废弃蛋壳源高性能钙基吸收剂的制备及其碳捕集性能

doi:10.16085/j.issn.1000-6613.2021-1841

化工进展 ›› 2022, Vol. 41 ›› Issue (3): 1289-1297.DOI: 10.16085/j.issn.1000-6613.2021-1841

• 二氧化碳的捕集、封存及利用 • 上一篇下一篇

废弃蛋壳源高性能钙基吸收剂的制备及其碳捕集性能

王保文¹(), 姜涛¹, 许炳辉¹, 梁彦琛¹, 郭超凡¹, 李旭刚¹, 周志永²

^1.华北水利水电大学电力学院，河南郑州 450045
^2.国家电力投资集团有限公司安徽分公司，安徽合肥 230601

收稿日期:2021-08-27 修回日期:2021-11-09 出版日期:2022-03-23 发布日期:2022-03-28
通讯作者: 王保文
作者简介:王保文（1975—），男，副教授，从事煤燃烧污染物控制研究。E-mail：david-wn@163.com。
基金资助:
国家自然科学基金(51776073);河南省科技攻关项目(162102210233);华北水利水电大学创新科技项目(2019XA014);华北水利水电大学研究生创新课题(YK2020-22)

Preparation of the calcium based adsorbent derived from egg shell waste and its CO₂ capture performance in the calcium looping

WANG Baowen¹(), JIANG Tao¹, XU Binghui¹, LIANG Yanchen¹, GUO Chaofan¹, LI Xugang¹, ZHOU Zhiyong²

^1.School of Electric Power, North China University of Water Resources and Electric Power, Zhengzhou 450045, Henan, China
^2.Anhui Branch of State Electric Power Investment Group Limited Corporation, Hefei 230601, Anhui, China

Received:2021-08-27 Revised:2021-11-09 Online:2022-03-23 Published:2022-03-28
Contact: WANG Baowen

摘要/Abstract

摘要：

基于食品工业废弃蛋壳，本文利用不同有机酸反应制取乙酸钙、柠檬酸钙及葡萄糖酸钙共三种蛋壳源有机钙。在高温固定床反应器及热重分析仪上研究了不同前体所制成钙基吸收剂的碳循环捕集性能及碳酸化特性。进一步通过XRD分析了不同钙基吸收剂的物相组成，通过N₂吸附仪及SEM分析了循环前后钙基吸收剂结构特性及微观形貌的变化。结果表明，在三种蛋壳源有机钙中，葡萄糖酸钙所制成的钙基吸收剂具有较高的反应活性和相对最佳的碳捕集性能，首次碳酸化转化率高达85.33%，其钙基吸收剂相比其他吸收剂晶粒更小，20~100nm孔径范围内的孔隙较为发达，具有相对较强的抗烧结能力。经过20次循环实验发现，随着循环次数的增加，几种钙基吸收剂小颗粒均团聚烧结成大颗粒，造成孔隙结构缺失，孔隙率降低，影响其后续碳捕集性能。

关键词: 碳捕集, 钙循环, 蛋壳源有机钙, 碳循环捕集性能, 结构演化

Abstract:

Based on the eggshell waste discarded in the food industry, three kinds of organic calcium adsorbents, including calcium acetate, calcium citrate and calcium gluconate, were prepared using the corresponding organic acids. Their cyclic CO₂ capture performance and carbonation characteristics were studied on a tailored dual temperature tubular reactor and thermogravimetric analyzer, respectively. Furthermore, variation of the crystalline phases, structural characteristic and microscopic morphology of the prepared CaO adsorbents over the cyclic CO₂ capture process were analyzed. The results indicated that the CaO adsorbent derived from calcium gluconate owned highest reactivity and the most pronounced CO₂ capture performance with the first carbonation conversion reaching as high as 85.33%, but it also had smaller crystalline grains of CaO than other absorbents with more developed pores within 20—100nm. After the twenty CO₂ capture cycles, the neighboring CaO particles involved were found to melt and agglomerate into larger particles, which resulted in loss of the pore structure and reduced porosity, and thereby its carbon capture performance decayed.

Key words: carbon capture, calcium looping, organic calcium derived from eggshell, CO₂ cyclic capture performance, structural evolution

中图分类号:

TK16

王保文, 姜涛, 许炳辉, 梁彦琛, 郭超凡, 李旭刚, 周志永. 废弃蛋壳源高性能钙基吸收剂的制备及其碳捕集性能[J]. 化工进展, 2022, 41(3): 1289-1297.

WANG Baowen, JIANG Tao, XU Binghui, LIANG Yanchen, GUO Chaofan, LI Xugang, ZHOU Zhiyong. Preparation of the calcium based adsorbent derived from egg shell waste and its CO₂ capture performance in the calcium looping[J]. Chemical Industry and Engineering Progress, 2022, 41(3): 1289-1297.

图/表 10

表1 蛋壳中各组分的质量分数 (%)

CaO	SO₃	P₂O₅	Na₂O	MgO	SiO₂	K₂O	Al₂O₃	其他
98.413	0.628	0.570	0.161	0.083	0.054	0.052	0.029	<0.10

图1 定制双温管式反应器系统示意图1—混气罐；2—温控仪；3—煅烧炉；4—碳化炉；5—电子秤

图2 五种CaO吸收剂循环性能随循环次数的变化（碳酸化条件: 650℃, 15%CO2, 85%N2, 30min; 煅烧条件: 900℃, 100%N2, 10min）

图3 五种CaO吸收剂循环稳定性随循环次数的变化

图4 单次循环蛋壳源吸收剂的碳酸化转化率随时间的变化（碳酸化条件: 650℃, 15%CO2, 85%N2, 30min）

图5 单次循环蛋壳源吸收剂碳酸化转化速率随时间的变化

图6 CaO吸收剂XRD分析

图7 吸收剂孔径分布

图8 吸收剂SEM图像

表2 吸收剂的比表面积及孔容参数

名称	比表面积/m²·g^-1	总孔容/mm³·g^-1
DCG-CaO	22.944	265.0
D-CaO	12.480	130.58
DCG-CaO-20	15.078	169.0
D-CaO-20	11.512	122.69

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废弃蛋壳源高性能钙基吸收剂的制备及其碳捕集性能

Preparation of the calcium based adsorbent derived from egg shell waste and its CO₂ capture performance in the calcium looping

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废弃蛋壳源高性能钙基吸收剂的制备及其碳捕集性能

Preparation of the calcium based adsorbent derived from egg shell waste and its CO2 capture performance in the calcium looping

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Preparation of the calcium based adsorbent derived from egg shell waste and its CO₂ capture performance in the calcium looping