镁负载CaO基吸附剂捕集CO2性能及抗烧结机理

doi:10.16085/j.issn.1000-6613.2020-2283

摘要/Abstract

摘要：

复合钙基吸附剂制备成本过高是限制其工业化应用的主要瓶颈问题。本文以不可溶的CaCO₃和Ca(OH)₂作为钙源，通过燃烧合成法制备钙镁复合吸附剂，在双固定床反应器上研究了其循环捕集CO₂性能。结果显示：制备得到的钙镁复合吸附剂具有更发达的孔隙结构，吸附剂表面Ca和Mg分散均匀，MgO均匀分布于CaO晶粒之间，有效提高了钙镁复合吸附剂的抗烧结特性，因此钙镁复合吸附剂循环反应过程中具有高捕集CO₂活性。以Ca(OH)₂作为钙源时，燃烧合成过程中Ca和Mg均匀同时析出，分散更加均匀，有效避免了CaCO₃作为钙源时Mg的团聚问题，因此得到的钙镁复合吸附剂循环捕集CO₂性能最优。最佳的Ca/Mg摩尔比为(8∶2)~(7.5∶2.5)。本研究以不可溶钙源制备得到高活性钙镁复合吸附剂，有效控制了吸附剂成本，具有更好的工程应用前景。

关键词: CO₂捕集, 吸附法, 钙镁复合吸附剂

Abstract:

The costs for the synthesis of calcium based sorbents are quite high, which has severely limited their industrial application. In this article, insoluble CaCO₃ and Ca(OH)₂ were used as raw materials to synthesize CaO/MgO sorbents by solution combustion. The CO₂ capture capacity of the synthesized sorbents was investigated in a double fixed-bed reactor. The results showed that the CaO/MgO sorbents presented highly porous microstructures, with MgO uniformly distributed on the surface of CaO and their anti-sintering performance was improved obviously. Therefore, the CaO/MgO sorbents showed much higher CO₂ capture capacities. When Ca(OH)₂ was used as calcium precursor, the Ca and Mg crystallized simultaneously during the solution combustion process and distribute more evenly on the obtained sorbent. The optimum Ca/Mg molar ratio range was (8∶2)~(7.5∶2.5). The synthetic cost is effectively controlled by using insoluble calcium precursors as raw materials and hence the produced CaO/MgO sorbent here has a better engineering application prospect.

Key words: CO₂ capture, adsorption method, CaO/MgO sorbents

中图分类号:

TQ534.9

孙荣岳, 彭超, 陈宇皇, 朱洪亮. 镁负载CaO基吸附剂捕集CO₂性能及抗烧结机理[J]. 化工进展, 2021, 40(11): 6385-6392.

SUN Rongyue, PENG Chao, CHEN Yuhuang, ZHU Hongliang. CO₂ capture capacity and anti-sintering mechanism of MgO supported CaO based sorbent[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6385-6392.

图/表 12

参考文献 26

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样品	Ca/Mg摩尔比	钙源及质量		镁源质量 /g	甘油 /mL	去离子水 /mL	合成温度 /℃	a/%	合成时间 /min
样品	Ca/Mg摩尔比	钙源	质量/g	镁源质量 /g	甘油 /mL	去离子水 /mL	合成温度 /℃	a/%	合成时间 /min
Ca8Mg2-CC	8∶2	CaCO₃	10	6.4	100	100	750	85	30
Ca7Mg3-CH	7∶3	Ca(OH)₂	7.4	11.0	100	100	750	77	30
Ca7.5Mg2.5-CH	7.5∶2.5	Ca(OH)₂	7.4	8.5	100	100	750	81	30
Ca8Mg2-CH	8∶2	Ca(OH)₂	7.4	6.4	100	100	750	85	30
Ca8.5Mg1.5-CH	8.5∶1.5	Ca(OH)₂	7.4	4.5	100	100	750	89	30
Ca9Mg1-CH	9∶1	Ca(OH)₂	7.4	2.9	100	100	750	93	30

样品	Ca/Mg摩尔比	钙源及质量		镁源质量 /g	甘油 /mL	去离子水 /mL	合成温度 /℃	a/%	合成时间 /min
样品	Ca/Mg摩尔比	钙源	质量/g	镁源质量 /g	甘油 /mL	去离子水 /mL	合成温度 /℃	a/%	合成时间 /min
Ca8Mg2-CC	8∶2	CaCO₃	10	6.4	100	100	750	85	30
Ca7Mg3-CH	7∶3	Ca(OH)₂	7.4	11.0	100	100	750	77	30
Ca7.5Mg2.5-CH	7.5∶2.5	Ca(OH)₂	7.4	8.5	100	100	750	81	30
Ca8Mg2-CH	8∶2	Ca(OH)₂	7.4	6.4	100	100	750	85	30
Ca8.5Mg1.5-CH	8.5∶1.5	Ca(OH)₂	7.4	4.5	100	100	750	89	30
Ca9Mg1-CH	9∶1	Ca(OH)₂	7.4	2.9	100	100	750	93	30

合成材料	方法	CaO/MgO质量比	碳酸化条件	煅烧条件	循环次数	CO₂捕集能力/g·g^-1	参考文献
CaCO₃、MgCO₃	干法物理混合	93∶7	650℃，15%CO₂，15min	850℃，N₂，10min	20	0.21	［15］
纳米CaCO₃、 MgO、柠檬酸	湿法混合	3∶1	650℃，15%CO₂，10min	850℃，N₂，6min	20	0.20	［20］
Mg(NO₃)₂、电石渣、甘油	燃烧合成	8∶2	700℃，15%CO₂，20min	850℃，N₂，10min	20	0.42	［22］
Ca(NO₃)₂、 Mg(NO₃)₂、柠檬酸	溶胶凝胶	93∶7	675℃，15%CO₂， 5%H₂O，60min	950℃，80%CO₂， 10%H₂O，10%O₂	50	0.58	［21］
Mg(NO₃)₂、 Ca(OH)₂、甘油	燃烧合成	85∶15	700℃，15%CO₂，10min	850℃，N₂，10min	50	0.37	本文

合成材料	方法	CaO/MgO质量比	碳酸化条件	煅烧条件	循环次数	CO₂捕集能力/g·g^-1	参考文献
CaCO₃、MgCO₃	干法物理混合	93∶7	650℃，15%CO₂，15min	850℃，N₂，10min	20	0.21	［15］
纳米CaCO₃、 MgO、柠檬酸	湿法混合	3∶1	650℃，15%CO₂，10min	850℃，N₂，6min	20	0.20	［20］
Mg(NO₃)₂、电石渣、甘油	燃烧合成	8∶2	700℃，15%CO₂，20min	850℃，N₂，10min	20	0.42	［22］
Ca(NO₃)₂、 Mg(NO₃)₂、柠檬酸	溶胶凝胶	93∶7	675℃，15%CO₂， 5%H₂O，60min	950℃，80%CO₂， 10%H₂O，10%O₂	50	0.58	［21］
Mg(NO₃)₂、 Ca(OH)₂、甘油	燃烧合成	85∶15	700℃，15%CO₂，10min	850℃，N₂，10min	50	0.37	本文

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镁负载CaO基吸附剂捕集CO₂性能及抗烧结机理

CO₂ capture capacity and anti-sintering mechanism of MgO supported CaO based sorbent

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