二氧化碳矿化高钙基固废制备微细碳酸钙研究进展

doi:10.16085/j.issn.1000-6613.2022-1012

摘要/Abstract

摘要：

微细碳酸钙作为一种重要的化工填充物，广泛地应用于造纸、油墨、橡胶、塑料等行业。随着当前碳减排行动的日趋深入，微细碳酸钙制备从原料到工艺路线已经越来越多元化。利用工业高钙原料，如钢渣、电石渣、废弃石膏等作为钙源耦合CO₂制备微细碳酸钙的技术越来越被关注。本文综述了CO₂矿化高钙固废制备微细碳酸钙的研究进展，分别对采用氧化钙、氢氧化钙、硫酸钙以及高钙基工业固废等材料制备微细碳酸钙进行了具体介绍。比较了在不同材料与CO₂矿化反应制备碳酸钙的技术特性以及优化碳酸钙产品性能方面的最新成果，并对最具代表性的工业固体废弃物制备微细碳酸钙技术规模化应用及环境经济性评价进行了总结归纳。在初步技术经济分析的基础上，发现当前CO₂矿化高钙固废制备微细碳酸钙的规模化应用主要受限于碳酸钙结晶速度快、运行成本高及能源强度大等方面。为更好地开展大规模工业化应用，建议如下：一是针对碳酸钙结晶过程，着眼于微观反应机制和高钙固废材料特性，开发有效适用于工业应用的控制方法；二是将工业固废资源化与合成精细化碳酸钙技术耦合，推进特定工艺开发和装置研发；三是基于控制方法和装备开发，对特定工艺路线展开全生命周期环境和经济性评估。

关键词: 高钙工业固废, CO₂矿化, 微细碳酸钙, 碳减排, 资源化利用

Abstract:

As an important chemical filler, ultrafine calcium carbonate is widely used in papermaking, ink, rubber, plastics and other industries. With the deepening of carbon emission reduction, the preparation of ultrafine calcium carbonate has become more and more diversified in terms of raw materials and process routes. The use of high-calcium industrial materials, such as steel slag, carbide slag, waste gypsum, etc., as a calcium source coupled with carbon dioxide to prepare ultrafine calcium carbonate has attracted more and more attention. In this paper, the research progress of CO₂ mineralization of high calcium solid waste to prepare ultrafine calcium carbonate is reviewed. The calcium oxide, calcium hydroxide, calcium sulfate and high-calcium industrial solid waste materials are considered and compared. This paper introduces the latest achievements on the preparation of ultrafine calcium carbonate via CO₂ mineralization based on different materials. Meanwhile, the large-scale application and environmental economy of the most representative technology of preparing ultrafine calcium carbonate by industrial solid waste are summarized. Based on the preliminary economic analysis, the reasons for the limitation of current scale-up applications are mainly the control of calcium carbonate crystallization, and the consumption of energy and cost. Thus, in order to better carry out large-scale industrial application, the following suggestions are proposed: firstly, to develop effective control methods for industrial applications aiming at the crystallization process of calcium carbonate based on the microscopic reaction mechanism and the characteristics of solid waste material properties; secondly, to couple the resource recovery of industrial solid waste and the synthesis of refined calcium carbonate technology to promote the development of specific process and devices; and thirdly, to carry out the life cycle environmental and economic assessment based on the development of control methods and equipment.

Key words: high calcium industrial solid waste, CO₂ mineralization, ultrafine calcium carbonate, carbon emission reduction, resource utilization

中图分类号:

X705

李文秀, 杨宇航, 黄艳, 王涛, 王镭, 方梦祥. 二氧化碳矿化高钙基固废制备微细碳酸钙研究进展[J]. 化工进展, 2023, 42(4): 2047-2057.

LI Wenxiu, YANG Yuhang, HUANG Yan, WANG Tao, WANG Lei, FANG Mengxiang. Preparation of ultrafine calcium carbonate by CO₂ mineralization using high calcium-based solid waste[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2047-2057.

图/表 8

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合成方法	条件参数	碳酸钙产品	参考文献
棕榈酸作模板剂	25℃，CO₂ 100mL/min	立方形单颗粒，无表面活性剂100nm；1.5%（质量分数）棕榈酸20~4nm；2.5%（质量分数）棕榈酸500~800nm	[19]
超声波碳酸化	30℃，CO₂ 45L/h，Ca(OH)₂ 20mL/min	菱面体方解石，224nm	[20]
微孔分散法	5℃/25℃，CO₂ 100mL/min，油酸作为表面活性剂	立方方解石单晶40~60nm，油酸作为表面活性剂时直径减小到30~40nm	[21]
超重力反应沉淀法	工业生产条件	方解石和球霰石碳酸钙，粒径80nm	[22]
连续喷雾法	CO₂ 8%，60%饱和度的Ca(OH)₂	纺锤状碳酸钙晶体，1~3µm	[23]
连续鼓泡搅拌法	CO₂ 452.30mL/min，Ca(OH)₂ 2mol/L	方解石晶体，0.1~0.5µm	[24]

合成方法	条件参数	碳酸钙产品	参考文献
棕榈酸作模板剂	25℃，CO₂ 100mL/min	立方形单颗粒，无表面活性剂100nm；1.5%（质量分数）棕榈酸20~4nm；2.5%（质量分数）棕榈酸500~800nm	[19]
超声波碳酸化	30℃，CO₂ 45L/h，Ca(OH)₂ 20mL/min	菱面体方解石，224nm	[20]
微孔分散法	5℃/25℃，CO₂ 100mL/min，油酸作为表面活性剂	立方方解石单晶40~60nm，油酸作为表面活性剂时直径减小到30~40nm	[21]
超重力反应沉淀法	工业生产条件	方解石和球霰石碳酸钙，粒径80nm	[22]
连续喷雾法	CO₂ 8%，60%饱和度的Ca(OH)₂	纺锤状碳酸钙晶体，1~3µm	[23]
连续鼓泡搅拌法	CO₂ 452.30mL/min，Ca(OH)₂ 2mol/L	方解石晶体，0.1~0.5µm	[24]

原料	CaO	MgO	SiO₂	Fe₂O₃	Al₂O₃	SO₃	参考文献
钢渣	30~60	5~20	10~45	3~9	1~18	<1	[29-32]
高炉渣	30~50	5~15	25~45	10~30	0~10	<1
电石渣	80~90	0.1~1.5	1~20	0.2~1.5	1~3	<1
废弃石膏	30~45	<1	0.1~6.5	<1	<1	40~45

原料	CaO	MgO	SiO₂	Fe₂O₃	Al₂O₃	SO₃	参考文献
钢渣	30~60	5~20	10~45	3~9	1~18	<1	[29-32]
高炉渣	30~50	5~15	25~45	10~30	0~10	<1
电石渣	80~90	0.1~1.5	1~20	0.2~1.5	1~3	<1
废弃石膏	30~45	<1	0.1~6.5	<1	<1	40~45

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