生物质壳聚糖基复合材料在CO<sub>2</sub>分离捕获和资源化利用中的应用

冯颖; 于汉哲; 张宏; 李可心; 董鑫; 张建伟

doi:10.13801/j.cnki.fhclxb.20230913.001

生物质壳聚糖基复合材料在CO₂分离捕获和资源化利用中的应用

doi: 10.13801/j.cnki.fhclxb.20230913.001

沈阳化工大学　机械与动力工程学院，沈阳 110142

基金项目: 国家自然科学基金(21406142)；辽宁省自然科学基金(2020-MS-230)；辽宁省教育厅科学研究项目(LJ2020036)；中央引导地方科技发展专项(2020JH6/10500051)

详细信息

通讯作者:
董鑫，博士，副教授，硕士生导师，研究方向为环境流体多相流传递理论与技术装备　E-mail:dongxin1106@syuct.edu.cn

中图分类号: X511；TB332
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- 文章访问数: 531
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- 被引次数: 0
出版历程
- 收稿日期: 2023-07-05
- 修回日期: 2023-08-09
- 录用日期: 2023-08-29
- 网络出版日期: 2023-09-13
- 刊出日期: 2024-03-01

Application of biomass chitosan-based composites for CO₂ separation and capture and resource utilization

College of Mechanical and Power Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China

Funds: National Natural Science Foundation of China (21406142); Natural Science Foundation of Liaoning Province (2020-MS-230); Liaoning Provincial Education Department Scientific Research Project (LJ2020036); Central Guidance for Local Science and Technology Development Special (2020JH6/10500051)

摘要

摘要: 二氧化碳过度排放导致的全球变暖、海平面上升和气候恶化等生态环境问题日益显著，亟需探寻新型处理技术和生物质材料来缓解这一问题。本文综述了生物质壳聚糖在二氧化碳分离、捕获和资源化利用领域的研究进展；详细阐述了壳聚糖膜对CO₂的分离机制及提高膜分离性能的方法；归纳了增强壳聚糖基活性炭对CO₂捕获性能的方法；对利用壳聚糖基催化剂将CO₂转化为碳酸酯、甲烷和烯烃等增值品的相关研究进行了总结。最后，对生物质壳聚糖在未来助力“双碳”战略目标实现过程中的发展趋势进行了展望。
- 碳达峰 /
- 碳中和 /
- 生物质 /
- 壳聚糖 /
- 二氧化碳 /
- 分离 /
- 捕获 /
- 资源化利用
Abstract: There is an urgent need to explore new treatment technologies and biomass materials to mitigate the growing ecological problems of global warming, sea level rise and climate degradation caused by excessive carbon dioxide emissions. This paper reviews the research progress of biomass chitosan in CO₂ separation, capture and resource utilization; details the mechanism of CO₂ separation by chitosan membranes and methods to improve membrane separation performance; summarizes the methods to enhance the CO₂ capture performance of chitosan-based activated carbon; and summarizes the research on the conversion of CO₂ into value-added products such as carbonate, methane and olefin by chitosan-based catalysts. Finally, the future development trend of biomass chitosan in the process of helping to achieve the "double carbon" strategic goal is presented.
- carbon peak /
- carbon neutrality /
- biomass materials /
- chitosan /
- carbon dioxide /
- separation /
- capture /
- resource utilization

HTML全文

图 1 聚集体对CO₂传输的阻碍作用

Figure 1. Obstruction of CO₂ transport by aggregates

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图 2 增强活性炭对CO₂捕获性能的方法

HAPS—Hydroquinonesulfonic acid potassium salt

Figure 2. Methods to enhance the CO₂ capture performance byactivated carbon

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图 3 不同炭化温度下CTS-NaNH₂活性炭的N元素含量^[35]

Figure 3. Elemental N content of CTS-NaNH₂ activated carbon at different carbonization temperatures^[35]

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图 4 利用响应曲面法分析不同因素对壳聚糖-漂白土CO₂去除率的影响：((a), (d)) 温度和CO₂浓度对吸附量的影响；((b), (e))温度和CTS用量对吸附量的影响；((c), (f)) CTS用量和CO₂浓度对吸附量的影响^[46]

Figure 4. Effect of different factors on CO₂ removal from chitosan-bleached soil using response surface methodology: ((a), (d)) Effect of temperature and CO₂ concentration on adsorption capacity; ((b), (e)) Effect of temperature and CTS dosage on adsorption capacity; ((c), (f)) Effect of CTS dosage and CO₂ concentration on adsorption capacity^[46]

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图 5 碳酸酯的分类

Figure 5. Classification of carbonate esters

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图 6 常见的环状碳酸酯合成方法^[52]

Figure 6. Common methods for synthesizing cyclic carbonates^[52]

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表 1 利用壳聚糖(CTS)/羧甲基壳聚糖(CMC)与填料制备混合基质膜

Table 1. Preparation of mixed matrix membrane using chitosan (CTS)/carboxymethyl chitosan (CMC) and filler

Membrane	Packing loading rate	Penetration rate of CO₂	CO₂/N₂ selectivity	Separation condition	Literature
CMC/PZ	PZ，20%	89 GPU	103	80℃, 120 kPa	[22]
CTS/GO/PVAm	HPEI-GO, 2% and 3%	36 GPU (2%)	107 (3%)	CO₂: N₂ =10 : 90	[23]
CTS/ZIF-8/IL	ZIF-8，10%	(5413±191) Barrer	11.5	50℃, 200 kPa	[24]
CTS/SF/GNP	GNP，0.5%	159 GPU	93	90℃, 200 kPa	[25]
CMC/HT	HT，1%	70 GPU	13	90℃, 200 kPa	[26]
Notes: PZ—Piperazine; PVAm—Polyvinylamine; HPEI-GO—Hyperbranched polyethyleneimine grafted graphene oxide; ZIF-8—Zinc(2-methylimidazole); IL—Ionic liquid; GNP—Graphene nanoparticles; HT—Hydrotalcite; SF—Silk fibroin.

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表 2 通过原子掺杂的方法制备壳聚糖基活性炭

Table 2. Preparation of chitosan-based activated carbon by atomic doping method

Carbon Source	Source of heteroatoms	Activator	Adsorption performance	Reusability	Literature
CTS	CTS provides N atoms	K₂CO₃	100 kPa, 25℃, adsorption capacity was 3.86 mmol/g	Adsorption capacity unchanged after five cycles	[37]
CTS	TMP and CTS provide N atoms	KOH	0℃, 100 kPa, the maximum CO₂ adsorption capacity was 4.74 mmol/g	After ten cycles, the adsorption capacity decreased by 8%	[38]
CTS	HMT and CTS provide N atoms	ZnCl₂	Adsorption capacity was smaller than undoped activated carbon	–	[39]
CTS	NaNH₂ and CTS provide N atoms	NaNH₂	0℃, 100 kPa, the adsorption amount of CO₂ was 6.33 mmol/g	After three cycles, the adsorption effect remains almost constant	[35]
CTS, SL	CTS and SL provide N and S atoms, respectively	KOH	0℃, 100 kPa, the adsorption amount of CO₂ was 215.2 mg/g	After three cycles, the adsorption capacity has decreased by 20%	[40]
CTS	CTS and HAPS provide N and S atoms, respectively	HAPS	25℃, 100 kPa, the adsorption amount of CO₂ was 2.4 mmol/g	–	[41]
CTS	CTS provides the N atoms and phytic acid provides the P atoms	NaNO₃	100 kPa, the adsorption amount of CO₂ was 3.02 mmol/g	After twenty cycles, the adsorption capacity remains unchanged	[42]
Notes: TMP—2, 4, 6-triaminopyrimidine; HMT—Hexamethylenetetramine; SL—Sodium lignosulfonate.

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表 3 改性壳聚糖基吸附剂用于CO₂捕获

Table 3. Modified chitosan-based sorbents for CO₂ capture

Adsorbent	Modification method	Modification advantages	Introduction of substances	Adsorption performance	Literature
Furfuryl- imine-CTS fibers	Imine formation	The introduction of imine groups produced a highly nucleophilic active surface		20℃, 61 kPa, the adsorption amount was 0.978 mmol/g	[47]
Chitosan based aerogel	Graft	Carboxyl, amino, imine, amide and other groups are introduced		35℃, the adsorption amount was 5.48 mmol/g	[48]
CTS/LS hydrogel	Cross-link	The introduction of Li⁺ and basic group, enhances the acid-base effect and electrostatic effect		100 kPa, 25℃, the maximum adsorption amount was 67.9 mg/g	[49]
CTS/MWCNTs	Graft	Increase the surface area of CTS and introduce hydroxyl and carboxyl groups		25℃, 100 kPa, the maximum adsorption amount was 1.92 cm³/g	[50]
Notes: MWCNTs—Multi-walled carbon nanotubes; LS—Lithium sulfonate.

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表 4 利用CO₂制备其他化学增值品

Table 4. Preparation of other chemical value-added products using CO₂

Catalyst	Raw materials	Reaction condition	Product	Production efficiency	Reusability	Literature
CTS/KOH/ Enzymes	Bicarbonate, CaCl_2, CO₂	pH 8, 35℃	CaCO₃	152 mg of CaCO₃ per gram of CO₂	No change after 7 repetitions	[61]
K-doped Fe/CTS complexes	CO_2, H₂	330℃, 1.5 MPa	Olefins	CO₂ conversion rate was 41% and olefin yield was 20.4%	–	[62]
CTS/CA/SiO₂	CaCl_2, CO₂	pH 7.6, 25℃	CaCO₃	230 mg CaCO₃ were gotten after 10 min	Can be reused up to 30 times	[63]
CTS/PEG	Ethanol, CO_2, H₂	6 MPa, 170℃	Methanol	Resulting methanol concentration was 472 mmol/L	Can be recycled up to 3 times	[64]
C/A/PEC	CaCl_2, CO₂	pH 8.2, pH 9.5	CaCO₃	1 g of catalyst can catalyze the synthesis of 253 mg of CaCO₃	No change after 10 repetitions	[65]
Cu/TiO₂/CTS	H₂O, CO₂	Xenon lamp irradiation	Methane	Yield of methane was 5.34 μmol/g	–	[66]
Notes: CA—Carbonic anhydrase; PEG—Polyethyleneglycol; C/A/PEC—Chitosan-alginate polyelectrolyte complex.

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