低湿CO2/H2O混合气体吸附特性实验

doi:10.16085/j.issn.1000-6613.2022-0246

摘要/Abstract

摘要：

CO₂捕集、封存及利用是实现“双碳”目标的重要途径，为将碳捕集后的低湿CO₂/H₂O进行CO₂提纯和资源化利用，采用动态吸附实验研究了不同温度（303K、313K）、H₂O含量（0.7%~3.0%）的CO₂/H₂O在活性炭、活性氧化铝、分子筛3A和13X四种吸附剂上的动态吸附穿透曲线、吸附床温度分布、吸附量，分析了CO₂/H₂O分离系数和吸附热。结果表明，在CO₂/H₂O动态吸附过程中，吸附床温度与各组分浓度随时间变化趋势相同。H₂O饱和时间随进气温度升高而缩短；H₂O含量增加，抑制CO₂吸附；活性炭和氧化铝中H₂O的饱和时间随H₂O含量增加而增长，但分子筛3A和13X饱和时间缩短。H₂O吸附量随H₂O含量增加而增加，吸附热随吸附量增加而减小，CO₂则相反。分子筛3A对CO₂吸附量最小且CO₂/H₂O分离系数最大。H₂O含量小于1%时，CO₂吸附量最大的分子筛13X分离系数大于活性氧化铝，分子筛3A和13X适合分离低湿CO₂/H₂O。

关键词: 碳捕集, CO₂/H₂O, 吸附, 活性炭, 活性氧化铝, 分子筛3A和13X, 选择性

Abstract:

Carbon capture, utilization and storage is an essential way to achieve the goal of carbon peak and neutrality, the gases exhaust from power industry and coal supercritical water gasification systems after condenser of carbon capture are mainly CO₂/H₂O with 1%—5% H₂O, which needs to separate using by adsorption. To purify and reutilize the low-moisture CO₂/H₂O, the adsorption breakthrough curve, temperature profiles, adsorption capacity of binary CO₂/H₂O at different temperature (303K, 313K) and H₂O mole fraction (0.7%—3.0%) were studied experimentally for four adsorbents of activated carbon, activated alumina, zeolites 3A and 13X. The separation factor and isosteric heat of binary CO₂/H₂O were also analyzed. Results show that as adsorption time increases, the bed temperature and the concentration of each component present the same trend. As the inlet temperature increases, the saturation time of H₂O decreases. As the mole fraction of H₂O increases, the adsorption of CO₂ was inhibited due to competitive adsorption, and the saturated time of H₂O in activated carbon and activated alumina increases, but that of H₂O in zeolite 3A and 13X decreased. The adsorption amounts of H₂O increased with the increase of H₂O concentration, while the isosteric heat decreased with the adsorption amounts, which presented the opposite for CO₂. Zeolite 3A had the smallest CO₂ adsorption amounts and the largest CO₂/H₂O separation factor. When H₂O mole fraction was less than 1%, the separation factor of zeolite 13X, which had the largest CO₂ adsorption amounts, was greater than that of activated alumina. Therefore, the zeolite 3A and 13X were suitable for the separation of CO₂/H₂O with low moisture.

Key words: carbon capture, CO₂/H₂O, adsorption, activated carbon, activated alumina, zeolite 3A and 13X, selectivity

中图分类号:

TQ028.2

任可欣, 鲁军辉, 王随林, 唐进京. 低湿CO₂/H₂O混合气体吸附特性实验[J]. 化工进展, 2022, 41(12): 6698-6710.

REN Kexin, LU Junhui, WANG Suilin, TANG Jinjing. Adsorption characteristics of CO₂/H₂O with low humidity[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6698-6710.

图/表 13

图1 吸附实验装置示意图和吸附段热电偶布置图

图2 实验系统再现性和吸附量实验结果与文献结果对比

图3 吸附剂SEM照片和实物图

图4 吸附剂在吸附前后红外光谱图

图5 不同吸附剂CO2/H2O穿透曲线和吸附床温度分布

图6 不同吸附剂CO2/H2O吸附量

表1 双组分吸附平衡R-LBET模型拟合参数

吸附剂	组分	M/mol·kg^-1	K/kPa^-1		R_ave/%
吸附剂	组分	M/mol·kg^-1	K/kPa^-1		303K	313K
活性炭	CO₂	1.108	0.083		2.291	3.018
	H₂O	25.709	0.333	0.051	7.561	7.638
	CO₂，H₂O	0.452	0.010		—	—
活性氧化铝	CO₂	1.110	0.025		2.216	1.447
	H₂O	9.878	0.096	0.188	2.411	5.476
	CO₂，H₂O	0.578	0.125		—	—
分子筛3A	CO₂	1.078	0.003		3.137	7.576
	H₂O	12.747	0.014	0.021	1.192	3.809
	CO₂，H₂O	0.019	1.415		—	—
分子筛13X	CO₂	1.008	0.010		3.089	0.881
	H₂O	11.088	0.038	0.082	0.742	1.951
	CO₂，H₂O	2.688	0.026		—	—

图7 不同进气温度下CO2/H2O穿透曲线

图8 不同进气温度下吸附床温度

图9 303K时不同H2O含量的CO2/H2O穿透曲线

图10 303K时不同H2O含量下吸附床温度

图11 CO2和H2O的等量吸附热

图12 CO2/H2O分离系数

参考文献 50

1	FU Wenfeng, WANG Lanjing, YANG Yongping. Optimal design for double reheat coal-fired power plants with post-combustion CO₂ capture: a novel thermal system integration with a carbon capture turbine[J]. Energy, 2021, 221: 119838.
2	GUAN Yuru, SHAN Yuli, HUANG Qi, et al. Assessment to China’s recent emission pattern shifts[J]. Earth’s Future, 2021, 9(11).
3	GOUEDARD C, PICQ D, LAUNAY F, et al. Amine degradation in CO₂ capture. I. A review[J]. International Journal of Greenhouse Gas Control, 2012, 10: 244-270.
4	WANG M, LAWAL A, STEPHENSON P, et al. Post-combustion CO₂ capture with chemical absorption: a state-of-the-art review[J]. Chemical Engineering Research and Design, 2011, 89(9): 1609-1624.
5	GUO Liejin, JIN Hui. Boiling coal in water: hydrogen production and power generation system with zero net CO₂ emission based on coal and supercritical water gasification[J]. International Journal of Hydrogen Energy, 2013, 38(29): 12953-12967.
6	CHEN Zhewen, ZHANG Xiaosong, HAN Wei, et al. A power generation system with integrated supercritical water gasification of coal and CO₂ capture[J]. Energy, 2018, 142: 723-730.
7	PFAFF I, OEXMANN J, KATHER A. Optimised integration of post-combustion CO₂ capture process in greenfield power plants[J]. Energy, 2010, 35(10): 4030-4041.
8	WEBLEY Paul A. Adsorption technology for CO₂ separation and capture: a perspective[J]. Adsorption, 2014, 20(2/3): 225-231.
9	BEN-MANSOUR R, HABIB M A, BAMIDELE O E, et al. Carbon capture by physical adsorption: materials, experimental investigations and numerical modeling and simulations—A review[J]. Applied Energy, 2016, 161: 225-255.
10	LU Junhui, CAO Haishan, LI Junming. Energy and cost estimates for separating and capturing CO₂ from CO₂/H₂O using condensation coupled with pressure/vacuum swing adsorption[J]. Energy, 2020, 202: 117604.
11	赵振国. 吸附作用应用原理[M]. 北京: 化学工业出版社, 2005.
	ZHAO Zhenguo. Application principle of adsorption[M]. Beijing: Chemical Industry Press, 2005.
12	近藤精一, 石川达雄, 安部郁夫. 吸附科学[M]. 李国希, 译. 北京: 化学工业出版社, 2006.
	SEIICHI Kondo, TATSUO Ishikawa, IKUO Abe. Science of adsorption[M]. LI Guoxi, trans. Beijing: Chemical Industry Press, 2006.
13	LIU X J, SHI Y F, KALBASSI M A, et al. A comprehensive description of water vapor equilibriums on alumina F-200: adsorption, desorption, and H₂O/CO₂ binary adsorption[J]. Separation and Purification Technology, 2014, 133: 276-281.
14	QASEM N A, BEN-MANSOUR R. Adsorption breakthrough and cycling stability of carbon dioxide separation from CO₂/N₂/H₂O mixture under ambient conditions using 13X and Mg-MOF-74[J]. Applied Energy, 2018, 230: 1093-1107.
15	LI G, XIAO P, WEBLEY P A, et al. Competition of CO₂/H₂O in adsorption based CO₂ capture[J]. Energy Procedia, 2009, 1(1): 1123-1130.
16	DANTAS T L, LUNA F M, SILVA I J, et al. Carbon dioxide-nitrogen separation through adsorption on activated carbon in a fixed bed[J]. Chemical Engineering Journal, 2011, 169(1/2/3): 11-19.
17	LI Gang, XIAO Penny, WEBLEY Paul. Binary adsorption equilibrium of carbon dioxide and water vapor on activated alumina[J]. Langmuir, 2009, 25(18): 10666-10675.
18	REGE S U, YANG R T. A novel FTIR method for studying mixed gas adsorption at low concentrations: H₂O and CO₂ on NaX zeolite and γ-alumina[J]. Chemical Engineering Science, 2001, 56(12): 3781-3796.
19	LI Gang, XIAO Penny, XU Dong, et al. Dual mode roll-up effect in multicomponent non-isothermal adsorption processes with multilayered bed packing[J]. Chemical Engineering Science, 2011, 66(9): 1825-1834.
20	唐进京, 鲁军辉, 李俊明, 等. CO₂/H₂O吸附分离特性研究[J]. 中国电机工程学报, 2022, 42(6): 2216-2228.
	TANG Jinjing, LU Junhui, LI Junming, et al. Study on adsorption characteristics of CO₂/H₂O[J]. Proceedings of the CSEE, 2022, 42(6): 2216-2228.
21	岑旗钢. 活性炭材料吸附分离烟气中二氧化碳研究[D]. 杭州: 浙江大学, 2017.
	CEN Qigang. Research on CO₂ adsorption from flue gas by activated carbons[D]. Hangzhou: Zhejiang University, 2017.
22	徐冬. 真空变压吸附分离燃烧后电厂废气中的高湿二氧化碳[D]. 沈阳: 东北大学, 2011.
	XU Dong. Post-combustion CO₂ capture from high humidity flue gas by vacuum swing adsorption[D]. Shenyang: Northeastern University, 2011.
23	叶贞成, 杨亚超, 罗娜. 真空变压吸附捕集烟道气中二氧化碳数值模拟研究[J]. 计算机与应用化学, 2016, 33(1): 21-26.
	YE Zhencheng, YANG Yachao, LUO Na. Simulation of vacuum pressure swing adsorption process for CO₂ capture from flue gas[J]. Computers and Applied Chemistry, 2016, 33(1): 21-26.
24	祝显强, 刘应书, 杨雄, 等. 中间气两步充压对快速真空变压吸附制氧的影响[J]. 化工学报, 2016, 67(10): 4264-4272.
	ZHU Xianqiang, LIU Yingshu, YANG Xiong, et al. Effect of two-step pressurization with intermediate gas on rapid vacuum pressure swing adsorption process for oxygen generation[J]. CIESC Journal, 2016, 67(10): 4264-4272.
25	欧阳少波, 徐绍平, 张俊杰, 等. N₂/CH₄在吸附剂上的动态吸附特性[J]. 化工进展, 2014, 33(10): 2546-2551.
	OUYANG Shaobo, XU Shaoping, ZHANG Junjie, et al. Study on N₂/CH₄ adsorption property in the adsorbents[J]. Chemical Industry and Engineering Progress, 2014, 33(10): 2546-2551.
26	GARCÍA S, GIL M V, MARTÍN C F, et al. Breakthrough adsorption study of a commercial activated carbon for pre-combustion CO₂ capture[J]. Chemical Engineering Journal, 2011, 171(2): 549-556.
27	XU Dong, GUO Hua, LIU Hanqiang, et al. CO₂ and H₂O capture from high humidity flue gas by single multi-layer vacuum swing adsorption unit[J]. Advanced Materials Research, 2012, 529: 402-407.
28	LI Gang, XIAO Penny, WEBLEY Paul, et al. Capture of CO₂ from high humidity flue gas by vacuum swing adsorption with zeolite 13X[J]. Adsorption, 2008, 14(2/3): 415-422.
29	KOLLE J M, FAYAZ M, SAYARI A. Understanding the effect of water on CO₂ adsorption[J]. Chemical Reviews, American Chemical Society, 2021, 121(13): 7280-7345.
30	杨祖保. 吸附剂原理与应用[M]. 马丽萍, 宁平, 田森林, 译. 北京: 高等教育出版社, 2010.
	YANG Ralph T. Adsorbents fundamentals and applications[M]. MA Liping, NING Ping, TIAN Senlin, trans. Beijing: Higher Education Press, 2010.
31	刘亚敏, 彭蕾, 苏凤英, 等. 多孔胺基化氧化石墨烯基材料对CO₂的吸附性能研究[J]. 化工学报, 2019, 70(5): 2016-2024.
	LIU Yamin, PENG Lei, SU Fengying, et al. Study of CO₂ adsorption on amine functionalized graphene oxide porous materials[J]. CIESC Journal, 2019, 70(5):2016-2024.
32	WURZBACHER J A, GEBALD C, STEINFELD A. Separation of CO₂ from air by temperature-vacuum swing adsorption using diamine-functionalized silica gel[J]. Energy & Environmental Science, 2011, 4(9): 3584-3592.
33	胡苏阳, 刘鑫博, 唐建峰, 等. 13X沸石分子筛对低浓度CO₂动态吸附的实验研究[J]. 化工进展, 2022, 41(1): 153-160.
	HU Suyang, LIU Xinbo, TANG Jianfeng, et al. Dynamic adsorption of low concentration CO₂ over 13X zeolite[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 153-160.
34	倪佳, 孙雪艳, 税子怡, 等. 湿法再生CO₂空气捕集材料的能耗与性能优化[J]. 化工学报, 2021, 72(3): 1409-1418.
	NI Jia, SUN Xueyan, SHUI Ziyi, et al. Energy consumption and performance optimization of moisture swing sorbents for direct air capture of CO₂ [J]. CIESC Journal, 2021,72(3):1409-1418.
35	DONG B X, ZHANG S Y, LIU W L, et al. Gas storage and separation in a water-stable [Cu^I₅BTT₃]^4- anion framework comprising a giant multi-prismatic nanoscale cage[J]. Chemical Communications, 2015, 51(26): 5691-5694.
36	费业泰. 误差理论与数据处理[M]. 北京: 机械工业出版社, 2010.
	FEI Yetai. Error analysis and data processing[M]. Beijing: China Machine Press, 2010.
37	SIRCAR S, MOHR R, RISTIC C, et al. Isosteric heat of adsorption: theory and experiment[J]. The Journal of Physical Chemistry B, 1999, 103(31): 6539-6546.
38	SIRCAR Shivaji. Excess properties and thermodynamics of multicomponent gas adsorption[J]. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1985, 81(7): 1527-1540.
39	SILVERSTEIN R M, WEBSTER F X, KIEMLE D J. 有机化合物的波谱解析[M]. 上海: 华东理工大学出版社, 2007.
	SILVERSTEIN R M, WEBSTER F X, KIEMLE D J. Spectrometric identification of organic compounds[M]. Shanghai: East China University of Science and Technology Press, 2007.
40	HERREROS Bruno, KLINOWSKI Jacek. Influence of the source of silicon and aluminium in the hydrothermal synthesis of sodalite[J]. Journal of the Chemical Society, Faraday Transactions, 1995, 91(7): 1147-1154.
41	MA Y K, RIGOLET S, MICHELIN L, et al. Facile and fast determination of Si/Al ratio of zeolites using FTIR spectroscopy technique[J]. Microporous and Mesoporous Materials, 2021, 311: 110683.
42	WANG Cheng, CAO Liyun, HUANG Jianfeng. Influences of acid and heat treatments on the structure and water vapor adsorption property of natural zeolite[J]. Surface and Interface Analysis, 2017, 49(12): 1249-1255.
43	YANG Kaizhong, YANG Guang, WU Jingyi. Insights into the enhancement of CO₂ adsorption on faujasite with a low Si/Al ratio: understanding the formation sequence of adsorption complexes[J]. Chemical Engineering Journal, 2021, 404: 127056.
44	AUERBACH S M, CARRADO K A, DUTTA P K. Handbook of zeolite science and technology[M]. Beijing: CRC Press, 2003.
45	邹勇, 吴肇亮, 陆绍信, 等. 微孔炭质吸附剂吸附贮存天然气的最佳孔径研究[J]. 石油与天然气化工, 1997(1): 15-16.
	ZOU Yong, WU Zhaoliang, LU Shaoxin, et al. Research on optimum pore diameter of micropore carbon for adsorption of storage natural gas[J]. Chemical Engineering of Oil and Gas, 1997, 26(1): 15-16.
46	PERI J B. A model for the surface of γ-alumina₁ [J]. The Journal of Physical Chemistry, 1965, 69(1): 220-230.
47	KOTOH Kenji, ENOEDA Mikio, MATSUI Tetsuya, et al. A multilayer model for adsorption of water on activated alumina in relation to adsorption potential[J]. Journal of Chemical Engineering of Japan, 1993, 26(4): 355-360.
48	MCCAFFERTY E, WIGHTMAN J P. Determination of the concentration of surface hydroxyl groups on metal oxide films by a quantitative XPS method[J]. Surface and Interface Analysis, 1998, 26(8): 549-564.
49	BOLIS Vera, BUSCO Claudia, UGLIENGO Piero. Thermodynamic study of water adsorption in high-silica zeolites[J]. The Journal of Physical Chemistry B, 2006, 110(30): 14849-4859.
50	MAURIN G, LLEWELLYN P L, BELL R G. Adsorption mechanism of carbon dioxide in faujasites: grand canonical Monte Carlo simulations and microcalorimetry measurements[J]. The Journal of Physical Chemistry B, 2005, 109(33): 16084-16091.

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低湿CO₂/H₂O混合气体吸附特性实验

Adsorption characteristics of CO₂/H₂O with low humidity

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