Preparation of vaterite CaCO3 by mineralizing CO2 from desulfurized gypsum

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

Abstract

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

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

CLC Number:

TQ177.3

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.

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.

Figures/Tables 17

References 33

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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

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

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

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

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

Preparation of vaterite CaCO₃ by mineralizing CO₂from desulfurized gypsum

脱硫石膏矿化CO₂制备球霰石碳酸钙

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References 33

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