CH3COONa-NH4OH-H2O体系下磷石膏矿化CO2-联产高纯CaCO3

doi:10.16085/j.issn.1000-6613.2022-1576

化工进展 ›› 2023, Vol. 42 ›› Issue (7): 3824-3833.DOI: 10.16085/j.issn.1000-6613.2022-1576

CH₃COONa-NH₄OH-H₂O体系下磷石膏矿化CO₂-联产高纯CaCO₃

丁文金¹^,²(), 刘卓齐¹^,², 卢海臣¹^,², 孙红娟¹^,², 彭同江¹^,²

^1.西南科技大学固体废物处理与资源化教育部重点实验室，四川绵阳 621010
^2.西南科技大学矿物材料及应用研究所，四川绵阳 621010

收稿日期:2022-08-25 修回日期:2022-11-13 出版日期:2023-07-15 发布日期:2023-08-14
通讯作者: 丁文金
作者简介:丁文金（1985—），男，博士后，硕士生导师，研究方向为固体废弃物的评价与资源化利用。E-mail：dwjdykclx@163.com。
基金资助:
科技部重点研发项目(2018YFC1802902);西南科技大学博士基金(17ZX7117);四川省城市固废能源与转化利用技术工程研究中心开放基金(GF2022ZD002)

Preparation of high-purity CaCO₃ from phosphogypsum for CO₂ mineralization in CH₃COONa-NH₄OH-H₂O system

DING Wenjin¹^,²(), LIU Zhuoqi¹^,², LU Haichen¹^,², SUN Hongjuan¹^,², PENG Tongjiang¹^,²

^1.Key Laboratory of Ministry of Education for Solid Waste Treatment and Resource Recycle, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China
^2.Institute of Mineral Materials and Application, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China

Received:2022-08-25 Revised:2022-11-13 Online:2023-07-15 Published:2023-08-14
Contact: DING Wenjin

摘要/Abstract

摘要：

基于我国面临CO₂减排与磷石膏资源化利用的巨大压力，本文提出助剂循环使用的CO₂矿化与磷石膏资源化利用过程耦合的学术思想，立题以磷石膏为原料，研究醋酸钠体系下氨水强化磷石膏浸出液矿化CO₂联产高纯CaCO₃的反应过程。实验过程中系统讨论了不同工艺条件对磷石膏中Ca²⁺的浸出及浸出液矿化CO₂反应效能的影响，并系统表征了反应条件对矿化产物晶粒尺寸、结构与形貌的影响。结果表明：低温常压条件下1t磷石膏可以矿化吸收208kg的CO₂，同时联产472kg纯度为99.63%的球形球霰石。通过调节矿化反应条件可有效调控矿化产物的晶粒尺寸；提高反应温度和延长反应时间有利于亚稳态的球霰石向热力学更稳定的文石和方解石转化。实验过程中实现了醋酸钠的循环利用与回收。本文为磷石膏的资源化利用与高纯CaCO₃的制备提供了新的思路。

关键词: 磷石膏, CO₂矿化, 碳酸钙, 循环利用, 产物调控

Abstract:

Based on the huge pressure of CO₂ emission reduction and resource utilization of phosphogypsum in China, the academic idea of coupling CO₂ mineralization and phosphogypsum resource utilization process of auxiliary recycling was put forward. In this paper, phosphogypsum was used as the raw material explore the reaction of ammonia-strengthened phosphogypsum leaching solution to mineralize CO₂ and produce high-purity CaCO₃ in a CH₃COONa-H₂O system. The effects of different process conditions on the leaching of Ca²⁺ from phosphogypsum and the reaction efficiency of the leaching solution to mineralize CO₂ were systematically discussed. The effects of process parameters on grain size, structure and morphology of mineralization product were analyzed systematically. According to the results, 1t of phosphogypsum could sequestrate 208kg of CO₂ at low temperature and atmospheric pressure, producing 472kg of spherical vaterite with a purity of 99.63%. The grain size of the product was controlled by adjusting reaction conditions. A rise in reaction temperature and a prolonged reaction time were conducive to transforming vaterite with metastable state to aragonite and calcite, two more thermodynamically stable phases. The experiment realized the successful recycling and recovery of CH₃COONa. This paper provided a new idea for the creative recycling of phosphogypsum and preparation of high-purity CaCO₃.

Key words: phosphogypsum, CO₂ mineralization, CaCO₃, cyclic utilization, product control

中图分类号:

X781

丁文金, 刘卓齐, 卢海臣, 孙红娟, 彭同江. CH₃COONa-NH₄OH-H₂O体系下磷石膏矿化CO₂-联产高纯CaCO₃[J]. 化工进展, 2023, 42(7): 3824-3833.

DING Wenjin, LIU Zhuoqi, LU Haichen, SUN Hongjuan, PENG Tongjiang. Preparation of high-purity CaCO₃ from phosphogypsum for CO₂ mineralization in CH₃COONa-NH₄OH-H₂O system[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3824-3833.

图/表 9

图1 磷石膏、浸出产物、碳酸化产物及碳酸化副产物的XRD图谱[(a)]；磷石膏、浸出产物和碳酸化产物的SEM图[(b)～(d)]

图2 不同工艺条件对Ca2+浸出率的影响

图3 不同工艺条件对Ca2+碳酸化转化率的影响

图4 碳酸化滤液循环次数与反应效能的关系(a)以及不同碳酸化滤液循环次数下所得产物的 XRD图谱(b)、FTIR图谱(c)、SEM图[(d)~(k)，循环次数分别为1次、2次、3次、4次、5次、6次、7次、8次]

表1 工业副产石膏制备CaCO3工艺的对比

原料	工艺条件	结果	文献
磷石膏	以碱性溶液为助剂，常温常压	产物为含有石英、三氧化二铝等杂质的方解石	[17]
	以氨水为助剂，采用直接碳酸化工艺，常温常压	产物为含有石英、三氧化二铝等杂质的纳米碳酸钙	[18]
	以氢氧化钠、盐酸、氨水为助剂，常温常压	产物为高纯、高白度碳酸钙，但整个工艺需消耗强酸强碱	[10]
脱硫石膏	通过超声强化碳酸化反应过程	产物为球霰石，工艺能耗较高，超声工艺不利于大规模工业化推广	[19]
脱硫石膏	通过超声波强化碳酸化反应，以氢氧化钠、氢氧化钾和氨水为助剂	产物为球霰石，工艺能耗较高且需要消耗一定量强碱	[20]
钛石膏	以硫酸和单乙醇胺为助剂，反应条件315℃、20MPa	产物为方解石，整个工艺需在高温高压下进行	[21]
磷石膏	以醋酸钠和氨水为助剂，低温常压	产物为高纯碳酸钙，颗粒尺寸、晶型和形貌可控，醋酸钠可循环利用与回收	本研究

图5 不同氨水添加量下所得产物的XRD图谱(a)、晶粒尺寸(b)、FTIR图谱(c)、SEM图[(d)～(j)，氨水添加量分别为5mL、8mL、10mL、12mL、15mL、20mL、25mL]

图6 不同CO2流速下所得产物的XRD图谱(a)、晶粒尺寸(b)、FTIR图谱(c)、SEM图[(d)～(h)，CO2流速分别为50mL/min、80mL/min、100mL/min、150mL/min、200mL/min]

图7 不同反应温度下所得产物的XRD图谱(a)、晶粒尺寸(b)、FTIR图谱(c)、SEM图[(d)～(i)，反应温度分别为30℃、40℃、50℃、60℃、80℃、100℃]

图8 不同反应时间下所得产物的XRD图谱(a)、晶粒尺寸(b)、FTIR图谱(c)、SEM图[(d)～(g)，反应时间分别为30min、60min、90min、120min]

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CH₃COONa-NH₄OH-H₂O体系下磷石膏矿化CO₂-联产高纯CaCO₃

Preparation of high-purity CaCO₃ from phosphogypsum for CO₂ mineralization in CH₃COONa-NH₄OH-H₂O system

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