工业固废和廉价矿石制备高循环稳定性高温CO2捕集材料的研究进展

doi:10.11896/cldb.20080091

材料导报

2021, Vol. 35

Issue (17): 17090-17102 https://doi.org/10.11896/cldb.20080091

材料与可持续发展(四)———材料再制造与废弃物料资源化利用*

工业固废和廉价矿石制备高循环稳定性高温CO₂捕集材料的研究进展

范文琦¹, 潘登², 黄亮¹, 王强¹

1 北京林业大学环境科学与工程学院,北京 100083
2 武汉凯迪水务有限公司,武汉 430000

Research Progress in the Preparation of High Cycling Stability and High Temperature CO₂ Capture Materials from Industrial Solid Waste and Cheap Ore

FAN Wenqi¹, PAN Deng², HUANG Liang¹, WANG Qiang¹

1 College of Environmental Science and Engineering, Beijing Forestry University,Beijing 100083, China
2 Wuhan Kaidi Water Service Co., Ltd., Wuhan 430000, China

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摘要全球范围已就“2 ℃气候红线”达成共识。为缓解气候变暖,同时满足经济发展的能源需求,CO₂大规模减排技术受到了广泛关注。其中,CO₂捕集、利用与封存(CCUS)技术被认为是实现减排的最理想途径。而无论对于CO₂的利用还是封存,CO₂捕集都是必要的前提。近年来,空气中CO₂的捕集开始逐渐受到关注,但从源头控制出发,工业源的CO₂捕集仍是减排的重点所在。目前工业应用的CO₂捕集技术——胺洗涤仍存在成本高且产物具有环境毒性等问题。与之相比,固体CO₂捕集材料在生产、运输、应用上都具有独特的优势,鉴于工业CO₂普遍温度较高,越来越多的研究致力于固体高温CO₂吸附剂的构建。
目前,固体材料高温CO₂捕集已进入中试阶段。为实现工业化应用,吸附材料的成本、吸附性能和循环稳定性都受到重点关注。常规的高温CO₂吸附材料CaO、Li₄SiO₄都存在多次循环后易发生烧结而导致吸附性能下降的问题,虽然可以通过改进合成方法、元素掺杂、表面修饰等手段对其进行改性,但这无疑会造成成本的增加。对此,许多研究者开始利用工业固体废弃物或廉价矿石合成高温CO₂吸附剂。大量研究结果表明,使用天然/废弃原料不仅可以降低吸附剂的生产成本,还可以实现固体废弃物的资源化,原料中的部分杂质组分还对吸附剂的抗烧结性能有着重要的促进作用,这对固体高温CO₂吸附剂的实际应用有着重要的价值。
基于天然/废弃原料合成高温CO₂吸附剂的良好应用前景,为助力廉价高效CO₂吸附剂的研发,本文综述了近十年来以工业固体废弃物和廉价矿石为原料制备CaO基和Li₄SiO₄基两种高温CO₂吸附剂的研究进展;分别介绍了制备高温吸附剂的各类前驱体及改性材料,如矿石(石灰石、白云石、高岭土、硅藻土、蛭石、方解石、埃洛石、铝土矿尾矿等)、生物质(蛋壳、贝壳、微生物、谷稻壳等)、水泥建筑工业废弃物(粉煤灰、电石渣、钢渣、铝酸钙水泥、造纸白泥、建筑废料、水泥生料、废弃大理石粉末等)等;整理了材料的合成及改性方法,如掺杂改性、酸浸、水洗、干燥、煅烧、造粒等预处理手段;综合对比了材料在不同条件下的吸附性能及吸-脱附循环稳定性,如不同温度或不同CO₂浓度下材料的性能变化;并讨论了其可能的优化机理,如表面孔径的优化,造粒耐磨损、耐烧结骨架的生成及离子的均衡扩散等;总结了各类材料存在的优点与不足,如CaO基材料来源广泛、成本低廉,但存在因循环煅烧而导致的吸附性能下降问题,Li₄SiO₄基材料具有较快的吸-脱附速率,但循环稳定性较差且受CO₂浓度影响大的问题有待解决。希望本文不仅能帮助研究者快速了解该领域的研究现状,还能为其后续的研究工作提供有价值的建议。

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关键词: 高温CO₂捕集材料矿石工业固体废物吸-脱附循环氧化钙硅酸锂

Abstract: Aglobal consensus has been reached on the “2 ℃ climate red line”. In order to mitigate climate warming and meet the energy needs of economic development, CO₂ emission reduction technologies have attracted wide attention. Among them, CO₂ capture, utilization and storage (CCUS) technology is considered as the most ideal way to achieve emission reduction. CO₂ capture is a necessary prerequisite for both utilization and storage of CO₂. In recent years, air CO₂ capture has been gradually concerned, but from the perspective of source control, CO₂ capture from industrial sources is still the focus of emission reduction. At present, the industrial application of CO₂ capture technology amine washing still has the problems of high cost and environmental toxicity. In contrast, solid CO₂ capture materials have unique advantages in production, transportation and application. In view of the generally high temperature of industrial CO₂, more and more researches are devoted to the construction of solid high-temperature CO₂ adsorbents.
At present, the high temperature CO₂ capture of solid materials has entered the pilot-scale. In order to realize industrial application, the cost, adsorption performance and cycling stability of adsorptive materials have been paid much attention. Conventional high temperature CO₂ adsorption materials, CaO and Li₄SiO₄, are prone to sintering after multiple cycles, resulting in a decline in adsorption performance. Although they can be modified by improving the synthesis method, element doping, surface modification and other means, there is no doubt that this will cause an increase in cost. In response, many researchers have begun to synthesize high-temperature CO₂ adsorbents from industrial solid waste or cheap ore. A large number of research results show that the use of natural/waste raw materials can not only reduce the production cost of the adsorbent and realize the recycling of solid waste, but also some of the impurities in the raw materials have an important role in promoting the anti-sintering performance of the adsorbent, which is of great value for the practical application of solid high-temperature CO₂ adsorbent.
Based on the good application prospect of high temperature CO₂ adsorbents synthesized from natural/waste raw materials, in order to facilitate the research and development of low cost and high efficiency CO₂ adsorbents, this paper summarizes the research progress of the preparation of CaO and Li₄SiO₄ based high temperature CO₂ adsorbents from industrial solid waste and cheap ore in the recent ten years. All kinds of precursors and modified materials are sorted out respectively, mainly include all kinds of ores (limestone, dolomite, kaolin, diatomite, vermiculite calcite, etc.), biomass (shell, shell, microorganism, valley, rice husk, etc.), cement building industrial waste (fly ash, calcium carbide slag, steel slag, calcium aluminate cement, papermaking white clay, construction waste, cement raw meal, waste marble powder, etc.), etc.; the synthesis conditions and modification methods of the materials are listed, such as doping modification, acid leaching, water washing, drying and calcination. Compared with CO₂ adsorption conditions and properties based on constant cycle times and adsorption amount. The possible mechanisms, such as the optimization of surface aperture, the formation of pellet wear resistance, sintering resistance skeleton and the equilibrium diffusion of ions, are integrated. The advantages and disadvantages of all kinds of materials are summarized. For example, CaO based materials have wide sources and low cost, but there is a problem of degradation of adsorption performance caused by sintering due to cyclic calcination. Li₄SiO₄ based materials have a faster rate of absorption and desorption, but the problem of poor cycling stability and large influence by CO₂ concentration remains to be solved. We hope that this paper can not only help researchers quickly understand the research status in this field, but also provide meaningful suggestions for their subsequent research work, so as to promote the industrial application of solid high-temperature CO₂ adsorbent.

Key words: high temperature CO₂ capture material ore industrial solid waste adsorption-desorption cycle calcium oxide lithium silicate

发布日期: 2021-09-26

ZTFLH:

X75

基金资助: 中央高校基本科研业务费专项资金(2019JQ03015);国家自然科学基金(U1810209);兵团国际科技合作计划(2018BC002);北京高校高精尖学科建设项目“生态修复工程学”

通讯作者: qiangwang@bjfu.edu.cn

作者简介: 范文琦,2019年6月毕业于北京林业大学,获得工学学士学位。现为北京林业大学环境科学与工程学院硕士研究生,在王强教授的指导下进行研究,目前主要研究领域为碱金属钛酸盐高温CO₂吸附材料。
王强,北京林业大学环境科学与工程学院副院长、教授、博士研究生导师。于2003年和2005年在哈尔滨工业大学获得学士和硕士学位,2009年在韩国浦项工业大学获得博士学位,2009—2011年在新加坡科研局化学与工程科学研究院任研究员,2011—2012年在英国牛津大学作博士后,2012年进入北京林业大学环境科学与工程学院工作。入选国家自然科学基金优秀青年基金项目、教育部“新世纪优秀人才支持计划”、第一批国家环境保护专业技术青年拔尖人才、第七批“北京市优秀青年人才”、北京市青年拔尖人才、北京市科技新星、北京林业大学“杰出青年人才培养计划”等。受聘SCI期刊Journal of Energy Chemistry责任编辑、Science of Advanced Materials副主编、Catalysts编委、Reaction Chemistry & Engineering和Frontiers in Chemistry客座编辑。已在Chem. Rev.、Energy Environ. Sci.和Appl. Catal. B: Environ.等发表SCI论文190余篇。主持项目10余项,获授权国际专利4项、国内专利7项。主编英文专著3部,撰写英文专著章节4个。主要研究方向包括:(1)二氧化碳捕集与利用;(2)烟气脱硝催化剂研发;(3)挥发性有机污染物吸附/催化材料研发。

引用本文:

范文琦, 潘登, 黄亮, 王强. 工业固废和廉价矿石制备高循环稳定性高温CO₂捕集材料的研究进展[J]. 材料导报, 2021, 35(17): 17090-17102.
FAN Wenqi, PAN Deng, HUANG Liang, WANG Qiang. Research Progress in the Preparation of High Cycling Stability and High Temperature CO₂ Capture Materials from Industrial Solid Waste and Cheap Ore. Materials Reports, 2021, 35(17): 17090-17102.

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http://www.mater-rep.com/CN/10.11896/cldb.20080091 或 http://www.mater-rep.com/CN/Y2021/V35/I17/17090

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