization experiment is carried out. And the above process is repeated 3 times (denoted as R1, R2, and R3 respectively).

[0082] After testing, the desulfurization efficiency of R1 is 92.57%, the desulfurization efficiency of R2 is 83.79%, and the desulfurization efficiency of R3 is 82.64%.

[0083] The removal efficiency and removal amount of CS2 by the carbon-based π complex material prepared in the above Examples 1-8 are as Figure 2 shown. The removal efficiency and removal amount of CS2 by the carbon-based π complex material regenerated multiple times in Example 9 are as Figure 3 shown. It can be seen from Figure 2 that when the mass ratio of hyaluronic acid, mannitol, and sodium alginate is 2:2:1, the adsorbent has the highest removal rate and the largest total adsorption amount for the longest time, and the removal effect is the best. It can be seen from Figure 3 that after the first thermal regeneration treatment, its CS2 adsorption capacity only decreases by 0.14%, and the adsorption efficiency of the adsorbent still remains at a relatively high level after three regenerations, showing good regeneration performance.

[0084] Comparative Example 1:

[0085] The difference from Example 1 is that: polystyrene microspheres and cetyltrimethylammonium chloride are not added.

[0086] The specific preparation steps are as follows:

[0087] Step 1: Weigh 2 g of sodium hyaluronate, 2 g of mannitol, and 1 g of sodium alginate dried at 600 °C for 2 h, and completely dissolve them in 600 mL of deionized water to prepare a first mixed solution; the total mass ratio of sodium alginate, sodium hyaluronate, and mannitol in the first mixed solution is 8%.

[0088] Step 2: Prepare solution A: Take 1 mL of dimethylformamide and 0.05 mL of methyl acrylate to form a mixed solution. Slowly add 1 mL of deionized water to the mixed solution to cause micelle aggregation, and then add the solution to 7 mL of deionized water to inhibit aggregation. Add distilled water to the total volume of the solution to 500 mL, heat to 60 °C, and stir at this temperature for 1 h; Prepare solution B: 1 g of polystyrene microspheres and 1 g of cetyltrimethylammonium chloride, add 0.3 g of phenylboronic acid to carry out a chemical bonding reaction with the polystyrene microspheres; Mix solution A and solution B to form a second mixed solution; Add the second mixed solution to the first mixed solution, and then add 3 g of sodium tripolyphosphate as a crosslinking agent, control the reaction temperature at 60 °C and stir for 3 h to obtain a third mixed solution;

[0089] Step 3: Weigh 1 g of Sr(NO3)2 and 1 g of Gd(NO3)3·6H2O, dissolve them in distilled water to make the mass ratio of Sr:Gd 1:1, and prepare a mixed salt solution. Using the microwave impregnation method, drop the evenly stirred third mixed solution into the mixed salt solution with the same mass fraction through a peristaltic pump. Use a microwave hydrothermal synthesizer, the microwave impregnation time is 30 min, the temperature is 45 °C, and the microwave frequency is 200 GHz to prepare a hydrogel doped with metal ions;

[0090] Step 4: Wash the hydrogel doped with metal ions 6 times with deionized water to remove excess metal ions. After placing the hydrogel doped with metal ions in a freeze dryer and freeze-drying for 24 h, vacuum freeze-dry it under the conditions of -60 °C and 10 Pa, and place it in a tube furnace to carbonize for 2 h under the conditions of 100% N2 atmosphere and 900 °C (heating rate 5 °C / min) to prepare an adsorbent material.

[0091] The adsorbent material prepared in this comparative example was tested under high space velocity conditions, and the specific steps refer to Example 1. The results show that: the removal efficiency of pollutants decreases, and the desulfurization efficiency is 87.14%.

[0092] Comparative Example 2:

[0093] The difference from Example 1 is that: sodium hyaluronate and mannitol are not added.

[0094] Step 1: Weigh 1 g of sodium alginate dried at 600 °C for 2 h and completely dissolve it in 600 mL of deionized water to prepare a first sodium alginate solution; the mass ratio of sodium alginate in the first mixed solution is 8%.

[0095] Step 2: Prepare Solution A: Take 1 mL of dimethylformamide and 0.05 mL of methyl acrylate to form a mixed solution. Slowly add 1 mL of deionized water to the mixed solution to cause micelle aggregation, and then add the solution to 7 mL of deionized water to inhibit aggregation. Add distilled water to the total volume of the solution to 500 mL, heat to 60 °C, and stir at this temperature for 1 h; Prepare Solution B: 1 g of polystyrene microspheres and 1 g of cetyltrimethylammonium chloride, add 0.3 g of phenylboronic acid to carry out chemical bonding with the polystyrene microspheres; Mix Solution A and Solution B to form Mixed Solution II; Add Mixed Solution II to Mixed Solution I, and then add 3 g of sodium tripolyphosphate as a crosslinking agent, control the reaction temperature at 60 °C and stir for 3 h to obtain Mixed Solution III;

[0096] Step 3: Weigh 1 g of Sr(NO3)2 and 1 g of Gd(NO3)3·6H2O, dissolve them in distilled water to make the mass ratio of Sr:Gd 1:1, and prepare a mixed salt solution. Using the microwave impregnation method, drip the well-stirred Mixed Solution III into the mixed salt solution with the same mass fraction through a peristaltic pump. Use a microwave hydrothermal synthesizer, the microwave impregnation time is 30 min, the temperature is 45 °C, and the microwave frequency is 200 GHz to prepare a hydrogel doped with metal ions;

[0097] Step 4: Wash the hydrogel doped with metal ions 6 times with deionized water to remove excess metal ions. After placing the hydrogel doped with metal ions in a freeze dryer for freeze drying for 24 h, carry out vacuum freeze drying under the conditions of -60 °C and 10 Pa, and place it in a tubular furnace for carbonization for 2 h under the conditions of 100% N2 atmosphere and 900 °C (heating rate 5 °C / min) to prepare an adsorbent material.

[0098] Perform experiments on the adsorbent material prepared in this comparative example under high space velocity conditions, and the specific steps refer to Example 1. The results show that: the removal efficiency of pollutants decreases, and the desulfurization efficiency is 88.03%.

[0099] Comparative Example 3:

[0100] The difference from Example 1 is that there is no Step 2 in the preparation process.

[0101] Step 1: Weigh 2 g of sodium hyaluronate, 2 g of mannitol, and 1 g of sodium alginate dried at 600 °C for 2 h, and completely dissolve them in 600 mL of deionized water to prepare Mixed Solution I; The total mass ratio of sodium hyaluronate, mannitol, and sodium alginate in Mixed Solution I is 8%.

[0102] Step 2: Weigh 1 g of Sr(NO3)2 and 1 g of Gd(NO3)3·6H2O, dissolve them in distilled water to make the mass ratio of Sr:Gd 1:1, and prepare a mixed salt solution. Using the microwave impregnation method, drop the uniformly stirred mixed solution into the mixed salt solution with the same mass fraction through a peristaltic pump. Use a microwave hydrothermal synthesizer, with the microwave impregnation time of 30 min, temperature of 45 °C, and microwave frequency of 200 GHz to prepare a hydrogel doped with metal ions;

[0103] Step 3: Wash the hydrogel doped with metal ions 6 times with deionized water to remove the excess metal ions. After placing the hydrogel doped with metal ions in a freeze dryer for freeze drying for 24 h, vacuum freeze dry it under the conditions of -60 °C and 10 Pa, and carbonize it in a tube furnace for 2 h under the conditions of 100% N2 atmosphere and 900 °C (heating rate 5 °C / min) to prepare an adsorbent material.

[0104] Experiment on the adsorbent material prepared in this comparative example was carried out under high airspeed conditions, and the specific steps refer to Example 1. The results show that the removal efficiency of pollutants decreases, and the desulfurization efficiency is 79.10%.

[0105] Comparative Example 4:

[0106] The difference from Example 1 is that in this comparative example, the crosslinking agent is phenylenediamine.

[0107] The specific steps are as follows:

[0108] Step 1: Weigh 2 g of sodium hyaluronate, 2 g of mannitol, and 1 g of sodium alginate dried at 600 °C for 2 h, and completely dissolve them in 600 mL of deionized water to prepare a mixed solution 1; the total mass ratio of sodium hyaluronate, mannitol, and sodium alginate in the mixed solution 1 is 8%.

[0109] Step 2: Prepare Solution A: Take 1 mL of dimethylformamide and 0.05 mL of methyl acrylate to form a mixed solution. Slowly add 1 mL of deionized water to the mixed solution to cause micelle aggregation, and then add the solution to 7 mL of deionized water to inhibit aggregation. Add distilled water to the total volume of the solution to 500 mL, heat it to 60 °C, and stir for 1 h at this temperature; Prepare Solution B: 1 g of polystyrene microspheres and 1 g of cetyltrimethylammonium chloride, add 0.3 g of phenylboronic acid to carry out a chemical bonding reaction with the polystyrene microspheres; Mix Solution A and Solution B to form a mixed solution 2; Add the mixed solution 2 to the mixed solution 1, and then add 3 g of phenylenediamine as a crosslinking agent thereto, control the reaction temperature at 60 °C and stir for 3 h to obtain a mixed solution 3;

[0110] Step 3: Weigh 1 g of Sr(NO3)2 and 1 g of Gd(NO3)3·6H2O, dissolve them in distilled water to make the mass ratio of Sr:Gd 1:1, and prepare a mixed salt solution. Using the microwave impregnation method, drip three drops of the well-stirred mixed solution into the mixed salt solution with the same mass fraction through a peristaltic pump. Use a microwave hydrothermal synthesizer, with the microwave impregnation time being 30 min, the temperature being 45 °C, and the microwave frequency being 200 GHz, thus preparing a hydrogel doped with metal ions;

[0111] Step 4: Wash the hydrogel doped with metal ions 6 times repeatedly with deionized water to remove the excess metal ions. After placing the hydrogel doped with metal ions in a freeze dryer for freeze drying for 24 h, conduct vacuum freeze drying under the conditions of -60 °C and 10 Pa, and then carbonize it in a tube furnace under the conditions of 100% N2 atmosphere and 900 °C (heating rate 5 °C / min) for 2 h to prepare an adsorbent material.

[0112] The adsorbent material prepared in this comparative example was experimented under high space velocity conditions, and the specific steps refer to Example 1. The results show that: the removal efficiency of pollutants decreases, and the desulfurization efficiency is 93.95%.

[0113] Comparative Example 5:

[0114] The difference from Example 1 is that the metal salt solution doped in this comparative example is AlCl3·6H2O.

[0115] Step 1: Weigh 2 g of sodium hyaluronate, 2 g of mannitol, and 1 g of sodium alginate dried at 600 °C for 2 h, and completely dissolve them in 600 mL of deionized water to prepare a mixed solution one; the total mass ratio of sodium hyaluronate, mannitol, and sodium alginate in the mixed solution one is 8%.

[0116] Step 2: Prepare solution A: Take 1 mL of dimethylformamide and 0.05 mL of methyl acrylate to form a mixed solution, slowly add 1 mL of deionized water to the mixed solution to cause micelle aggregation, and then add the solution to 7 mL of deionized water to inhibit aggregation. Add distilled water to the total volume of the solution to 500 mL, heat it to 60 °C, and stir for 1 h at this temperature; Prepare solution B: 1 g of polystyrene microspheres and 1 g of cetyltrimethylammonium chloride, add 0.3 g of phenylboronic acid to carry out a chemical bonding reaction with the polystyrene microspheres; Mix solution A and solution B to form a mixed solution two; Add the mixed solution two to the mixed solution one, and then add 3 g of sodium tripolyphosphate as a crosslinking agent, control the reaction temperature at 60 °C and stir for 3 h to obtain a mixed solution three;

[0117] Step 3: Weigh 1 g of AlCl3·6H2O and dissolve it in distilled water to prepare a salt solution. Using the microwave impregnation method, three drops of the uniformly stirred mixed solution are dropped into the salt solution with the same mass fraction through a peristaltic pump. Using a microwave hydrothermal synthesizer, the microwave impregnation time is 30 min, the temperature is 45 °C, and the microwave frequency is 200 GHz to prepare a hydrogel doped with metal ions;

[0118] Step 4: Wash the hydrogel with deionized water repeatedly for 6 times to remove the excess metal ions. After placing the hydrogel doped with metal ions in a freeze dryer and freeze-drying for 24 h, vacuum freeze-dry it under the conditions of -60 °C and 10 Pa, and carbonize it in a tubular furnace under the conditions of 100% N2 atmosphere and 900 °C (heating rate 5 °C / min) for 2 h to prepare an adsorbent material.

[0119] The adsorbent material prepared in this comparative example was tested under high air velocity conditions, and the specific steps refer to Example 1. The results show that the removal efficiency of pollutants decreases, and the desulfurization efficiency is 90.13%.

[0120] Comparative Example 6:

[0121] The difference from Example 1 is that sodium alginate without high-temperature drying is used as the carbon source.

[0122] Step 1: Weigh 2 g of sodium hyaluronate, 2 g of mannitol, and 1 g of sodium alginate and completely dissolve them in 600 mL of deionized water to prepare a mixed solution I; the total mass ratio of sodium hyaluronate, mannitol, and sodium alginate in the mixed solution I is 8%.

[0123] Step 2: Prepare Solution A: Take 1 mL of dimethylformamide and 0.05 mL of methyl acrylate to form a mixed solution. Slowly add 1 mL of deionized water to the mixed solution to cause micelle aggregation, and then add the solution to 7 mL of deionized water to inhibit aggregation. Add distilled water to the total volume of the solution to 500 mL, heat it to 60 °C, and stir it at this temperature for 1 h; prepare Solution B: 1 g of polystyrene microspheres and 1 g of cetyltrimethylammonium chloride, add 0.3 g of phenylboronic acid to carry out a chemical bonding reaction with the polystyrene microspheres; mix Solution A and Solution B to form a mixed solution II; add the mixed solution II to the mixed solution I, and then add 3 g of sodium tripolyphosphate as a cross-linking agent, control the reaction temperature at 60 °C and stir for 3 h to obtain a mixed solution III;

[0124] Step 3: Weigh 1 g of Sr(NO3)2 and 1 g of Gd(NO3)3·6H2O, dissolve them in distilled water to make the mass ratio of Sr:Gd 1:1, and prepare a mixed salt solution. Using the microwave impregnation method, three drops of the uniformly stirred mixed solution are dropped into the mixed salt solution with the same mass fraction through a peristaltic pump. Using a microwave hydrothermal synthesizer, the microwave impregnation time is 30 min, the temperature is 45 °C, and the microwave frequency is 200 GHz to prepare a hydrogel doped with metal ions;

[0125] Step 4: Wash the hydrogel with deionized water repeatedly 6 times to remove excess metal ions. After placing the hydrogel doped with metal ions in a freeze dryer and freeze-drying for 24 h, vacuum freeze-dry it under the conditions of -60 °C and 10 Pa, and place it in a tube furnace to carbonize for 2 h under the conditions of 100% N2 atmosphere and 900 °C (heating rate 5 °C / min) to prepare an adsorbent material with adjustable pore size loaded with metal oxides.

[0126] The adsorbent material prepared in this comparative example was tested under high air velocity conditions, and the specific steps refer to Example 1. The results show that the removal efficiency of pollutants decreases, and the desulfurization efficiency is 86.62%.

[0127] The removal efficiency and removal amount of CS2 by the adsorbent materials prepared in the above Comparative Examples 1-6 are shown in Table 1. It can be seen from Table 1 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, it can be obtained that the experimental conditions of Example 1 are the best, and the removal efficiency of CS2 is the best.

[0128] Table 1

[0129] Adsorption efficiency (%) <![CDATA[Adsorption capacity (mg / m 3 )]]> Comparative example 1 87.14 273.19 Comparative example 2 88.03 279.82 Comparative example 3 79.10 234.78 Comparative example 4 93.95 317.36 Comparative example 5 90.13 302.89 Comparative example 6 86.62 269.57

[0130] Those of ordinary skill in the art in this technical field should recognize that the above embodiments are only used to illustrate the present application, rather than to limit the present application. As long as it is within the scope of the essential spirit of the present application, appropriate changes and variations made to the above embodiments fall within the scope of protection required by the present application.

Claims

1. A method for preparing a carbon-based π-complex material for removing CS2 from organic solid waste gasification gas, characterized in that: The following steps are involved: a. Mixing sodium hyaluronate, mannitol and dried sodium alginate in a certain ratio to prepare a mixed solution 1; b. Prepare solution A: mix dimethylformamide and methyl acrylate; Prepare solution B: mix polystyrene microspheres with a surfactant, add phenylboric acid thereto, and chemically bond the polystyrene microspheres with the phenylboric acid; Mixing solution A and solution B to form mixed solution 2; The mixed solution 2 is added to the mixed solution 1, and then sodium tripolyphosphate is added thereto as a cross-linking agent, and the reaction temperature is controlled to be 40-60° C. and stirred to obtain a mixed solution 3; c. Using microwave impregnation method, add three drops of the mixed solution to the Sr 2+ , Gd 3+ A hydrogel doped with metal ions is obtained in a salt solution; d. The hydrogel doped with metal ions is dried, frozen, and carbonized by high-temperature calcination in a nitrogen atmosphere to obtain a carbon-based π-complex material.

2. The method for preparing a carbon-based π-complex material for removing CS2 from organic solid waste gasification gas according to claim 1, characterized in that: In step a, the mass ratio of sodium hyaluronate, mannitol and sodium alginate is 1-2:1-4:1-4, the solvent of the mixed solution one is water, and the total mass proportion of sodium hyaluronate, mannitol and sodium alginate in the mixed solution one is 6-8%.

3. The method for preparing a carbon-based π-complex material for removing CS2 from organic solid waste gasification gas according to claim 1, characterized in that: In step b, the total amount of dimethylformamide and methyl acrylate added is 15-35% of the total mass of sodium hyaluronate, mannitol and sodium alginate; the amount of polystyrene microspheres and surfactant added is 3-5% of the total mass of sodium hyaluronate, mannitol and sodium alginate; the surfactant is hexadecyltrimethylammonium chloride; the amount of cross-linking agent added is 60% of the total mass of sodium hyaluronate, mannitol and sodium alginate; the amount of phenylboric acid added is 0.3 times the amount of polystyrene microspheres added.

4. The method for preparing a carbon-based π-complex material for removing CS2 from organic solid waste gasification gas according to claim 1, characterized in that: In step c, Sr 2+ , Gd 3+ The mass ratio of the two metals in the salt solution is 1:1, Sr 2+ , Gd 3+ The salt solutions are Sr(NO3)2 and Gd(NO3)3·6H2O.

5. The method for preparing a carbon-based π-complex material for removing CS2 from organic solid waste gasification gas according to claim 1, characterized in that: In step c, the microwave immersion time is 20 to 40 minutes, the immersion temperature is 40 to 50° C., and the microwave frequency is 200 GHz.

6. The method for preparing a carbon-based π-complex material for removing CS2 from organic solid waste gasification gas according to claim 1, characterized in that: In step d, the carbonization temperature is 300-900° C., and the carbonization time is 1-3 hours. After carbonization, the metal ions in the metal ion-doped hydrogel are oxidized to their corresponding oxides to adsorb CS2 in the organic solid waste gasification gas.

7. The method for preparing a carbon-based π-complex material for removing CS2 from organic solid waste gasification gas according to claim 1, characterized in that: In step a, sodium alginate is used as a carrier, mannitol is used as an excipient for the sodium alginate carrier, and sodium hyaluronate is used as a water retaining agent to facilitate the removal of CS2.

8. A carbon-based π-complex material for removing CS2 from organic solid waste gasification gas, characterized in that: It is prepared by the preparation method described in any one of claims 1 to 7, and the carbon-based π complex material is a lamellar structure.

9. The use of a carbon-based π-complex material for removing CS2 from organic solid waste gasification gas according to claim 8, characterized in that: The carbon-based π complex material is introduced into a fixed bed reactor under the condition of passing simulated gas at a space velocity of 60000 h -1 , removing CS2 from the gasification gas of organic solid waste at a temperature of 25°C; the composition of the simulated gas includes 40% CH4, 20% CO, 35% H2 and 5% CS2 in terms of mass percentage, wherein the concentration of CS2 is 200ppm.

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