脱硫石膏矿化CO2制备球霰石碳酸钙

doi:10.16085/j.issn.1000-6613.2024-0483

化工进展 ›› 2025, Vol. 44 ›› Issue (4): 2328-2337.DOI: 10.16085/j.issn.1000-6613.2024-0483

脱硫石膏矿化CO₂制备球霰石碳酸钙

窦玉¹^,²(), 王文选³, 范春雷⁴, 马吉亮¹^,², 梁财¹^,², 陈晓平¹^,²()

^1.东南大学能源与环境学院，江苏南京 210096
^2.东南大学能源热转换及其过程测控教育部重点实验室，江苏南京 210096
^3.江苏峰业环境科技集团股份有限公司，江苏扬州 225236
^4.华能南京金陵发电有限公司，江苏南京 210096

收稿日期:2024-03-25 修回日期:2024-06-24 出版日期:2025-04-25 发布日期:2025-05-07
通讯作者: 陈晓平
作者简介:窦玉（1999—），男，硕士研究生，研究方向为CO₂减排技术与固废资源化利用。E-mail：2281396412@qq.com。
基金资助:
国家重点研发计划(2020YFC1908700);江苏省碳达峰碳中和专项(BK20220001)

Preparation of vaterite CaCO₃ by mineralizing CO₂from desulfurized gypsum

DOU Yu¹^,²(), WANG Wenxuan³, FAN Chunlei⁴, MA Jiliang¹^,², LIANG Cai¹^,², CHEN Xiaoping¹^,²()

^1.School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, China
^2.Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, Southeast University, Nanjing 210096, Jiangsu, China
^3.Fengye Technology & Environment Group Co. , Ltd. , Yangzhou 225263, Jiangsu, China
^4.Huaneng Nanjing Jinling Power Generation Co. , Ltd. , Nanjing 210096, Jiangsu, China

Received:2024-03-25 Revised:2024-06-24 Online:2025-04-25 Published:2025-05-07
Contact: CHEN Xiaoping

摘要/Abstract

摘要：

为了资源化利用脱硫石膏以及封存CO₂，研究在常温常压条件下脱硫石膏矿化反应制备球霰石型碳酸钙的工艺，探究了晶型控制剂对于矿化固体产物碳酸钙纯度、球霰石含量的影响，并对球霰石的稳定性进行了分析，检测了矿化反应副产的硫酸铵晶体重金属含量，初步讨论了丝氨酸促进球霰石形成的影响机制。结果表明，脱硫石膏矿化反应获得的碳酸钙的纯度随丝氨酸与脱硫石膏质量比的增大呈先增加后逐渐降低的趋势，但丝氨酸与脱硫石膏的质量比基本不影响碳酸钙中球霰石的含量；在搅拌速率为1000r/min、氨当量比为1.2、CO₂流量为400mL/min、固液比为15%条件下，丝氨酸与脱硫石膏最优质量比为30%；球霰石样品在367℃时开始发生晶型转变，当煅烧温度为450℃时样品中方解石质量分数为74.36%。研究表明，丝氨酸的极性侧链羟基与钙离子相互作用，促进了球霰石型碳酸钙晶核的形成，同时丝氨酸择优吸附在球霰石上，稳定球霰石晶核，阻碍其向方解石转化。在脱硫石膏矿化CO₂过程中添加丝氨酸是一种简易高效制备球霰石型碳酸钙的工艺方法，能够同步实现CO₂的封存和资源化利用。

关键词: 废物处理, 二氧化碳捕集, 方解石, 脱硫石膏, 球霰石, 丝氨酸

Abstract:

For resource utilization of desulfurization gypsum and CO₂ sequestration, the process of producing vaterite CaCO₃ by mineralization reaction of desulfurization gypsum under normal temperature and pressure was studied. The influence of crystal control agent on the purity of calcium carbonate and vaterite content of mineralized solid product was investigated and the stability of vaterite was analyzed. The heavy metal content of ammonium sulfate crystals by-products of mineralization was determined and the mechanism of influence of serine on promoting the formation of vaterite CaCO₃ was preliminarily discussed. The results indicated that the purity of calcium carbonate obtained from the mineralization reaction of desulfurization gypsum showed an increasing and then decreasing trend with the increase of the mass ratio of serine to desulfurization gypsum, but the mass ratio of serine to desulfurization gypsum basically did not affect the content of vaterite in the calcium carbonate. Under the condition of stirring rate of 1000r/min, ammonia equivalent ratio of 1.2, CO₂ flow rate of 400mL/min and solid-liquid ratio of 15%, the optimum quality ratio of serine to desulfurization gypsum was 30%. The crystalline transformation of vaterite samples started at 367℃, and the content of calcite in the samples was 74.36% when the calcination temperature was 450℃. Research indicated that the polar side chain hydroxyl group of serine interacted with calcium ions, facilitating the nucleation of vaterite calcium carbonate. Additionally, serine selectively adsorbed onto vaterite, stabilizing its nuclei and inhibiting its transformation into calcite. The addition of serine during the mineralization of CO₂ by desulfurization gypsum was a simple and efficient process method for the preparation of vaterite CaCO₃, which could simultaneously achieve the sequestration and resource utilization of CO₂.

Key words: waste treatment, CO₂ capture, calcite, desulfurized gypsum, vaterite, serine

中图分类号:

TQ177.3

窦玉, 王文选, 范春雷, 马吉亮, 梁财, 陈晓平. 脱硫石膏矿化CO₂制备球霰石碳酸钙[J]. 化工进展, 2025, 44(4): 2328-2337.

DOU Yu, WANG Wenxuan, FAN Chunlei, MA Jiliang, LIANG Cai, CHEN Xiaoping. Preparation of vaterite CaCO₃ by mineralizing CO₂from desulfurized gypsum[J]. Chemical Industry and Engineering Progress, 2025, 44(4): 2328-2337.

图/表 17

表1 脱硫石膏的主要化学组成

成分	质量分数/%
CaO	36.40
SO₃	38.00
SiO₂	2.65
Fe₂O₃	0.22
Al₂O₃	0.61
K₂O	0.08
MgO	0.36
结晶水	20.91

图1 实验装置系统

图2 丝氨酸与脱硫石膏质量比对矿化反应固体产物的影响

图3 不同丝氨酸与脱硫石膏质量比下固体产物XRD谱图和固体产物CaCO3中球霰石含量

图4 固体产物SEM形貌随丝氨酸与脱硫石膏质量比的变化

图5 钙的回收率随丝氨酸与脱硫石膏质量比的变化

表2 碳酸钙产品中杂质元素含量

元素	质量分数/%
S	1.38
Si	1.36
F	0.82
Al	0.64
Fe	0.60
Na	0.25
K	0.15
Mg	0.13
Ti	0.08
Sr	0.08
Cl	0.03
Zn	0.02
P	0.02

图6 球霰石水稳定性随搅拌时间的变化

图7 在水中搅拌不同时间后球霰石的SEM图

图8 不同煅烧温度下脱硫石膏矿化固体产物XRD谱图

图9 不同煅烧温度下脱硫石膏矿化固体产物SEM图

图10 球霰石和方解石含量随煅烧温度的变化

图11 碳酸钙样品TG-DSC曲线

图12 不同pH下固体产物SEM图

图13 不同pH下固体产物XRD谱图

图14 球霰石形成机理

表3 硫酸铵晶体重金属含量

取样质量/g	定容体积/mL	稀释系数	所测元素	仪器读数 /mg·L^-1	换算含量 /mg·kg^-1	国家标准 /mg·kg^-1
0.1058	25	1	As	0.0033	0.8	≤10
0.1058	25	1	Cd	0.0004	0.1	≤10
0.1058	25	1	Co	0.0114	2.7
0.1058	25	1	Cr	0.0361	8.5	≤50
0.1058	25	1	Cu	0.0057	1.3
0.1058	25	1	Ni	0.0023	0.5
0.1058	25	1	Pb	0.0019	0.4	≤50
0.1058	25	1	Sb	0.0027	0.6
0.1058	25	1	Tl	0.0013	0.3
0.1058	25	1	V	0.0009	0.2

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脱硫石膏矿化CO₂制备球霰石碳酸钙

Preparation of vaterite CaCO₃ by mineralizing CO₂from desulfurized gypsum

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