Biomass-based porous carbon material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of carbon materials, and particularly relates to a biomass-based porous carbon material and a preparation method and application thereof. The preparation method of the biomass-based porous carbon material comprises the following steps: S1, adding sodium polyaspartate, carboxylated chitosan, soluble starch, glutaraldehyde, ammonium persulfate and zinc acrylate into water, and carrying out a ball-milling reaction to obtain a cross-linked substance; s2, freezing the cross-linked product obtained in the S1, and drying under a vacuum condition to obtain dry gel; and S3, carrying out high-temperature carbonization on the xerogel obtained in S2 in a carbon dioxide atmosphere to obtain the biomass-based porous carbon material. The preparation method provided by the invention is simple and efficient, and can be applied to large-scale industrial production, so that the production cost can be saved, and the economic benefit can be improved. Experiments prove that the carbon material provided by the invention has a good carbon dioxide adsorption effect, can be used as an excellent rubber additive for reducing the wear rate of rubber, and has a wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of carbon materials technology, specifically relating to a biomass-based porous carbon material, its preparation method, and its application. Background Technology

[0002] Porous carbon materials are widely used in gas adsorption and separation, material modification, and additive fields due to their good chemical and thermal stability, tunable physicochemical properties, and relatively low cost. The main sources of these carbon materials are biomass and polymer precursors.

[0003] Although polymer precursors can achieve certain structural regulation through molecular design, they generally suffer from problems such as high synthesis costs and the generation of toxic byproducts during the preparation process. Furthermore, finished carbon materials often lack a natural pore structure and require complex subsequent activation processes to construct pores, which does not conform to the development trend of green and low-carbon materials.

[0004] In comparison, biomass has become a research focus in recent years due to its natural advantages: it possesses a highly interconnected macroporous structure, providing a natural framework for subsequent pore optimization; it is also rich in oxygen-containing functional groups such as hydroxyl and carboxyl groups, allowing for simple chemical modification to regulate surface properties; and it has low ash content, is widely available and renewable, significantly reducing preparation costs. For example, CN120483107 A discloses an oxygen-nitrogen-phosphorus-doped porous carbon material prepared using polyvinyl alcohol ammonium phosphate, carboxylated chitosan, glutaraldehyde, and furfural, which exhibits certain carbon dioxide adsorption performance. However, the application and development of biomass-based porous carbon materials depend on the selection of raw materials, composite ratios, and the design of preparation processes, requiring further in-depth research.

[0005] In summary, this application studies biomass-based porous carbon materials and provides a porous carbon material with good carbon dioxide adsorption performance and which can be used as an excellent rubber additive. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a biomass-based porous carbon material, its preparation method and application, which has a good carbon dioxide adsorption effect and can be used as an excellent rubber additive to reduce rubber wear rate.

[0007] Technical Topic 1 A biomass-based porous carbon material, the key to which lies in its preparation method is as follows: S1: Sodium polyaspartate, carboxylated chitosan, soluble starch, glutaraldehyde, ammonium persulfate, and zinc acrylate are added to water and ball-milled to obtain a crosslinked compound; S2: The crosslinked material obtained in S1 is frozen and then dried under vacuum to obtain a dry gel; S3: The dry gel obtained in S2 is carbonized at high temperature in a carbon dioxide atmosphere to obtain biomass-based porous carbon material.

[0008] As a further improvement of the present invention, the dosage relationship of sodium polyaspartate, carboxylated chitosan, soluble starch, glutaraldehyde, ammonium persulfate, zinc acrylate and water in S1 is 3-6g: 3-6g: 3-6g: 1-3ml: 0.3-0.6g: 3-6g: 100-200mL.

[0009] As a further improvement of the present invention, the dosage relationship of sodium polyaspartate, carboxylated chitosan, soluble starch, glutaraldehyde, ammonium persulfate and zinc acrylate in S1 is 5g:5g:5g:2ml:0.5g:5g.

[0010] As a further improvement of the present invention, the ball milling rate described in S1 is 200-500 r / min, and the time is 3-5 h.

[0011] As a further improvement of the present invention, the freezing temperature described in S2 is -50℃ to -90℃, and the freezing time is 12-36h.

[0012] As a further improvement of the present invention, drying is carried out in S2 under vacuum conditions, with a vacuum degree of 2-10 Pa and a time of 40-56 h.

[0013] As a further improvement of the present invention, the carbonization described in S3 is carried out in a carbon dioxide atmosphere by heating from room temperature to 600~900°C at a rate of 3-8°C / minute, holding at that temperature for 0.5~3 hours, and then naturally cooling to room temperature.

[0014] Technical Theme Two A method for preparing biomass-based porous carbon materials as described in Technical Subject 1.

[0015] Technical Theme 3 Application of a biomass-based porous carbon material as described in Technical Subject 1 in the field of carbon dioxide adsorption.

[0016] Technical Theme 4 Application of a biomass-based porous carbon material as described in Technical Subject 1 in the field of rubber additives.

[0017] As a further improvement of the present invention, the amount of biomass-based porous carbon material added is 5-20 wt% of the rubber raw material.

[0018] The beneficial effects of adopting the above technical solution are as follows: 1. This invention prepares a porous carbon material with high specific surface area by using sodium polyaspartate, carboxylated chitosan, soluble starch, glutaraldehyde, ammonium persulfate, and zinc acrylate in combination. Experimental verification shows that the carbon material provided by this invention has good carbon dioxide adsorption effect and can be used as an excellent rubber additive to reduce rubber wear rate, with broad application prospects.

[0019] 2. The preparation method provided by this invention is simple and efficient. When applied to large-scale industrial production, it can save production costs and improve economic benefits. Attached Figure Description

[0020] Figure 1 This is a graph showing the nitrogen adsorption-desorption experimental results of the biomass-based porous carbon material obtained in Example 1 of this invention; Figure 2 This is a graph showing the carbon dioxide adsorption experiment results of the biomass-based porous carbon material obtained in Example 1 of the present invention. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of this invention clearer, the following description is provided in conjunction with specific examples. Examples provide a clear and complete description of the invention.

[0022] The various instruments, equipment, raw materials or reagents used in the embodiments of this invention are not subject to any special restrictions on their source. They are all conventional products that can be purchased through regular commercial channels and can be prepared according to conventional methods known to those skilled in the art.

[0023] The sodium polyaspartate used in this application was purchased from Aladdin (item number: P477791). Carboxylated chitosan was purchased from Aladdin (item number: C105800). Soluble starch was purchased from Aladdin (item number: S104452).

[0024] Example 1 S1: Add 5g sodium polyaspartate, 5g carboxylated chitosan, 5g soluble starch, 2ml glutaraldehyde, 0.5g ammonium persulfate, and 5g zinc acrylate to 150ml deionized water and ball mill them at a rate of 400r / min for 4h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions were: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0025] Example 2 S1: Add 3g sodium polyaspartate, 6g carboxylated chitosan, 3g soluble starch, 1ml glutaraldehyde, 0.3g ammonium persulfate, and 6g zinc acrylate to 150ml deionized water and ball mill at a rate of 400r / min for 4h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions were: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0026] Example 3 S1: Add 6g of sodium polyaspartate, 3g of carboxylated chitosan, 6g of soluble starch, 3ml of glutaraldehyde, 0.6g of ammonium persulfate, and 3g of zinc acrylate to 150ml of deionized water and ball mill them at a rate of 400r / min for 4h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions were: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0027] Example 4 S1: Add 5g sodium polyaspartate, 5g carboxylated chitosan, 5g soluble starch, 2ml glutaraldehyde, 0.5g ammonium persulfate, and 5g zinc acrylate to 150ml deionized water and ball mill at a rate of 200r / min for 5h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -50°C for 36 hours in a freeze dryer, and then dried at room temperature for 56 hours in a vacuum drying chamber with a vacuum degree of 10 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions were: heating from room temperature to 600℃ at a rate of 3℃ / min, holding at that temperature for 3 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0028] Example 5 S1: Add 5g sodium polyaspartate, 5g carboxylated chitosan, 5g soluble starch, 2ml glutaraldehyde, 0.5g ammonium persulfate, and 5g zinc acrylate to 150ml deionized water and ball mill them at a rate of 500r / min for 3h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -90°C for 12 hours in a freeze dryer, and then dried at room temperature for 40 hours in a vacuum drying chamber with a vacuum degree of 2 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions were: heating from room temperature to 900℃ at a rate of 8℃ / min, holding at that temperature for 0.5h, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0029] Comparative Example 1 S1: Add 5g sodium polyaspartate, 5g carboxylated chitosan, 5g soluble starch, 0.5g ammonium persulfate, and 5g zinc acrylate to 150ml deionized water and ball mill them at a rate of 400r / min for 4h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions were: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0030] Comparative Example 2 S1: Add 5g sodium polyaspartate, 5g carboxylated chitosan, 5g soluble starch, 2ml glutaraldehyde, and 0.5g ammonium persulfate to 150ml deionized water and ball mill at a rate of 400r / min for 4h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions were: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0031] Comparative Example 3 S1: Add 5g sodium polyaspartate, 5g carboxylated chitosan, 5g soluble starch, 2ml glutaraldehyde, and 5g zinc acrylate to 150ml deionized water and ball mill them at a rate of 400r / min for 4h to obtain a mixture. S2: The mixture obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a solid. S3: The solid obtained in S2 is carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions are: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0032] Comparative Example 4 S1: Add 5g polyaspartic acid, 5g carboxylated chitosan, 5g soluble starch, 2ml glutaraldehyde, 0.5g ammonium persulfate, and 5g zinc acrylate to 150ml deionized water and ball mill them at a rate of 400r / min for 4h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions were: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0033] Comparative Example 5 S1: Add 5g sodium polyaspartate, 5g carboxylated chitosan, 5g soluble starch, 2ml glutaraldehyde, 0.5g ammonium persulfate, and 5g acrylic acid to 150ml deionized water and ball mill them at a rate of 400r / min for 4h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions were: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0034] Comparative Example 6 S1: Add 5g sodium polyaspartate, 5g carboxylated chitosan, 5g soluble starch, 2ml glutaraldehyde, 0.5g ammonium persulfate, and 5g zinc acrylate to 150ml deionized water and ball mill them at a rate of 400r / min for 4h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a dry gel; Comparative Example 7 S1: Add 5g sodium polyaspartate, 5g carboxylated chitosan, 5g soluble starch, 2ml glutaraldehyde, 0.5g ammonium persulfate, and 5g zinc acrylate to 150ml deionized water and mix well. S2: The mixture obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa. S3: The dried product obtained in S2 is carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions are: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0035] Comparative Example 8 S1: Add 7.5g sodium polyaspartate, 7.5g carboxylated chitosan, 2ml glutaraldehyde, 0.5g ammonium persulfate, and 5g zinc acrylate to 150ml deionized water and ball mill at a rate of 400r / min for 4h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions were: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0036] Comparative Example 9 S1: Add 7.5g sodium polyaspartate, 7.5g soluble starch, 2ml glutaraldehyde, 0.5g ammonium persulfate, and 5g zinc acrylate to 150ml deionized water and ball mill at a rate of 400r / min for 4h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature in a carbon dioxide atmosphere. The carbonization conditions were: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0037] Comparative Example 10 S1: Add 5g sodium polyaspartate, 5g carboxylated chitosan, 5g soluble starch, 2ml glutaraldehyde, 0.5g ammonium persulfate, and 5g zinc acrylate to 150ml deionized water and ball mill them at a rate of 400r / min for 4h to obtain the crosslinked product. S2: The crosslinked material obtained in S1 was pre-frozen at -70°C for 24 hours in a freeze dryer, and then dried at room temperature for 48 hours in a vacuum drying chamber with a vacuum degree of 5 Pa to obtain a dry gel; S3: The dry gel obtained in S2 was carbonized at high temperature under a nitrogen atmosphere. The carbonization conditions were: heating from room temperature to 900℃ at a rate of 5℃ / min, holding at that temperature for 2 hours, and then naturally cooling to room temperature to obtain biomass-based porous carbon material.

[0038] Test Example 1 Nitrogen adsorption-desorption experiments were conducted on the porous carbon materials obtained in Examples 1-5 and Comparative Examples 1-10. The structural data of the obtained carbon materials were measured, and the structural data of the obtained carbon materials are shown in Table 1. The nitrogen adsorption-desorption curve of the carbon material corresponding to Example 1 is shown in Table 1. Figure 1 As shown.

[0039] Table 1 Application Examples Rubber supports were prepared using the carbon materials obtained in Examples 1-5 and Comparative Examples 1-10 as follows: Natural rubber was placed in a mixer, and a certain amount of carbon material was added. The mixture was plasticized at 140°C for 15 minutes, then cut and turned three times on the mixer. The mixture was then poured into a support mold and cooled to obtain the rubber support. Samples 1-5 correspond to the carbon materials prepared in Examples 1-5, with the amount of carbon material added being 10 wt% of the rubber raw material. Comparative samples 1-10 correspond to the carbon materials prepared in Comparative Examples 1-10, with the amount of carbon material added being 10 wt% of the rubber raw material. The natural rubber was purchased from Shanghai Ruixun Polymer Materials Co., Ltd., and was a full-latex rubber (item number: SCRWF).

[0040] Example 1 The carbon dioxide adsorption capacity of the carbon materials obtained in Examples 1-5 and Comparative Examples 1-10 was tested using a Micron instrument. 0.2 g of sample was added to the instrument's sample tube, and the sample was degassed under vacuum at 200°C for 12 h at a degassing station. Then, the carbon dioxide adsorption capacity was analyzed using a Micron ASAP2460 instrument, and the results are shown in Table 2. The carbon dioxide adsorption curves for the carbon materials in Example 1 are shown in Table 2. Figure 2 As shown.

[0041] Example 2 According to Appendix B of JT / T901-2014, the friction performance (wear rate) of the rubber bearing obtained in the application example was tested. The indoor temperature was 21℃, and the humidity was controlled at 40%-50% using a compressed air refrigerated dryer. Circulating alcohol was introduced into the stainless steel sliding layer to control the temperature between the rubber bearing and the stainless steel plate at 21℃. The test was conducted on an abrasion testing machine, using a "four-in, three-out" method to install the specimen. The friction sliding speed was 15mm / s, the compressive stress was uniformly taken as 45MPa, a sinusoidal load was used, and the single-sided sliding distance was 10mm. The results are shown in Table 2.

[0042] Table 2 Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A biomass-based porous carbon material, characterized in that, Its preparation method is as follows: S1: Sodium polyaspartate, carboxylated chitosan, soluble starch, glutaraldehyde, ammonium persulfate, and zinc acrylate are added to water and ball-milled to obtain a crosslinked compound; S2: The cross-linked material obtained in S1 is frozen and then vacuum dried to obtain a dry gel; S3: Carbonize the dry gel obtained in S2 under a carbon dioxide atmosphere to obtain biomass porous carbon material.

2. The biomass-based porous carbon material according to claim 1, characterized in that, The dosage relationship of sodium polyaspartate, carboxylated chitosan, soluble starch, glutaraldehyde, ammonium persulfate and zinc acrylate in S1 is 3-6g: 3-6g: 3-6g: 1-3ml: 0.3-0.6g: 3-6g.

3. The biomass-based porous carbon material according to claim 1, characterized in that, The dosage relationship of sodium polyaspartate, carboxylated chitosan, soluble starch, glutaraldehyde, ammonium persulfate and zinc acrylate in S1 is 5g:5g:5g:2ml:0.5g:5g.

4. The biomass-based porous carbon material according to claim 1, characterized in that, The ball milling rate described in S1 is 200-500 r / min, and the time is 3-5 h.

5. The biomass-based porous carbon material according to claim 1, characterized in that, The freezing temperature described in S2 is -50℃ to -90℃, and the freezing time is 12-36 h.

6. The biomass-based porous carbon material according to claim 1, characterized in that, The vacuum drying time in S2 is 40-56 hours.

7. The biomass-based porous carbon material according to claim 1, characterized in that, The carbonization described in S3 involves heating from room temperature to 600-900°C at a rate of 3-8°C / minute in a carbon dioxide atmosphere, holding at that temperature for 0.5-3 hours, and then allowing it to cool naturally back to room temperature.

8. A method for preparing a biomass porous carbon material as described in any one of claims 1 to 7.

9. The application of a biomass porous carbon material as described in any one of claims 1 to 7 in the field of carbon dioxide adsorption.

10. The application of a biomass porous carbon material as described in any one of claims 1 to 7 in the field of rubber additives.

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