气泡扰动强化撞击流共沉淀法合成碳酸钙粉体

doi:10.11949/0438-1157.20250029

摘要/Abstract

摘要：

为了探究气泡扰动强化撞击流反应器制备碳酸钙（CaCO₃）粉体机制，通过撞击流共沉淀法，制备了具有不同晶体结构和含量的CaCO₃粉体，考察了气泡扰动下反应温度对CaCO₃晶体析出形式和转化过程的影响，研究了不同气液流量比下CaCO₃晶体的晶相含量、成核速率及粒径尺寸。实验结果表明，反应温度是影响晶体形貌的关键因素，随着温度升高，CaCO₃晶体析出形式依次为方解石、球霰石、文石。气泡扰动可有效调控CaCO₃晶体含量和粒径尺寸。随着气液流量比增大，球霰石型CaCO₃含量先降低后升高，成核速率先增大后减小，平均粒径先减小后增大。当气液流量比r=1.00时，产物中球霰石的含量达到最高水平，且平均粒径最小。为撞击流反应器可控制备CaCO₃提供了参考。

关键词: 撞击流反应器, 粒子, 粉体技术, 结晶, 碳酸钙

Abstract:

In order to investigate the mechanism of the preparation of calcium carbonate (CaCO₃) powders by the bubble disturbance enhanced impinging stream reactor, CaCO₃ powders with different crystal structures and contents were prepared by the impinging stream co-precipitation method. The effects of reaction temperature on the precipitation form and transformation process of CaCO₃ crystals under bubble disturbance were investigated, and the crystal phase content, nucleation rate and particle size of CaCO₃ crystals at different gas-liquid flow ratios were studied. The experimental results show that the reaction temperature is the key factor affecting the crystal morphology, and with the increase of temperature, the precipitation form of CaCO₃ crystals changes in the order of calcite, vaterite and aragonite. The bubble disturbance can effectively regulate the CaCO₃ crystal content and particle size. With the increase of gas-liquid flow ratio, the content of vaterite CaCO₃first decreases and then increases, the nucleation rate first increases and then decreases, and the average particle size first decreases and then increases. When the gas-liquid flow ratio r=1.00, the content of vaterite in the product reaches the highest level and the average particle size is the smallest. This research provides a reference for regulating the morphology of CaCO₃ crystals in impinging stream reactor.

Key words: impinging stream reactor, particle, powder technology, crystallized, calcium carbonate

中图分类号:

TQ 027.1

张建伟, 刘玉成, 董鑫, 冯颖. 气泡扰动强化撞击流共沉淀法合成碳酸钙粉体[J]. 化工学报, 2025, 76(8): 4052-4060.

Jianwei ZHANG, Yucheng LIU, Xin DONG, Ying FENG. Preparation of calcium carbonate by bubble disturbance enhanced impinging stream co-precipitation method[J]. CIESC Journal, 2025, 76(8): 4052-4060.

图/表 13

图1 撞击流反应器实验系统图1—feed bucket; 2—charge pump; 3—air pump; 4—gas flowmeter; 5—thermometer; 6—impinging stream reactor; 7—electromagnetic flowmeter; 8—intelligent temperature regulator; 9—discharge bucket; 10—circulating pump; 11—valve

Fig.1 Experimental system diagram of impinging stream reactor

图2 撞击流反应器结构图（单位：mm）

Fig.2 Structure of impinging stream reactor

表1 实验参数

Table 1 Experimental parameter

组别	反应温度T/℃	气液流量比r	组别	反应温度T/℃	气液流量比r
1	20	1.00	10	30	0.75
2	30	1.00	11	30	1.00
3	40	1.00	12	30	1.25
4	50	1.00	13	50	0
5	60	1.00	14	50	0.25
6	70	1.00	15	50	0.50
7	30	0	16	50	0.75
8	30	0.25	17	50	1.00
9	30	0.50	18	50	1.25

图3 碳酸钙制备实验工艺流程

Fig.3 Preparation process of calcium carbonate

图4 不同反应温度下制备的CaCO3的扫描电镜图

Fig.4 SEM images of CaCO3 prepared at different reaction temperatures

图5 不同反应温度下制备的CaCO3的XRD谱图

Fig.5 XRD patterns of CaCO3 prepared at different reaction temperatures

图6 不同反应温度下三种晶体形式溶解度的变化趋势

Fig.6 Trends in the solubility of the three crystals at different reaction temperatures

图7 不同反应温度下碳酸钙晶体析出形式转变过程

Fig.7 The transformation process of CaCO3 crystals at different reaction temperatures

图8 不同反应温度下CaCO3三种晶体的含量

Fig.8 Content of three crystals of CaCO3 at different reaction temperatures

图9 不同气液流量比下晶体含量

Fig.9 Content of crystals of CaCO3 at different gas-liquid flow ratio

图10 不同气液流量比下晶体粒数密度

Fig.10 Crystal particle number density under different gas-liquid flow ratio

表2 不同气液流量比下结晶动力学参数

Table 2 Crystallization kinetics parameters under different gas-liquid flow ratio

流量比 $r$	晶核粒数密度n⁰/(10⁹ μm^-1·ml^-1)	生长速率G/(μm/min)	成核速率B⁰/ (10⁸ ml^-1·min^-1)	悬浮密度M_T/(g/ml)
0	4.995	0.0432	2.159	0.0114
0.25	15.037	0.0386	5.810	0.0115
0.50	25.693	0.0322	8.265	0.0122
0.75	23.595	0.0332	7.843	0.0119
1.00	3.287	0.0581	1.910	0.0127
1.25	4.825	0.0497	2.397	0.0115

表2 不同气液流量比下结晶动力学参数

Table 2 Crystallization kinetics parameters under different gas-liquid flow ratio

流量比 $r$	晶核粒数密度n⁰/(10⁹ μm^-1·ml^-1)	生长速率G/(μm/min)	成核速率B⁰/ (10⁸ ml^-1·min^-1)	悬浮密度M_T/(g/ml)
0	4.995	0.0432	2.159	0.0114
0.25	15.037	0.0386	5.810	0.0115
0.50	25.693	0.0322	8.265	0.0122
0.75	23.595	0.0332	7.843	0.0119
1.00	3.287	0.0581	1.910	0.0127
1.25	4.825	0.0497	2.397	0.0115

图11 不同气液流量比下球霰石晶体的平均粒径

Fig.11 Mean particle size of vaterite at different gas-liquid flow ratio

参考文献 37

[9]	Yu H, Wang M, Zhou J, et al. Microreactor-assisted synthesis of α-alumina nanoparticles[J]. Ceramics International, 2020, 46(9): 13272-13281.
[10]	姚瀚植, 游攀, 张俊杰, 等. 微型Y型撞击流混合器强化快速沉淀反应可控制备碳酸锶微球[J]. 无机化学学报, 2022, 38(10): 2103-2110.
	Yao H Z, You P, Zhang J J, et al. Controllable preparation of strontium carbonate microspheres by fast precipitation reaction in a miniature Y-jet mixer[J]. Chinese Journal of Inorganic Chemistry, 2022, 38(10): 2103-2110.
[11]	Lin X Y, Wang K, Zhang J S, et al. Liquid-liquid mixing enhancement rules by microbubbles in three typical micro-mixers[J]. Chemical Engineering Science, 2015, 127: 60-71.
[12]	Zhang J W, Zhang J, Dong X, et al. Flow regime transition and bubble behavior in gas-liquid two-phase impinging jet reactor[J]. Chemical Engineering Research & Design, 2024, 201: 275-285.
[13]	Schlickmann K P, Howarth J L L, Silva D A K, et al. Effect of the incorporation of micro and nanoparticles of calcium carbonate in poly(vinyl chloride) matrix for industrial application[J]. Materials Research, 2019, 22: e20180870.
[14]	Chen P, Liu Y, Di M W. The effect of nano-filler on the damping properties of polyacrylic damping paint[J]. Advanced Materials Research, 2011, 1154(183/184/185): 2154-2157.
[15]	Svenskaya Y I, Fattah H, Inozemtseva O A, et al. Key parameters for size- and shape-controlled synthesis of vaterite particles[J]. Crystal Growth & Design, 2018, 18(1): 331-337.
[16]	Trushina D B, Bukreeva T V, Kovalchuk M V, et al. CaCO₃ vaterite microparticles for biomedical and personal care applications[J]. Materials Science and Engineering C, 2014, 45: 644-658.
[17]	Kawano J, Shimobayashi N, Miyake A, et al. Precipitation diagram of calcium carbonate polymorphs: its construction and significance[J]. Journal of Physics: Condensed Matter, 2009, 21(42): 425102.
[18]	Ma M G, Sun R C. Biomineralization and biomimetic synthesis of biomineral and nanomaterials[M]//Cavrak M. Advances in Biomimetics. Rijeka, Croatia: InTech, 2011. DOI:10.5772/13838 .
[19]	Ohgushi H, Okumura M, Yoshikawa T, et al. Bone formation process in porous calcium carbonate and hydroxyapatite[J]. Biomedical Materials, 1992, 26: 885-895.
[20]	Diego J R, Samuel S, G B L. The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite[J]. Nanoscale, 2011, 3(1): 265-271.
[21]	Liendo F, Arduino M, Deorsola F A, et al. Optimization of CaCO₃ synthesis through the carbonation route in a packed bed reactor[J]. Powder Technology, 2021, 377: 868-881.
[22]	Bots P, Benning L G, Rodriguez-Blanco J D, et al. Mechanistic insights into the crystallization of amorphous calcium carbonate (ACC)[J]. Crystal Growth & Design, 2012, 12(7): 3806-3814.
[23]	Declet A, Reyes E, Suárez O M. Calcium carbonate precipitation: a review of the carbonate crystallization process and applications in bioinspired composites[J]. Nanoscale, 2016, 44: 87-107.
[24]	Nehrke G, Cappellen V P. Framboidal vaterite aggregates and their transformation into calcite: a morphological study[J]. Journal of Crystal Growth, 2005, 287(2): 528-530.
[25]	Han Y S, Hadiko G, Fuji M, et al. Effect of flow rate and CO₂ content on the phase and morphology of CaCO₃ prepared by bubbling method[J]. Journal of Crystal Growth, 2005, 276(3/4): 541-548.
[26]	Hu Z S, Shao M H, Cai Q, et al. Synthesis of needle-like aragonite from limestone in the presence of magnesium chloride[J]. Journal of Materials Processing Technology, 2008, 209(3): 1607-1611.
[27]	Chang R, Choi D, Kim M H, et al. Tuning crystal polymorphisms and structural investigation of precipitated calcium carbonates for CO₂ mineralization[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(2): 1659-1667.
[28]	Udrea I, Capat C, Olaru E A, et al. Vaterite synthesis via gas-liquid route under controlled pH conditions[J]. Industrial & Engineering Chemistry Research, 2012, 51(24): 8185-8193.
[29]	Hu Q, Zhang J M, Teng H, et al. Growth process and crystallographic properties of ammonia-induced vaterite[J]. American Mineralogist, 2015, 97(8/9): 1437-1445.
[30]	Dai Y Z, Zou H F, Zhu H, et al. Controlled synthesis of calcite/vaterite/aragonite and their applications as red phosphors doped with Eu³⁺ ions[J]. CrystEngComm, 2017, 19(20): 2758-2767.
[31]	Flaten E M, Seiersten M, Andreassen J P. Polymorphism and morphology of calcium carbonate precipitated in mixed solvents of ethylene glycol and water[J]. Journal of Crystal Growth, 2009, 311(13): 3533-3538.
[32]	Hussein A I, Ab-Ghani Z, Mat A N C, et al. Synthesis and characterization of spherical calcium carbonate nanoparticles derived from cockle shells[J]. Applied Sciences, 2020, 10(20): 7170.
[33]	Huang Z Q, Huang Y Z, Yang A, et al. Formation and breakage of chain-like in preparation of nano-sized precipitated calcium carbonate[J]. Journal of Crystal Growth, 2025, 652: 128010.
[1]	伍沅. 撞击流性质及其应用[J]. 化工进展, 2001(11): 8-13.
	Wu Y. Properties and application of impinging streams[J]. Chemical Industry and Engineering Progress, 2001(11): 8-13.
[2]	Yue S, Liu X Q. Study of the drying characteristics in an asymmetric impinging stream reactor[J]. Chemical Papers, 2021, 8(75): 4355-4370.
[3]	方书起, 张欣悦, 李思齐, 等. 撞击流式反应器内水合物法分离沼气中CO₂研究[J]. 化工学报, 2020, 71(5): 2099-2108.
	Fang S Q, Zhang X Y, Li S Q . et al. Investigation on separation of CO₂ from biogas by hydrate method in impinging stream reactor[J]. CIESC Journal, 2020, 71(5): 2099-2108.
[4]	Chen L M, Dong B, Guo Y Q, et al. CFD modelling of the effects of local turbulence intensification on synthesis of LiFePO₄ particles in an impinging jet reactor[J]. Chemical Engineering and Processing-Process Intensification, 2020, 155: 11.
[5]	Dong B, Qian H L, Xue C Y, et al. Controllable synthesis of hierarchical micro/nano structured FePO₄ particles under synergistic effects of ultrasound irradiation and impinging stream[J]. Advanced Powder Technology, 2020, 10(31): 4292-4300.
[6]	Sahoo K, Kumar S. Green synthesis of sub 10 nm silver nanoparticles in gram scale using free impinging jet reactor[J]. Chemical Engineering and Processing-Process Intensification, 2021, 165: 12.
[7]	Zhang J W, Zhang J, Dong X, et al. Preparation of Ca(OH)₂ nanoparticles by impinging stream reaction precipitation method[J]. The Canadian Journal of Chemical Engineering, 2023, 101(12): 7251-7262.
[8]	Jiao W, Qin Y, Luo S, et al. Continuous preparation of nanoscale zero-valent iron using impinging stream-rotating packed bed reactor and their application in reduction of nitrobenzene[J]. Journal of Nanoparticle Research, 2017, 19(2): 52.
[34]	Kontoyannis C G, Vagenas N V. Calcium carbonate phase analysis using XRD and FT-Raman spectroscopy[J]. Analyst, 2000, 125(2): 251-255.
[35]	Shu Y D, Liu J J, Zhang Y, et al. Considering nucleation, breakage and aggregation in morphological population balance models for crystallization processes[J]. Computers & Chemical Engineering, 2020, 136: 106781-106781.
[36]	Khoshkhoo S, Anwar J. Crystallization of polymorphs: the effect of solvent[J]. Journal of Physics D: Applied Physics, 1993, 26: B90-B93.
[37]	Masayoshi T. Zeta potential of microbubbles in aqueous solutions: electrical properties of the gas-water interface[J]. The Journal of Physical Chemistry. B, 2005, 109(46): 21858-21864.