钙基CO2吸附剂的惰性掺杂和形貌调控研究进展

doi:10.16085/j.issn.1000-6613.2018-1340

摘要/Abstract

摘要：

有效捕集CO₂对于缓解亟待解决的温室效应、气候变暖、环境污染和能源危机问题具有重大意义。钙基吸附材料因为CO₂吸附容量高及成本低廉而受到了广泛关注。本文介绍了钙基吸附剂的CO₂吸附机理，着重阐述了显著提高吸附性能的两种改性方法，包括惰性掺杂和形貌调控。归纳了利用Zr、Ce、Mn、Mg、Al等塔曼温度较高或富含氧空穴的金属氧化物对氧化钙进行单掺杂和复合掺杂改性，针对合成方法、吸脱附条件、惰性组分掺杂量、钙基前体等不同参数对掺杂改性钙基CO₂吸附剂性能的影响进行总结。同时指出，采用聚苯乙烯小球、碳凝胶、碳球、表面活性剂等制备得到的中空结构球形钙基吸附剂或实心结构球形钙基吸附剂，具有良好的CO₂吸附容量和吸附稳定性。提出两种改性方法距离工业化应用还有较大的差距，亟需深入探讨吸附剂的结构与性能之间的关系，从而为吸附剂的设计提供理论指导。

关键词: CO₂吸附, 钙基吸附剂, 改性, 掺杂, 形貌

Abstract:

Carbon capture/storage (CCS) is of great significance to solve the problems of greenhouse effect, climate warming, environmental pollution and energy crisis. More attention has been paid on Ca-based sorbents because their high adsorption capacity and lower cost. The characteristics and adsorption mechanism of calcium-based CO₂ sorbents are introduced. This paper focuses on two modification methods of calcium-based sorbents, including incorporation of refractory metals into CaO and morphology modification, which are effective to improve the stability. Single and co-doping by metal oxides with high Tamman temperatures or more oxygen vacancies, such as Zr, Ce, Mn, Mg, Al, are introduced. The influence of synthetic methods, conditions of adsorption-desorption, content of inert material, and the precursor on the performance of calcium-based sorbents is discussed. The hollow and solid spherical particles of calcium-based sorbents prepared by polystyrene beads, carbon aerogels, and carbon sphere, have favorable adsorption capacity and stability. However, there is still a long way to go for realizing the industrial application. It is urgent to explore the relationship between the structure and the performance, so as to provide the theoretical guidance.

Key words: CO₂ adsorption, calcium-based sorbent, modification, doping, morphology

中图分类号:

TQ028

郭红霞, 南雁, 寇晓晨, 王胜平, 赵玉军, 马新宾. 钙基CO₂吸附剂的惰性掺杂和形貌调控研究进展[J]. 化工进展, 2019, 38(01): 457-466.

Hongxia GUO, Yan NAN, Xiaochen KOU, Shengping WANG, Yujun ZHAO, Xinbin MA. Research on doping modification and morphology control of calcium-based CO₂ sorbents[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 457-466.

图/表 1

参考文献 64

1	郭庆杰．温室气体二氧化碳捕集和利用技术进展[M]．北京：化学工业出版社，2010：5-10．
	GUO Qingjie . The progress of CO₂ capture and utilization[M]. Beijing: Chemical Industry Publisher, 2010: 5-10.
2	朱战敏．钙基高温CO₂吸附剂的研究[D]．西安：西北大学，2016.
	ZHU Zhanmin . Research on calcium based high temperature carbon dioxide adsorbent[D]. Xi’an: Northwest University, 2016.
3	BHATIA S K , PERLMUTER D D . Effect of the product layer on the kinetics of the CO₂-lime reaction[J]. AIChE Journal, 1983, 29: 79-86.
4	LU H , KHAN A , PRATSINIS S E , et al . Flame-made durable doped-CaO nanosorbents for CO₂ capture[J]. Energy & Fuel, 2009, 23(1/2): 1093-1100.
5	WU S F , BEUM T H , YANG J I , et al . Properties of Ca-base CO₂ sorbent using Ca(OH)₂ as precursor[J]. Industrial & Engineering Chemistry Research, 2007, 46: 7896-7899.
6	SULTANA K S , CHEN D . Enhanced hydrogen production by in situ CO₂ removal on CaCeZrO _x nanocrystals[J]. Catalysis Today, 2011, 171: 43-51.
7	KOIRALA R , GUNUGUNURI K R , PRATSINIS S E , et al . Effect of zirconia doping on the structure and stability of CaO-based sorbents for CO₂ capture during extended operating cycles[J]. Journal of Physical Chemistry C, 2011, 115 (50): 24804-24812.
8	RADFARNIA H R , ILIUTA M C . Metal oxide-stabilized calcium oxide CO₂ sorbent for multicycle operation[J]. Chemical Engineering Journal, 2013, 232: 280-289.
9	ZHAO M , BILTON M , BROWN A P , et al . Durability of CaO-CaZrO₃ sorbents for high-temperature CO₂ capture prepared by a wet chemical method[J]. Energy & Fuel, 2014, 28(2): 1275-1283.
10	ZHAO C J , ZHOU Z M , CHENG Z M . Sol-gel-derived synthetic CaO-based CO₂ sorbents incorporated with different inert materials[J]. Industrial & Engineering Chemistry Research, 2014, 53(36): 14065-14074.
11	BRODA M , MÜLLER C R . Sol-gel-derived, CaO-based, ZrO₂-stabilized CO₂ sorbents[J]. Fuel, 2014, 127: 94-100.
12	MOHAMMADI M , LAHIJANI P , MOHAMED A R . Refractory dopant-incorporated CaO from waste eggshell as sustainable sorbent for CO₂ capture: experimental and kinetic studies[J]. Chemical Engineering Journal, 2014, 243: 455-464.
13	RADFARNIA H R , ILIUTA M C . Development of zirconium-stabilized calcium oxide absorbent for cyclic high-temperature CO₂ capture[J]. Industrial & Engineering Chemistry Research, 2012, 51(31): 10390-10398.
14	REDDY G K , QUILLIN S , SMIRNIOTIS P . Influence of the synthesis method on the structure and CO₂ adsorption properties of Ca/Zr sorbents[J]. Energy & Fuels, 2014, 28 (5): 3292-3299.
15	PHROMPRASIT J , POWELL J , WONGSAKULPHASATCH S , et al . H₂ production from sorption enhanced steam reforming of biogas using multifunctional catalysts of Ni over Zr-, Ce- and La-modified CaO sorbents[J]. Chemical Engineering Journal, 2017, 313: 1415-1425.
16	WANG S P , FAN S S , FAN L J , et al . Effect of cerium oxide doping on the performance of CaO-based sorbents during calcium looping cycles[J]. Environmental Science & Technology, 2015, 49(8): 5021-5027.
17	LIU X T , SHI J F , HE L , et al . Modification of CaO-based sorbents prepared from calcium acetate for CO₂ capture at high temperature[J]. Chinese Journal of Chemical Engineering, 2017, 25: 572-580.
18	YANASE I , MAEDA T , KOBAYASHI H . The effect of addition of a large amount of CeO₂ on the CO₂ adsorption properties of CaO powder[J]. Chemical Engineering Journal, 2017, 327: 548-554.
19	张雷，张力，闫云飞，等 . 掺杂Ce、Zr对CO₂钙基吸附剂循环特性的影响[J]. 化工学报, 2015, 66（2）：612-617.
	ZHANG Lei , ZHANG Li , YAN Yunfei , et al . Effect of Ce, Zr on cyclic performance of CaO-based CO₂ sorbents[J]. CIESC Journal, 2015, 66(2): 612-617.
20	CHEN H , ZHANG P , DUAN Y , et al . Reactivity enhancement of calcium based sorbents by doped with metal oxides through the sol-gel process[J]. Applied Energy, 2016, 162: 390-400.
21	LI Y J , ZHAO C S , DUAN L B , et al . Cyclic calcination/ carbonation looping of dolomite modified with acetic acid for CO₂ capture[J]. Fuel Processing Technology, 2008, 89(12): 1461-1469.
22	REDDY E P , SMIRNIOTIS P G . High-temperature sorbents for CO₂ made of alkali metals doped on CaO supports [J]. Journal of Physical Chemistry B, 2004, 108 (23): 7794-7800.
23	CHEN H , ZHANG P , DUAN Y , et al . Reactivity enhancement of calcium based sorbents by doped with metal oxides through the sol-gel process[J]. Applied Energy, 2016, 162: 390-400.
24	SUN R , LI Y , LIU H , et al . CO₂ capture performance of calcium-based sorbent doped with manganese salts during calcium looping cycle[J]. Applied Energy, 2012, 89 (1): 368-373.
25	LI L , KING D L , NIE Z , et al . Magnesia-stabilized calcium oxide absorbents with improved durability for high temperature CO₂ capture[J]. Industrial & Engineering Chemistry Research, 2009, 48(23): 10604-10613.
26	PARK J , YI K B . Effects of preparation method on cyclic stability and CO₂ absorption capacity of synthetic CaO-MgO absorbent for sorption-enhanced hydrogen production[J]. International Journal of Hydrogen Energy, 2012, 37(1): 95-102.
27	LAN P Q , WU S F . Synthesis of a porous nano-CaO/MgO-based CO₂ adsorbent[J]. Chemical Engineering Technology, 2014, 37 (4): 580-586.
28	LIU W , FENG B , WU Y , et al . Synthesis of sintering-resistant sorbents for CO₂ capture[J]. Environmental Science & Technology, 2010, 44(8): 3093-3097.
29	LI Z S , CAI N S , HUANG Y Y , et al . Synthesis, experimental studies, and analysis of a new calcium-based carbon dioxide absorbent[J]. Energy & Fuels, 2005, 19(4): 1447-1452.
30	PACCIANI R , MULLER C R , DAVIDSON J F , et al . Synthetic Ca-based solid sorbents suitable for capturing CO₂ in a fluidized bed[J]. The Canadian Journal of Chemical Engineering, 2008, 86(3): 356-366.
31	KOIRALA R , REDDY G K , SMIRNIOTIS P G . Single nozzle flame-made highly durable metal doped Ca-based sorbents for CO₂ capture at high temperature[J]. Energy & Fuels, 2012, 26 (5): 3103-3109.
32	DENNIS J S , PACCIANI R . The rate and extent of uptake of CO₂ by a synthetic, CaO-containing sorbent[J]. Chemical Engineering Science, 2009, 64 (9): 2147-2157.
33	ZHOU Z M , QI Y , XIE M M , et al . Synthesis of CaO-based sorbents through incorporation of alumina/aluminate and their CO₂ capture performance[J]. Chemical Engineering Science, 2012, 74: 172-180.
34	MARTAVALTZI C S , LEMONIDOU A A . Development of new CaO based sorbent materials for CO₂ removal at high temperature[J]. Microporous and Mesoporous Materials, 2008, 110 (1): 119-127.
35	WU S F , LI Q H , KIM J N , et al . Properties of a nano CaO/Al₂O₃ CO₂ sorbent[J]. Industrial & Engineering Chemistry Research, 2008, 47(1): 180-184.
36	RADFARNIA H R , ILIUTA M C . Metal oxide-stabilized calcium oxide CO₂ sorbent for multicycle operation[J]. Chemical Engineering Journal, 2013, 232: 280-289.
37	STENDARDO S , ANDERSEN L K , HERCE C . Self-activation and effect of regeneration conditions in CO₂-carbonate looping with CaO-Ca₁₂Al₁₄O₃₃ sorbent[J]. Chemical Engineering Journal, 2013, 220: 383-394.
38	SAYYAH M , ITO B R , ROSTAM-ABADI M , et al . CaO-based sorbents for CO₂ capture prepared by ultrasonic spray pyrolysis[J]. RSC Advances, 2013, 43: 19872-19875.
39	KIM J N , KO C H , YI K B . Sorption enhanced hydrogen production using one-body CaO-Ca₁₂Al₁₄O₃₃-Ni composite as catalytic absorbent[J]. International Journal of Hydrogen Energy, 2013, 38 (14): 6072-6078.
40	KIERZKOWSKA A M , POULIKAKOS L V , BRODA M , et al . Synthesis of calcium-based, Al₂O₃-stabilized sorbents for CO₂ capture using a coprecipitation technique[J]. International Journal of Greenhouse Gas Control, 2013, 15: 48-54.
41	MARTAVALTZI C S , LEMONIDOU A A . Parametric study of the CaO-Ca₁₂Al₁₄O₃₃ synthesis with respect to high CO₂ sorption capacity and stability on multicycle operation[J]. Industrial & Engineering Chemistry Research, 2008, 47 (23): 9537-9543.
42	ANGELI S D , MARTAVALTZI C S , LEMONIDOU A A . Development of a novel synthesized Ca-based CO₂ sorbent for multicycle operation: parametric study of sorption[J]. Fuel, 2014, 127: 62-69.
43	RADFARNIA H R , SAYARI A . A highly efficient CaO-based CO₂ sorbent prepared by a citrate-assisted sol-gel technique[J]. Chemical Engineering Journal, 2015, 262: 913-920.
44	XU Y Q , DING H R , LUO C , et al . Effect of lignin, cellulose and hemicellulose on calcium looping behavior of CaO-based sorbents derived from extrusion-spherization method[J]. Chemical Engineering Journal, 2018, 334: 2520-2529.
45	FLORIN N H , BLAMEY J , FENNELL P S . Synthetic CaO-based sorbent for CO₂ capture from large-point sources[J]. Energy & Fuels, 2010, 24(8): 4598-4604.
46	CHANG P H , CHANG Y P , CHEN S Y , et al . Ca-rich Ca-Al oxide, high-temperature-stable sorbents prepared from hydrotalcite precursors: synthesis, characterization, and CO₂ capture capacity[J]. ChemSusChem, 2011, 4 (12): 1844-1851.
47	CHANG P H , LEE T J , CHANG Y P , et al . CO₂ sorbents with scaffold-like Ca-Al layered double hydroxides as precursors for CO₂ capture at high temperatures[J]. ChemSusChem, 2013, 6 (6): 1076-1083.
48	CHANG P H , CHANG Y P , LAI Y H , et al . Synthesis, characterization and high temperature CO₂ capture capacity of nanoscale Ca-based layered double hydroxides via reverse microemulsion[J]. Journal of Alloys and Compounds, 2014, 586(s1): S498-S505.
49	YU C T , CHEN W C . Hydrothermal preparation of calcium-aluminum carbonate sorbent for high-temperature CO₂ capture in fixed-bed reactor[J]. Fuel, 2014, 122: 179-185.
50	KOU X C , LI C , ZHAO Y J , et al . CO₂ sorbents derived from capsule-connected Ca-Al hydrotalcite-like via low-saturated coprecipitation[J].Fuel Processing Technology, 2018, 177: 210-218.
51	HU Y C , LIU W Q , CHEN H Q , et al . Screening of inert solid supports for CaO -based sorbents for high temperature CO₂ capture[J]. Fuel, 2016, 181: 199-206.
52	ALBRECHT K O , WAGENBACH K S , SATRIO J A , et al . Development of a CaO-based CO₂ sorbent with improved cyclic stability[J]. Industrial & Engineering Chemistry Research, 2008, 47 (20): 7841-7848.
53	LUO C , ZHENG Y , DING N , et al . Development and performance of CaO/La₂O₃ sorbents during calcium looping cycles for CO₂ capture[J]. Industrial & Engineering Chemistry Research, 2010, 49 (22):11778-11784.
54	KOIRALA R , REDDY G K , LEE J Y , et al . Influence of foreign metal dopants on the durability and performance of Zr/Ca sorbents during high temperature CO₂ capture[J]. Separation Science and Technology, 2014, 49: 47-54.
55	HLAING N N , SREEKANTAN S , OTHMAN R , et al . A novel (Zr-Ce) incorporated Ca(OH)₂ nanostructure as a durable adsorbent for CO₂ capture[J]. Materials Letters, 2014, 133: 204-207.
56	GUO H X , FENG J Q , ZHAO Y J , et al . Effect of micro-structure and oxygen vacancy on the stability of (Zr-Ce)-additive CaO-based sorbent in CO₂ adsorption[J]. Journal of CO₂ Utilization, 2017, 19: 165-176.
57	GUO H X , KOU X C , ZHAO Y J , et al . Effect of synergistic interaction between Ce and Mn on the CO₂ capture of calcium-based sorbent: textural properties, electron donation, and oxygen vacancy[J]. Chemical Engineering Journal, 2018, 334: 237-246.
58	GUO H X , KOU X C , ZHAO Y J , et al . Role of microstructure, electron transfer, and coordination state in the CO₂ capture of calcium-based sorbent by doping (Zr-Mn) [J]. Chemical Engineering Journal, 2018, 336: 376-385.
59	LIU F Q , LI W H , LIU B C , et al . Synthesis, characterization, and high temperature CO₂ capture of new CaO based hollow sphere sorbents[J]. Journal of Materials Chemistry A, 2013, 27: 8037-8044.
60	BRODA M , MÜLLER C R . Synthesis of highly efficient, Ca-based, Al₂O₃-stabilized, carbon gel-templated CO₂ sorbents[J]. Advanced Materials, 2012, 24 (22): 3059-3064.
61	沈辉 . 氧化钙基吸附剂的制备及其CO₂吸附性能研究[D]. 天津：天津大学，2018.
	SHEN Hui . Research on the preparation and CO₂ capture performance of CaO based adsorbents[D]. Tianjin: Tianjin University, 2018.
62	FENG J Q , GUO H X , WANG S P , et al . Fabrication of multi-shelled hollow Mg-modified CaCO₃ microspheres and their improved CO₂ adsorption performance[J]. Chemical Engineering Journal, 2017, 321: 401-411.
63	赵丽娜，孔治国，王继库．聚丙烯酸钠存在下蝶状文石型碳酸钙的合成研究[J]. 化学通报，2012，75(12)：1140-1144．
	ZHAO Lina , KONG Zhiguo , WANG Jiku . Synthesis of butterfly-like aragonite calcium carbonate in the presence of sodium polyacrylate[J]. Chemistry, 2012, 75(12): 1140-1144.
64	WANG S P , FAN L J , LI C , et al . Porous spherical CaO-based sorbents via PSS-assisted fast precipitation for CO₂ capture[J]. ACS Applied Materials & Interfaces, 2014, 6: 18072-18077.

掺杂量 Ca/Zr（摩尔比）	制备方法	吸脱附温度/℃	循环次数	反应器	吸附容量/g·g^-1	参考文献
10/3	火焰喷雾法	700/700	100	TGA	64%（X _CaO）	[6]
10/5	火焰喷雾法	700/700	1200	TGA	60%（X _CaO）	[7]
10/1	湿混合	650/930	25	IGA	0.30	[8]
30/1	湿化学法	650/800	30	TGA	0.37	[9]
13.2/1	溶胶-凝胶法	650/900	30	TGA	0.45	[10]
95/5	溶胶-凝胶法	800/800	90	TGA	0.34	[11]
8.5/1	高温固相法	650/700	20	TGA	0.48	[12]
3.3/1	表面活性剂模板/超声法	600/750	15	TGA	0.15	[13]
10/5	溶胶-凝胶法	700/700	1200	TGA	0.30	[14]

掺杂量 Ca/Zr（摩尔比）	制备方法	吸脱附温度/℃	循环次数	反应器	吸附容量/g·g^-1	参考文献
10/3	火焰喷雾法	700/700	100	TGA	64%（X _CaO）	[6]
10/5	火焰喷雾法	700/700	1200	TGA	60%（X _CaO）	[7]
10/1	湿混合	650/930	25	IGA	0.30	[8]
30/1	湿化学法	650/800	30	TGA	0.37	[9]
13.2/1	溶胶-凝胶法	650/900	30	TGA	0.45	[10]
95/5	溶胶-凝胶法	800/800	90	TGA	0.34	[11]
8.5/1	高温固相法	650/700	20	TGA	0.48	[12]
3.3/1	表面活性剂模板/超声法	600/750	15	TGA	0.15	[13]
10/5	溶胶-凝胶法	700/700	1200	TGA	0.30	[14]

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钙基CO₂吸附剂的惰性掺杂和形貌调控研究进展

Research on doping modification and morphology control of calcium-based CO₂ sorbents

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