超重力反应结晶碳化法制备球形碳酸钙

doi:10.16085/j.issn.1000-6613.2020-2505

化工进展 ›› 2021, Vol. 40 ›› Issue (11): 6323-6331.DOI: 10.16085/j.issn.1000-6613.2020-2505

超重力反应结晶碳化法制备球形碳酸钙

刘晨民¹^,²(), 刘曦曦¹^,², 陈小鹏¹^,², 王伟超¹^,², 廖丹葵¹^,², 蒙秀松²^,³, 童张法¹^,²()

^1.广西大学化学化工学院，广西南宁 530004
^2.广西大学广西碳酸钙产业化工程院广西钙基材料协同创新中心，广西南宁 530004
^3.崇左南方水泥有限公司广西钙基材料协同创新中心，广西崇左 532200

收稿日期:2020-12-15 修回日期:2021-05-05 出版日期:2021-11-05 发布日期:2021-11-19
通讯作者: 童张法
作者简介:刘晨民（1996—），男，硕士研究生，研究方向为碳酸钙形貌制备。E-mail：1436402239@qq.com。
基金资助:
广西创新驱动发展专项资金项目(桂科AA18242015);广西研究生创新创业教育暨联合培养基地示范建设项目(BB30400069)

Preparation of spherical calcium carbonate by high-gravity reaction crystallization carbonization

LIU Chenmin¹^,²(), LIU Xixi¹^,², CHEN Xiaopeng¹^,², WANG Weichao¹^,², LIAO Dankui¹^,², MENG Xiusong²^,³, TONG Zhangfa¹^,²()

^1.School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China
^2.Guangxi Cooperative Innovation Centre for Calcium-based Materials (GCICCM), Guangxi Engineering Academy for Calcium Carbonate Industry, Guangxi University, Nanning 530004, Guangxi, China
^3.Guangxi Cooperative Innovation Centre for Calcium-based Materials (GCICCM), Chongzuo South Cement Company Limited, Chongzuo 532200, Guangxi, China

Received:2020-12-15 Revised:2021-05-05 Online:2021-11-05 Published:2021-11-19
Contact: TONG Zhangfa

摘要/Abstract

摘要：

超重力反应结晶法在碳酸钙制备中具有强化传质作用、产品粒度分布窄等优点。本文以高浓度氢氧化钙浆液作为原料，氯化铵与L-谷氨酸为添加剂，使用超重力反应器成功制备粒径分布较为均匀、形貌较为规整的球形碳酸钙。探究了各因素在超重力反应结晶法制备碳酸钙中的影响，通过改变添加剂的量与超重力因子等考察球形碳酸钙的最佳制备条件。采用扫描电子显微镜（SEM）、X射线衍射（XRD）、傅里叶变换红外光谱仪（FTIR）和静态颗粒图像分析等测试手段对碳酸钙产物进行分析，并通过在反应过程中抽样测试的方法探究反应全过程中添加剂对碳酸钙的影响。结果表明，所制备的碳酸钙为粒径约500nm、晶型为球霰石的球形碳酸钙，同时在L-谷氨酸和氯化铵添加量分别为氢氧化钙质量的4%与20%、超重力因子为161.0的条件下所制备的球形碳酸钙形貌最为规整。

关键词: 超重力反应, 球形碳酸钙, 球霰石, L-谷氨酸, 氯化铵

Abstract:

The high-gravity reaction crystallization method has the advantages of intensifying mass transporting function and the grain sizes of the product are distributed within a narrow range in the preparation of calcium carbonate. Spherical calcium carbonate with uniform size distribution and regular morphology was successfully prepared by using high concentration calcium hydroxide slurry as raw material, ammonium chloride and L-glutamic acid as additives in a high-gravity reactor. The effects of various factors on the preparation of spherical calcium carbonate by high-gravity reactive crystallization were studied and the optimal preparation conditions of spherical calcium carbonate were also investigated by changing the amount of additives and the high-gravity factor. The product of calcium carbonate was analyzed by SEM, XRD, FTIR and static particle image analysis, and the influence of additives on calcium carbonate in the whole reaction process was explored by sampling test. The test results indicated that the prepared product was spherical calcium carbonate with a particle size of about 500nm and a crystal form of vaterite. At the same time, it showed that the spherical calcium carbonate had the most regular morphology when L-glutamic acid and ammonium chloride were 4% and 20% of the mass of calcium hydroxide, respectively, and the high gravity factor was 161.0.

Key words: high-gravity reaction, spherical calcium carbonate, vaterite, L-glutamic acid, ammonium chloride

中图分类号:

TQ13

刘晨民, 刘曦曦, 陈小鹏, 王伟超, 廖丹葵, 蒙秀松, 童张法. 超重力反应结晶碳化法制备球形碳酸钙[J]. 化工进展, 2021, 40(11): 6323-6331.

LIU Chenmin, LIU Xixi, CHEN Xiaopeng, WANG Weichao, LIAO Dankui, MENG Xiusong, TONG Zhangfa. Preparation of spherical calcium carbonate by high-gravity reaction crystallization carbonization[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6323-6331.

图/表 17

图1 超重力反应结晶实验装置1—CO2气体钢瓶；2—阀门；3—流量计；4—pH计；5—循环料液釜；6—排气口；7—液体出口；8—旋转填充床；9—出料口

表1 旋转填充床的内部结构参数

参数	数值
转子填料内半径r_i/m	0.050
转子填料外半径r_o/m	0.150
转子填料轴长h/m	0.050
转子体积V_B/m³	1.57×10^-4
转子填料单位体积内表面积a_f/m²·m^-3	2.73×10³
转子填料空隙率?/m³·m^-3	0.950

图2 球形碳酸钙SEM图

图3 球形碳酸钙XRD谱图

图4 球形碳酸钙红外谱图

图5 不同氯化铵添加量下所制备的碳酸钙的SEM图

图6 不同氯化铵添加量下所制备的碳酸钙XRD图

a—0；b—5%；c—10%；d—15%；e—20%；f—25%

表2 不同氯化铵添加量下碳酸钙样品的球形度

氯化铵添加量（质量分数）/%	球形度
0	0.833
5	0.876
10	0.911
15	0.934
20	0.944
25	0.767

图7 不同L-谷氨酸添加量下所制备的碳酸钙SEM图

图8 不同L-谷氨酸添加量下所制备的碳酸钙XRD图

a—0；b—1%；c—2%；d—3%；e—4%；f—5%

表3 不同L-谷氨酸添加量下碳酸钙样品的球形度

L-谷氨酸添加量（质量分数）/%	球形度
0	—
1	0.816
2	0.889
3	0.935
4	0.951
5	0.843

图9 不同超重力水平下所制备的碳酸钙的SEM图

表4 不同超重力因子下碳酸钙样品的球形度

超重力因子	球形度
40.2	0.685
71.5	0.719
111.7	0.898
161.0	0.937
219.1	0.827

图10 不同pH下碳酸钙样品的红外光谱图

图11 L-谷氨酸中间体结构

图12 不同pH下取得样品的XRD图

图13 碳酸钙成球的机理示意图

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超重力反应结晶碳化法制备球形碳酸钙

Preparation of spherical calcium carbonate by high-gravity reaction crystallization carbonization

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