磷石膏矿化固定CO2制备碳酸钙微粉

doi:10.16085/j.issn.1000-6613.2023-2224

化工进展 ›› 2025, Vol. 44 ›› Issue (1): 66-74.DOI: 10.16085/j.issn.1000-6613.2023-2224

磷石膏矿化固定CO₂制备碳酸钙微粉

刘冬梅¹^,²(), 庄昭霖¹^,², 王青¹^,²(), 刁华利¹^,², 徐港¹^,², 彭艳周¹^,², 鲍浩¹^,², 李东升³

^1.防灾减灾湖北省重点实验室，湖北宜昌 443002
^2.三峡大学土木与建筑学院，湖北宜昌 443002
^3.湖北三峡实验室，湖北宜昌 443007

收稿日期:2023-12-19 修回日期:2024-05-07 出版日期:2025-01-15 发布日期:2025-02-13
通讯作者: 王青
作者简介:刘冬梅（1977—），女，副教授，硕士生导师，研究方向为工业固体废弃物在水泥混凝土中的应用。E-mail：58983701@qq.com。
基金资助:
国家级地方高校能源和环境材料化学学科创新引智基地项目(D20015);土木工程防灾减灾湖北省引智创新示范基地项目(2021EJD026);国家自然科学基金(52308266);湖北三峡实验室开放/创新基金(SC211006)

Preparation of calcium carbonate powder by phosphogypsum mineralization for CO₂ capture

LIU Dongmei¹^,²(), ZHUANG Zhaolin¹^,², WANG Qing¹^,²(), DIAO Huali¹^,², XU Gang¹^,², PENG Yanzhou¹^,², BAO Hao¹^,², LI Dongsheng³

^1.Hubei Key Laboratory of Disaster Prevention and Mitigation, Yichang 443002, Hubei, China
^2.College of Civil Engineering & Architecture, China Three Gorges University, Yichang 443002, Hubei, China
^3.Hubei Three Gorges Laboratory, Yichang 443007, Hubei, China

Received:2023-12-19 Revised:2024-05-07 Online:2025-01-15 Published:2025-02-13
Contact: WANG Qing

摘要/Abstract

摘要：

以磷石膏为原料，采用D-葡萄糖酸钠浸取磷石膏中Ca²⁺，再以该浸出液固定CO₂制备碳酸钙微粉。研究了液固质量比、反应温度对Ca²⁺浸出率的影响，以及氨水添加量、碳化时间对Ca²⁺转化率的影响。通过扫描电子显微镜、X射线衍射仪、粒度分析等方法分析了不同氨水添加量、碳化时间下碳化产物的形态特征及生成机理。结果表明，随着液固质量比增大，Ca²⁺浸出率增加；反应温度由85℃降到25℃时，磷石膏Ca²⁺浸出率由91%增至100%。在反应温度20℃、CO₂体积分数为20%下，随氨水添加量、碳化时间增加，碳酸钙粒径分布区间呈减小趋势，且Ca²⁺转化率不断增加。氨水添加量为20mL、碳化时间为150min时，碳酸钙的转化率可达92.7%，碳化产物为圆角菱形方解石，峰值粒径以及中值粒径分别为1.5μm和5μm。反应溶液中氨水添加量增加更有利于方解石的形成，而碳化时间增加会促进球霰石的形成，但随着反应溶液中Ca²⁺减少，碳化产物数量骤减，由于已生成的球霰石稳定性较差以及有机溶剂D-葡萄糖酸钠溶液作用，反应产物会发生溶解重结晶，形成粒径小且均匀的圆角菱形方解石。本研究为磷石膏综合利用以及CO₂的捕集并制备碳酸钙微粉提供了一种新的工艺方法。

关键词: 磷石膏, 碳化, D-葡萄糖酸钠, 碳酸钙微粉

Abstract:

Phosphogypsum (PG) was used as raw material, Ca²⁺ was leached from PG by sodium D-gluconate, and then CO₂ was captured by the leaching solution to prepare calcium carbonate powder. The effects of liquid-solid mass ratio and reaction temperature on leaching rate of Ca²⁺, as well as the effects of ammonia addition and carbonization time on the conversion rate of Ca²⁺ were studied. The morphological characteristics and formation mechanism of carbonized products under different ammonia additions and carbonization times were analyzed by scanning electron microscope, X-ray diffraction and particle size analysis. The results showed that the Ca²⁺ leaching rate increased with the increase of liquid-solid mass ratio and the Ca²⁺ leaching rate of PG increased from 91% to 100% when the reaction temperature decreased from 85℃ to 25℃. Under the reaction temperature of 20℃ and CO₂ concentration of 20%, the calcium carbonate particle size distribution interval showed a decreasing trend with the increase of ammonia addition and carbonization time, and the Ca²⁺ conversion rate was increasing. When the amount of ammonia added was 20mL and the carbonization time was 150min, the conversion rate of CaCO₃ was up to 92.7% and the carbonization product was rounded rhombic calcite with the peak particle size as well as the median particle size of 1.5μm and 5μm, respectively. The increase of ammonia addition in the reaction solution was more conducive to the formation of calcite, and the increase of carbonation time promoted the formation of spherulite aragonite. However, the number of carbonization products decreased abruptly with the decrease of Ca²⁺ in the reaction solution. Due to the poor stability of the generated spherical chalcocite and the role of the organic solvent D-gluconate sodium solution, the reaction products would undergo dissolution and recrystallization, and form rounded rhombic calcite with a small and uniform particle size. This study provided a new process method for the comprehensive utilization of PG as well as the capture of CO₂ and preparation of calcium carbonate powder.

Key words: phosphogypsum, carbonization, sodium D-gluconate, calcium carbonate powder

中图分类号:

TQ09

刘冬梅, 庄昭霖, 王青, 刁华利, 徐港, 彭艳周, 鲍浩, 李东升. 磷石膏矿化固定CO₂制备碳酸钙微粉[J]. 化工进展, 2025, 44(1): 66-74.

LIU Dongmei, ZHUANG Zhaolin, WANG Qing, DIAO Huali, XU Gang, PENG Yanzhou, BAO Hao, LI Dongsheng. Preparation of calcium carbonate powder by phosphogypsum mineralization for CO₂ capture[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 66-74.

图/表 10

表1 磷石膏化学成分

化学成分	质量分数/%
SO₃	54.683
CaO	34.334
SiO₂	8.841
Fe₂O₃	0.614
K₂O	0.539
CuO	0.015
BaO	0.171
TiO₂	0.112
SrO	0.371
P₂O₅	0.32

图1 不同液固质量比下石膏的Ca2+浸出率

图2 不同反应温度下石膏的Ca2+浸出率

图3 不同氨水添加量下浸出液Ca2+转化率及pH

图4 不同碳化时间下浸出液Ca2+转化率

图5 不同氨水添加量下碳酸钙的粒径

图 6 不同碳化时间下碳酸钙的粒径

图 7 不同氨水添加量下碳化产物的SEM图像及XRD图谱

图8 不同碳化时间下碳化产物的SEM图像及XRD图谱

图9 磷石膏碳化生成碳酸钙微粉的机理

参考文献 41

1	崔荣政, 白海丹, 高永峰, 等. 磷石膏综合利用现状及“十四五”发展趋势[J]. 无机盐工业, 2022, 54(4): 1-4.
	CUI Rongzheng, BAI Haidan, GAO Yongfeng, et al. Current situation of comprehensive utilization of phosphogypsum and its development trend of 14th Five-Year Plan[J]. Inorganic Chemicals Industry, 2022, 54(4): 1-4.
2	许金辉, 邵龙义, 侯海海, 等. 磷石膏综合利用背景下的环境影响研究现状[J]. 矿业科学学报, 2023, 8(1): 115-126.
	XU Jinhui, SHAO Longyi, HOU Haihai, et al. Review of environmental impact of comprehensive utilization of phosphogypsum[J]. Journal of Mining Science and Technology, 2023, 8(1): 115-126.
3	张贤, 李凯, 马乔, 等. 碳中和目标下CCUS技术发展定位与展望[J]. 中国人口·资源与环境, 2021, 31(9): 29-33.
	ZHANG Xian, LI Kai, MA Qiao, et al. Orientation and prospect of CCUS development under carbon neutrality target[J]. China Population, Resources and Environment, 2021, 31(9): 29-33.
4	KOBELEVA A R, POILOV V Z. Technology for production of calcium carbonate with prescribed properties[J]. Russian Journal of Applied Chemistry, 2007, 80(9): 1447-1452.
5	FADIA Preksha, TYAGI Simona, BHAGAT Stuti, et al. Calcium carbonate nano- and microparticles: Synthesis methods and biological applications[J]. 3 Biotech, 2021, 11(11): 457.
6	JIMOH Onimisi A, ARIFFIN Kamar Shah, HUSSIN Hashim Bin, et al. Synthesis of precipitated calcium carbonate: A review[J]. Carbonates and Evaporites, 2018, 33(2): 331-346.
7	ZHAO Hongtao, LI Huiquan, BAO Weijun, et al. Experimental study of enhanced phosphogypsum carbonation with ammonia under increased CO₂ pressure[J]. Journal of CO₂ Utilization, 2015, 11: 10-19.
8	贺翩翩, 刘晓静, 范勇, 等. 磷石膏固碳制备CaCO₃的实验研究[J]. 非金属矿, 2015, 38(2): 28-30.
	HE Pianpian, LIU Xiaojing, FAN Yong, et al. Study on the preparation of CaCO₃ by phosphogypsum solid carbon through orthogonal experiment[J]. Non-Metallic Mines, 2015, 38(2): 28-30.
9	BAO Weijun, ZHAO Hongtao, LI Huiquan, et al. Process simulation of mineral carbonation of phosphogypsum with ammonia under increased CO₂ pressure[J]. Journal of CO₂ Utilization, 2017, 17: 125-136.
10	LEE Myung gyu, JANG Young Nam, Kyung won RYU, et al. Mineral carbonation of flue gas desulfurization gypsum for CO₂ sequestration[J]. Energy, 2012, 47(1): 370-377.
11	ZHANG Man, FAN Xing. Preparation of gypsum with high purity and whiteness from phosphogypsum for CO₂ mineral sequestration[J]. Scientific Reports, 2023, 13(1): 4156.
12	WU Baizhi, WANG Haibin, LI Chunlei, et al. Progress in the preparation of calcium carbonate by indirect mineralization of industrial by-product gypsum[J]. Sustainability, 2023, 15(12): 9629.
13	刘健, 解田, 朱云勤, 等. 硝酸浸取磷石膏钙渣制备高品质轻质碳酸钙[J]. 环境化学, 2010, 29(4): 772-773.
	LIU Jian, XIE Tian, ZHU Yunqin, et al. Preparation of high quality light calcium carbonate by leaching phosphogypsum calcium slag with nitric acid[J]. Environmental Chemistry, 2010, 29(4): 772-773.
14	RAHMANI Omeid, JUNIN Radzuan, TYRER Mark, et al. Mineral carbonation of red gypsum for CO₂ sequestration[J]. Energy & Fuels, 2014, 28(9): 5953-5958.
15	ALTINER Mahmut. Effect of alkaline types on the production of calcium carbonate particles from gypsum waste for fixation of CO₂ by mineral carbonation[J]. International Journal of Coal Preparation and Utilization, 2019, 39(3): 113-131.
16	LACHEHAB Adil, MERTAH Oumaima, KHERBECHE Abdelhak, et al. Utilization of phosphogypsum in CO₂ mineral sequestration by producing potassium sulphate and calcium carbonate[J]. Materials Science for Energy Technologies, 2020, 3: 611-625.
17	ZDAH Ilham, ALAOUI-BELGHITI Hanan EL, CHERRAT Ayoub, et al. Temperature effect on phosphogypsum conversion into potassium fertilizer K₂SO₄ and portlandite[J]. Nanotechnology for Environmental Engineering, 2021, 6(2): 27.
18	田萍, 宁朋歌, 曹宏斌, 等. 二水硫酸钙在铵盐溶液中溶解度测定及热力学计算[J]. 过程工程学报, 2012, 12(4): 625-630.
	TIAN Ping, NING Pengge, CAO Hongbin, et al. Solubility measurement of calcium sulfate dihydrate in NH₄Cl-‍(NH₄)₂SO₄ solutions and thermodynamic calculation[J]. The Chinese Journal of Process Engineering, 2012, 12(4): 625-630.
19	LIANG Ya qing, SUN Hong juan, PENG Tong Jiang. Effect of pH and concentration of Ca²⁺ on spherical calcium carbonate crystallization by continuous CO₂ gas bubbling into phosphogypsum leaching solution[J]. Materials Science Forum, 2015, 814: 552-558.
20	乔静怡, 陈秋菊, 刘卓齐, 等. 磷石膏矿化CO₂制备球霰石型碳酸钙试验研究[J]. 化工矿物与加工, 2023, 52(9): 14-18, 25.
	QIAO Jingyi, CHEN Qiuju, LIU Zhuoqi, et al. Experimental study on preparation of vaterite-based calcium carbonate by CO₂ mineralization with phosphogypsum[J]. Industrial Minerals & Processing, 2023, 52(9): 14-18, 25.
21	梁亚琴, 孙红娟, 彭同江. 磷石膏固碳制备不同球形碳酸钙的实验研究[J]. 宁夏大学学报(自然科学版), 2015, 36(1): 51-55.
	LIANG Yaqin, SUN Hongjuan, PENG Tongjiang. Experimental study on preparation different spherical calcium carbonate with ardealite carbon sequestration[J]. Journal of Ningxia University (Natural Science Edition), 2015, 36(1): 51-55.
22	时婷, 王新刚, 巫建锋, 等. 磷石膏脱硫钙渣制备轻质碳酸钙[J]. 化工进展, 2015, 34(1): 178-182.
	SHI Ting, WANG Xingang, WU Jianfeng, et al. Preparation of light calcium carbonate from phosphorus gypsum desulfurization slag[J]. Chemical Industry and Engineering Progress, 2015, 34(1): 178-182.
23	DING Wenjin, CHEN Qiuju, SUN Hongjuan, et al. Modified mineral carbonation of phosphogypsum for CO₂ sequestration[J]. Journal of CO₂ Utilization, 2019, 34: 507-515.
24	CHEN Qiuju, DING Wenjin, SUN Hongjuan, et al. Indirect mineral carbonation of phosphogypsum for CO₂ sequestration[J]. Energy, 2020, 206: 118148.
25	刘禄, 乔静怡, 刘卓齐, 等. 磷石膏制备高纯碳酸钙的试验研究[J]. 矿产保护与利用, 2022, 42(5): 126-131.
	LIU Lu, QIAO Jingyi, LIU Zhuoqi, et al. Experimental study on preparation of high-purity CaCO₃ from phosphogypsum[J]. Conservation and Utilization of Mineral Resources, 2022, 42(5): 126-131.
26	QI Huahui, MA Baoguo, TAN Hongbo, et al. Effect of sodium gluconate on molecular conformation of polycarboxylate superplasticizer studied by the molecular dynamics simulation[J]. Journal of Molecular Modeling, 2020, 26(3): 45.
27	Xingdong LYU, LI Jiazheng, LU Chao, et al. The effect of sodium gluconate on pastes’ performance and hydration behavior of ordinary Portland cement[J]. Advances in Materials Science and Engineering, 2020(1): 9231504.
28	史刘宾, 唐名德, 汤勇, 等. 高压碳化法可控制备微纳米分级结构中空棒状碳酸钙及其表征[J]. 化工进展, 2020, 39(11): 4742-4748.
	SHI Liubin, TANG Mingde, TANG Yong, et al. Preparation and characterization of micro-nano hierarchical hollow rod-like calcium carbonate by high pressure carbonization[J]. Chemical Industry and Engineering Progress, 2020, 39(11): 4742-4748.
29	杨敏. 磷石膏的溶解度研究[J]. 广州化工, 2016, 44(15): 62-63, 72.
	YANG Min. Study on solubility of phosphogypsum[J]. Guangzhou Chemical Industry, 2016, 44(15): 62-63, 72.
30	李美, 彭家惠, 张欢, 等. 共晶磷对石膏性能的影响及其作用机理[J]. 四川大学学报(工程科学版), 2012, 44(3): 200-204.
	LI Mei, PENG Jiahui, ZHANG Huan, et al. Influence of P₂O₅ in crystal lattice on gypsum properties and its mechanisms[J]. Journal of Sichuan University (Engineering Science Edition), 2012, 44(3): 200-204.
31	梁玺, 赵改菊, 路春美, 等. 葡萄糖酸钙结晶的热力学特性[J]. 化学工程, 2021, 49(3): 22-27.
	LIANG Xi, ZHAO Gaiju, LU Chunmei, et al. Thermodynamic properties of calcium gluconate crystallization[J]. Chemical Engineering (China), 2021, 49(3): 22-27.
32	DE LUNA Mark Daniel G, SIOSON Arianne S, CHOI Angelo Earvin Sy, et al. Operating pH influences homogeneous calcium carbonate granulation in the frame of CO₂ capture[J]. Journal of Cleaner Production, 2020, 272: 122325.
33	HU Yubin, WOLTHERS Mariëtte, WOLF-GLADROW Dieter A, et al. Effect of pH and phosphate on calcium carbonate polymorphs precipitated at near-freezing temperature[J]. Crystal Growth & Design, 2015, 15(4): 1596-1601.
34	丁光月, 李岳, 樊彩梅, 等. 杂质对磷石膏与碳酸铵反应及产物碳酸钙结晶的影响[J]. 太原理工大学学报, 2011, 42(6): 593-597.
	DING Guangyue, LI Yue, FAN Caimei, et al. Effect of impurities on conversion of gypsum and crystallization of calcium carbonate[J]. Journal of Taiyuan University of Technology, 2011, 42(6): 593-597.
35	钟汝永. 扑朔迷离的碳酸氢钙[J]. 化学教学, 2014(10): 78-79.
	ZHONG Ruyong. The confusing calcium bicarbonate[J]. Education in Chemistry, 2014(10): 78-79.
36	Donata KONOPACKA-ŁYSKAWA, CZAPLICKA Natalia, Barbara KOŚCIELSKA, et al. Influence of selected saccharides on the precipitation of calcium-vaterite mixtures by the CO₂ bubbling method[J]. Crystals, 2019, 9(2): 117.
37	Romuald BABOU-KAMMOE, HAMOUDI Safia, LARACHI Faïçal, et al. Synthesis of CaCO₃ nanoparticles by controlled precipitation of saturated carbonate and calcium nitrate aqueous solutions[J]. The Canadian Journal of Chemical Engineering, 2012, 90(1): 26-33.
38	陈秋鸽, 王戬, 张志业, 等. 磷石膏脱硫钙渣浸取液中杂质对碳酸钙晶型的影响[J]. 化工进展, 2016, 35(11): 3714-3719.
	CHEN Qiuge, WANG Jian, ZHANG Zhiye, et al. Effects of impurities in leaching liquid of phosphogypsum desulfurization slag on crystal form of calcium carbonate[J]. Chemical Industry and Engineering Progress, 2016, 35(11): 3714-3719.
39	RODRIGUEZ-BLANCO Juan Diego, SHAW Samuel, BENNING Liane G. The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite[J]. Nanoscale, 2011, 3(1): 265-271.
40	Donata KONOPACKA-ŁYSKAWA. Synthesis methods and favorable conditions for spherical vaterite precipitation: A review[J]. Crystals, 2019, 9(4): 223.
41	Donata KONOPACKA-ŁYSKAWA, CZAPLICKA Natalia, Marcin ŁAPIŃSKI, et al. Precipitation and transformation of vaterite calcium carbonate in the presence of some organic solvents[J]. Materials, 2020, 13(12):2742.

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磷石膏矿化固定CO₂制备碳酸钙微粉

Preparation of calcium carbonate powder by phosphogypsum mineralization for CO₂ capture

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