Preparation of spheroidal nano-calcium carbonate via high gravity-microinterface method

doi:10.16085/j.issn.1000-6613.2024-0731

Abstract

Abstract:

Using polyethyleneimine (PEI) as a morphological control agent, methanol as a dispersant, calcium hydroxide solution and CO₂ as raw materials, the preparation of spheroidal nano-calcium carbonate was investigated via a high gravity-microinterface method. The size of gas bubbles within the reactor was analyzed using a high-speed camera. The effects of reaction temperature, CO₂ flow rate, concentration of calcium hydroxide solution, volume fraction of methanol, and amount of PEI added on the morphology of the calcium carbonate product were investigated. An orthogonal experimental design was used to optimize the carbonation reaction conditions of calcium hydroxide. The morphology of the reaction products was characterized using SEM, XRD, and FTIR analytical methods. The results demonstrated that the high gravity-microinterface carbonation reactor effectively transformed CO₂ bubbles from millimeter scale to micrometer scale, enlarging the gas-liquid interfacial area and enhancing mass transfer between phases. The optimal conditions for the carbonation reaction of calcium hydroxide with CO₂ were found to be a calcium hydroxide concentration of 8%, a PEI addition of 4% by mass of calcium hydroxide, a methanol volume fraction of 20%, a CO₂ flow rate of 2.5L/min, and 12℃. Under these conditions, the prepared spheroidal nano-calcium carbonate particles ranged in size from 40nm to 60nm.

Key words: spheroidal nano-calcium carbonate, high gravity, microinterface, bubble, mass transfer

摘要：

以聚乙烯亚胺（PEI）为晶型控制剂、甲醇为分散剂、氢氧化钙溶液和CO₂为原料，采用超重力-微界面法进行类球形纳米碳酸钙制备研究。利用高速摄像机对反应器中气泡粒径进行分析；考察反应温度、CO₂流量、氢氧化钙溶液质量分数、甲醇体积分数、PEI添加量对碳酸钙产物形貌的影响；应用正交实验方法优化氢氧化钙碳化反应条件；利用扫描电子显微镜、X射线衍射和傅里叶变换红外光谱分析方法对反应产物的形貌进行表征。结果表明，超重力-微界面碳化反应器可以将CO₂气泡由毫米级高效转化为微米级，增大了气液相界面积，提高了气液传质；氢氧化钙与CO₂碳化反应最佳反应条件是氢氧化钙质量分数为8%、PEI添加量为氢氧化钙质量的4%、甲醇体积分数为20%、CO₂流量为2.5L/min、反应温度为12℃，所制备的类球形纳米碳酸钙粒径为40~60nm。

关键词: 类球形纳米碳酸钙, 超重力, 微界面, 气泡, 传质

CLC Number:

TQ13

SUN Jinlei, LIAO Dankui, CHEN Xiaopeng, TONG Zhangfa. Preparation of spheroidal nano-calcium carbonate via high gravity-microinterface method[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 3757-3769.

孙金磊, 廖丹葵, 陈小鹏, 童张法. 超重力-微界面法制备类球形纳米碳酸钙[J]. 化工进展, 2025, 44(7): 3757-3769.

Figures/Tables 14

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反应器类型	反应时间/min	CO₂气体流量/m³·h^-1	CO₂利用率/%
鼓泡碳化塔	50	1.4	10.39
超重力-微界面碳化反应装置	50	0.5	58.06

反应器类型	反应时间/min	CO₂气体流量/m³·h^-1	CO₂利用率/%
鼓泡碳化塔	50	1.4	10.39
超重力-微界面碳化反应装置	50	0.5	58.06

序号	温度/℃	PEI添加量/%	甲醇体积分数/%	CO₂流量/L·min^-1	氢氧化钙质量分数/%	球形度
序号	温度/℃	PEI添加量/%	甲醇体积分数/%	CO₂流量/L·min^-1	氢氧化钙质量分数/%	1	2	3	均值
a	12	4	25	2	6	0.91	0.912	0.902	0.908
b	12	5	15	2.5	7	0.929	0.914	0.923	0.922
c	12	6	20	3	8	0.947	0.944	0.947	0.946
d	12	7	30	3.5	9	0.847	0.858	0.851	0.852
e	15	4	15	3	9	0.916	0.925	0.922	0.921
f	15	5	25	3.5	8	0.888	0.883	0.887	0.886
g	15	6	30	2	7	0.882	0.885	0.882	0.883
h	15	7	20	2.5	6	0.918	0.911	0.916	0.915
i	18	4	20	3.5	7	0.888	0.889	0.884	0.887
j	18	5	30	3	6	0.93	0.929	0.925	0.928
k	18	6	25	2.5	9	0.916	0.919	0.916	0.917
l	18	7	15	2	8	0.869	0.864	0.868	0.867
m	21	4	30	2.5	8	0.879	0.872	0.871	0.874
n	21	5	20	2	9	0.848	0.853	0.855	0.852
o	21	6	15	3.5	6	0.814	0.821	0.816	0.817
p	21	7	25	3	7	0.802	0.809	0.807	0.806
K₁	3.628	3.59	3.517	3.51	3.568
K₂	3.605	3.588	3.527	3.628	3.498
K₃	3.599	3.563	3.6	3.601	3.573
K₄	3.349	3.44	3.537	3.442	3.542
k₁	1.209	1.197	1.172	1.170	1.189
k₂	1.207	1.196	1.176	1.209	1.166
k₃	1.200	1.188	1.200	1.200	1.191
k₄	1.116	1.147	1.179	1.147	1.181
R	0.093	0.050	0.028	0.062	0.025

序号	温度/℃	PEI添加量/%	甲醇体积分数/%	CO₂流量/L·min^-1	氢氧化钙质量分数/%	球形度
序号	温度/℃	PEI添加量/%	甲醇体积分数/%	CO₂流量/L·min^-1	氢氧化钙质量分数/%	1	2	3	均值
a	12	4	25	2	6	0.91	0.912	0.902	0.908
b	12	5	15	2.5	7	0.929	0.914	0.923	0.922
c	12	6	20	3	8	0.947	0.944	0.947	0.946
d	12	7	30	3.5	9	0.847	0.858	0.851	0.852
e	15	4	15	3	9	0.916	0.925	0.922	0.921
f	15	5	25	3.5	8	0.888	0.883	0.887	0.886
g	15	6	30	2	7	0.882	0.885	0.882	0.883
h	15	7	20	2.5	6	0.918	0.911	0.916	0.915
i	18	4	20	3.5	7	0.888	0.889	0.884	0.887
j	18	5	30	3	6	0.93	0.929	0.925	0.928
k	18	6	25	2.5	9	0.916	0.919	0.916	0.917
l	18	7	15	2	8	0.869	0.864	0.868	0.867
m	21	4	30	2.5	8	0.879	0.872	0.871	0.874
n	21	5	20	2	9	0.848	0.853	0.855	0.852
o	21	6	15	3.5	6	0.814	0.821	0.816	0.817
p	21	7	25	3	7	0.802	0.809	0.807	0.806
K₁	3.628	3.59	3.517	3.51	3.568
K₂	3.605	3.588	3.527	3.628	3.498
K₃	3.599	3.563	3.6	3.601	3.573
K₄	3.349	3.44	3.537	3.442	3.542
k₁	1.209	1.197	1.172	1.170	1.189
k₂	1.207	1.196	1.176	1.209	1.166
k₃	1.200	1.188	1.200	1.200	1.191
k₄	1.116	1.147	1.179	1.147	1.181
R	0.093	0.050	0.028	0.062	0.025

因素	离差平方和	自由度	均方	F值	显著性
温度	0.039	3	0.013	846.053	**
PEI	0.011	3	0.004	248.535	**
甲醇体积分数	0.003	3	0.001	68.518	**
CO₂流量	0.016	3	0.005	356.878	**
氢氧化钙浓度	0.003	3	0.001	57.635	**
误差	0	32	0	—	—