低温碳化法制备高分散性纳米碳酸钙的研究

人工晶体学报 ›› 2024, Vol. 53 ›› Issue (5): 864-872.

低温碳化法制备高分散性纳米碳酸钙的研究

邢佳斌, 李威, 贾松岩, 马亚丽, 李雪, 郑强

1.沈阳化工大学化学工程学院,沈阳 110142;
2.辽宁省镁钙无机功能材料工程研究中心,沈阳 110142;
3.沈阳市镁钙资源利用技术重点实验室,沈阳 110142

收稿日期:2023-12-19 出版日期:2024-05-15 发布日期:2024-05-21
通信作者: 郑强,博士,讲师。E-mail:zhengq_neu@163.com
作者简介:邢佳斌(1997—),男,辽宁省人,硕士研究生。E-mail:820798796@qq.com
基金资助:
辽宁省教育厅青年研究项目(JYTQN2023368);2020—2022年辽宁省普通本科高等学校校际合作项目(辽教发〔2020〕28号文件);2021—2023年辽宁省科技厅创新能力提升联合基金(2021-NLTS-12-04)

Preparation of Highly Dispersed Nano Calcium Carbonate by Low-Temperature Carbonization Method

XING Jiabin, LI Wei, JIA Songyan, MA Yali, LI Xue, ZHENG Qiang

1. College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China;
2. Liaoning Engineering Research Center for Magnesium and Calcium Inorganic Functional Materials, Shenyang 110142, China;
3. Shenyang Key Laboratory for the Utilization Technology of Magnesium and Calcium Resources, Shenyang 110142, China

Received:2023-12-19 Online:2024-05-15 Published:2024-05-21

摘要/Abstract

摘要： 以石灰石为原料,采用低温碳化法制备了高分散性纳米碳酸钙。通过XRD、SEM、TEM等对纳米碳酸钙样品进行表征,考察了浆料比、碳化温度、CO₂通气速率、陈化时间、晶型控制剂对纳米碳酸钙粒径和分散程度的影响。研究结果表明,制备纳米碳酸钙的最佳工艺条件为:浆料比为5%,碳化温度为15 ℃,CO₂通气速率为200 mL/min,陈化时间2 h,并选用ZnCl₂为添加剂。在此条件下,制得晶粒尺寸为25~35 nm、分布均匀的立方体状纳米碳酸钙。结合Materials Studio对纳米碳酸钙的生长机理进行了分析,结果表明:碳酸钙的(104)和(116)2个晶面具有热力学稳定性,最终会成为顽强显露的晶面,促使生成立方体型纳米碳酸钙。

关键词: 石灰石, 纳米碳酸钙, 低温碳化法, 晶体生长, 生长机理, 晶型控制剂

Abstract: Highly dispersed nano calcium carbonate was prepared using limestone as raw material by low-temperature carbonization method. The nano calcium carbonate samples were characterized by XRD, SEM, TEM, etc. The effects of slurry ratio, carbonization temperature, CO₂ aeration rate, aging time, and crystal control agent on the particle size and dispersion degree of nano calcium carbonate were investigated. The process conditions for preparing nano calcium carbonate were obtained as follows: slurry ratio of 5%, carbonization temperature of 15 ℃, CO₂ aeration rate of 200 mL/min, aging time of 2 h, and ZnCl₂ as the crystal control agent. Under these conditions, cubic nano calcium carbonate with a grain size of 25~35 nm and uniform distribution was prepared. The growth mechanism of nano calcium carbonate was analyzed by Materials Studio. The results show that the (104) and (116) crystal planes of calcium carbonate were thermodynamically stable and would eventually become tenacious exposed crystal planes, which promots the generation of cubic nano calcium carbonate.

Key words: limestone, nano calcium carbonate, low-temperature carbonization, crystal growth, growth mechanism, crystalline controlling agent

中图分类号:

邢佳斌, 李威, 贾松岩, 马亚丽, 李雪, 郑强. 低温碳化法制备高分散性纳米碳酸钙的研究[J]. 人工晶体学报, 2024, 53(5): 864-872.

XING Jiabin, LI Wei, JIA Songyan, MA Yali, LI Xue, ZHENG Qiang. Preparation of Highly Dispersed Nano Calcium Carbonate by Low-Temperature Carbonization Method[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(5): 864-872.

参考文献

[1] BARHOUM A, VAN ASSCHE G, MAKHLOUF A S H, et al. A green, simple chemical route for the synthesis of pure nanocalcite crystals[J]. Crystal Growth & Design, 2015, 15(2): 573-580.
[2] 汤勇, 唐名德, 焦妍惠, 等. 加压碳酸化法制备片状纳米碳酸钙及其表征[J]. 材料导报, 2023, 37(17): 126-132.
TANG Y, TANG M D, JIAO Y H, et al. Preparation and characterization of flake-like nano calcium carbonate by pressurized carbonation[J]. Materials Reports, 2023, 37(17): 126-132 (in Chinese).
[3] NESSIA E, DIMOLIANIA M, PAPADOPOULOSA A I, et al. Experimental testing for calcium carbonate nanoparticles production in a rotating packed bed[J]. Chemical Engineering Transactions, 2022, 94: 727-732.
[4] 邓晓阳, 郑强, 曲笑原, 等. 白云石制备似立方体状方解石型碳酸钙晶体及其机理研究[J]. 人工晶体学报, 2022, 51(4): 704-715.
DENG X Y, ZHENG Q, QU X Y, et al. Preparation of near cube form calcite type calcium carbonate crystal from dolomite and its mechanism[J]. Journal of Synthetic Crystals, 2022, 51(4): 704-715 (in Chinese).
[5] RANJAN R, NARNAWARE S D, PATIL N V. A novel technique for synthesis of calcium carbonate nanoparticles[J]. National Academy Science Letters, 2018, 41(6): 403-406.
[6] CHESNEAU C, SOW A O, HAMACHI F, et al. Cyclodextrin-calcium carbonate micro- to nano-particles: targeting vaterite form and hydrophobic drug loading/release[J]. Pharmaceutics, 2023, 15(2): 653.
[7] CAO M L, YUAN X L, MING X, et al. Effect of high temperature on compressive strength and microstructure of cement paste modified by micro- and nano-calcium carbonate particles[J]. Fire Technology, 2022, 58(3): 1469-1491.
[8] ZHAO T B, XU C, MA Y T, et al. Study on preparation and structure of chrysanthemum-shaped micron calcium carbonate based on inverse microemulsion[J]. Micro & Nano Letters, 2020, 15(15): 1151-1155.
[9] 苏晴, 燕溪溪, 王爽, 等. 影响纳米碳酸钙性能的制备方法研究进展[J]. 上海第二工业大学学报, 2021, 38(3): 175-183.
SU Q, YAN X X, WANG S, et al. Research progress of preparation methods affecting the properties of nano calcium carbonate[J]. Journal of Shanghai Polytechnic University, 2021, 38(3): 175-183 (in Chinese).
[10] 程娜, 周梅芳, 陈鹏宇, 等. 碳化法可控制备纳米碳酸钙研究进展[J]. 过程工程学报, 2017, 17(2): 412-419.
CHENG N, ZHOU M F, CHEN P Y, et al. Controlled synthesis of nano-calcium carbonate via carbonization method: a review[J]. The Chinese Journal of Process Engineering, 2017, 17(2): 412-419 (in Chinese).
[11] YANG A M, HUANG Z Q, ZHU Y, et al. Preparation of nano-sized calcium carbonate in solution mixing process[J]. Journal of Crystal Growth, 2021, 571: 126247.
[12] 刘越, 郑强, 邢佳斌, 等. 石灰石干法制备高性能氢氧化钙的工艺及应用研究[J]. 无机盐工业, 2023, 55(10): 42-49+85.
LIU Y, ZHENG Q, XING J B, et al. Study on process and application of high-performance calcium hydroxide prepared by dry digestion from limestone[J]. Inorganic Chemicals Industry, 2023, 55(10): 42-49+85 (in Chinese).
[13] RACCA L M, BERTOLINO L C, NASCIMENTO C R, et al. Myristic acid as surface modifier of calcium carbonate hydrophobic nanoparticles[J]. Journal of Nanoparticle Research, 2019, 21(11): 232.

[1]	艾家辛, 万洪平, 钱俊兵, 韦华. VGF法磷化铟单晶炉加热器对炉内热场分布影响的研究[J]. 人工晶体学报, 2024, 53(5): 781-791.
[2]	黄昌保, 胡倩倩, 朱志成, 李亚, 毛长宇, 徐俊杰, 吴海信, 倪友保. 中长波Cr²⁺/Fe²⁺∶CdSe激光晶体生长及元件制备[J]. 人工晶体学报, 2024, 53(4): 551-553.
[3]	秦峰, 吴金杰, 邓宁勤, 焦志伟, 朱伟峰, 汤显强, 赵瑞. 基于溶液法制备卤化铅钙钛矿的直接型辐射探测器研究进展[J]. 人工晶体学报, 2024, 53(4): 554-571.
[4]	曹聪, 刘江高, 范叶霞, 李振兴, 周振奇, 马启司, 牛佳佳. 碲锌镉晶体生长温度梯度与界面形状稳定性关系的研究[J]. 人工晶体学报, 2024, 53(4): 641-648.
[5]	王萌萌, 尹延如, 丁晓圆, 张晶, 付秀伟, 贾志泰, 陶绪堂. 倍半氧化物晶体及其1~3 μm波段激光性能研究进展[J]. 人工晶体学报, 2023, 52(7): 1169-1194.
[6]	刘小虎, 李坚富, 朱昭捷, 涂朝阳, 王阁阳, 杨金芳, 朱江峰, 王燕. Yb∶CaGdAlO₄晶体及其超快激光技术研究进展[J]. 人工晶体学报, 2023, 52(7): 1195-1207.
[7]	孙贵花, 张庆礼, 李加红, 罗建乔, 王小飞, 高进云. Yb,Ho∶GdScO₃晶体生长及光谱性能分析[J]. 人工晶体学报, 2023, 52(7): 1243-1249.
[8]	刘青雄, 王天予, 刘孚安, 吴倩, 尹延如, 赫崇君, 高泽亮, 夏明军. 非线性光学晶体K₃B₆O₁₀Br的生长与光电性能研究[J]. 人工晶体学报, 2023, 52(7): 1296-1301.
[9]	颜涛, 范雨杰, 徐峰, 陈昱, 罗敏. KLi(HC₃N₃O₃)·2H₂O晶体的电光效应和生长研究[J]. 人工晶体学报, 2023, 52(7): 1302-1307.
[10]	魏玲莉, 倪友保, 黄昌保, 吴海信, 王振友, 胡倩倩, 余学舟, 刘国晋, 周强. 大尺寸ZnTe晶体的生长与性能[J]. 人工晶体学报, 2023, 52(7): 1317-1324.
[11]	郭俊, 刘坚, 陈鹏, 宋青松, 张志恒, 徐晓东, 徐军. Nd∶CaYAlO₄单晶光纤的生长及光谱性能研究[J]. 人工晶体学报, 2023, 52(7): 1345-1351.
[12]	隋占仁, 徐凌波, 崔灿, 王蓉, 杨德仁, 皮孝东, 韩学峰. 数值模拟顶部籽晶溶液生长法制备单晶碳化硅的研究进展[J]. 人工晶体学报, 2023, 52(6): 1067-1085.
[13]	张鑫, 沈俊, 湛立, 崔恒清, 葛炳辉, 武传强. 枝晶WS₂/单层WS₂薄膜的CVD可控制备与表征[J]. 人工晶体学报, 2023, 52(5): 909-917.
[14]	李大鹏, 孙国富, 葛素香. 溶剂热法制备金属酞菁晶体的研究进展[J]. 人工晶体学报, 2023, 52(4): 678-687.
[15]	丁羽, 张金才, 王宝凤, 郭彦霞, 薛芳斌, 程芳琴. 电石渣可控制备多晶型、多形貌纳米碳酸钙的研究进展[J]. 人工晶体学报, 2023, 52(4): 710-720.