纳米纤维素嵌合型晶胶微球的多微管成形与模拟

doi:10.11949/0438-1157.20240027

化工学报 ›› 2024, Vol. 75 ›› Issue (5): 2060-2071.DOI: 10.11949/0438-1157.20240027

• 材料化学工程与纳米技术 • 上一篇下一篇

纳米纤维素嵌合型晶胶微球的多微管成形与模拟

王文雅¹^,²(), 张玮¹^,²(), 楼小玲³, 钟若菲³, 陈冰冰¹^,², 贠军贤³

^1.浙江工业大学机械工程学院，浙江杭州 310023
^2.浙江工业大学绿色制药技术与装备教育部重点实验室，浙江杭州 310023
^3.浙江工业大学化学工程学院绿色化学合成技术国家重点实验室培育基地，浙江杭州 310014

收稿日期:2024-01-05 修回日期:2024-03-14 出版日期:2024-05-25 发布日期:2024-06-25
通讯作者: 张玮
作者简介:王文雅（1998—），男，硕士研究生，wwenya2713@163.com
基金资助:
国家自然科学基金项目(22078296);浙江省自然科学基金重大项目(LD21B060001)

Multi-microtubes formation and simulation of nanocellulose-embedded cryogel microspheres

Wenya WANG¹^,²(), Wei ZHANG¹^,²(), Xiaoling LOU³, Ruofei ZHONG³, Bingbing CHEN¹^,², Junxian YUN³

^1.College of Mechanical Engineering, Zhejiang University of Technology, Hangzhou 310023, Zhejiang, China
^2.Key Laboratory for Green Pharmaceutical Technologies and Related Equipment of Ministry of Education, Zhejiang University of Technology, Hangzhou 310023, Zhejiang, China
^3.State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2024-01-05 Revised:2024-03-14 Online:2024-05-25 Published:2024-06-25
Contact: Wei ZHANG

摘要/Abstract

摘要：

利用多微管反应器，采用结晶致孔与低温聚合方法可实现纳米纤维素嵌合型晶胶微球的规模化制备。该过程中内嵌纳米纤维素的甲基丙烯酸羟乙酯单体溶液经多微管反应器的成形是首要条件，研究其成形过程的动力学特性具有重要意义。利用高速成像和计算流体力学（CFD）模拟方法对不同入口流速（6、8、10 mm·s^-1）下内嵌不同比例（单体质量的1%、3%、5%）纳米纤维素的甲基丙烯酸羟乙酯液滴形成过程进行可视化研究，考察了纳米纤维素含量对液滴成形、液滴直径分布、颈缩线长度、液滴下落速度等因素的影响规律。结果表明，内嵌纳米纤维素的甲基丙烯酸羟乙酯液滴经多微管反应器的成形及滴落，会经历拉伸与压缩过程，最后稳定为球状，测得液滴直径和颈缩线长度与纤维素浓度呈正相关，纤维素含量的增加使得单体溶液黏度和表面张力系数增加，从而增大液滴尺寸和颈缩线长度，模拟得到的结果与实验基本一致，液滴直径差异为2.1%~6.3%，颈缩线长度差异为7.2%~11.9%；在对液滴成形的放大模拟中，10 mm·s^-1的入口流速下液滴平均直径为3.98 mm，平均颈缩线长为4.14 mm。最终，利用多微管反应器成功制备了纳米纤维素嵌合型晶胶微球，微球有效孔隙率可达80%以上，绝干孔隙率接近90%，是生物分离领域与微生物贴壁生长的理想载体。

关键词: 嵌合型晶胶微球, 纳米纤维素, 多微管反应器, 液滴, 动力学, 成像, 数值模拟

Abstract:

The large-scale preparation of nanocellulose-embedded cryogel microspheres can be realized by crystallization pore-forming and low-temperature polymerization in a multi-microtube reactor. In this process, the formation of hydroxyethyl methacrylate monomer solution embedded with nanocellulose through multi-microtube reactor is the primary condition. It is of great significance to study the dynamic characteristics of the forming process. Using high-speed imaging and computational fluid dynamics (CFD) simulation methods, the droplet formation process of hydroxyethyl methacrylate embedded with different proportions (1%, 3%, 5% of monomer mass) of nanocellulose at different inlet flow rates (6, 8, 10 mm·s^-1) was visualized. The effects of nanocellulose content on droplet formation, droplet diameter distribution, necking line length, droplet falling speed and other factors were investigated. The results show that the hydroxyethyl methacrylate droplets embedded with nanocellulose undergo stretching and compression processes after forming and dripping in a multi-microtube reactor, and finally stabilized into a spherical shape. The measured droplet diameter and necking line length were positively correlated with the cellulose concentration in the monomer solution. The increase of cellulose content increased the viscosity and surface tension coefficient of the monomer solution, thus increasing the droplet size and necking line length. The simulation results are basically consistent with the experimental results. The difference of droplet diameter is 2.1%—6.3%, and the difference of necking line length is 7.2%—11.9%. In the amplification simulation of droplet formation, the average droplet diameter is 3.98 mm and the average necking line length is 4.14 mm at the inlet velocity of 10 mm·s^-1. Finally, a multi-microtube reactor was used to successfully prepare nanocellulose chimeric crystalline microspheres. The effective porosity of the microspheres can reach more than 80%, and the absolute dry porosity is close to 90%. It is an ideal carrier for the field of biological separation and the adherent growth of microorganisms.

Key words: chimeric crystal glue microspheres, nanocellulose, multi-microtube reactor, droplet, kinetics, imaging, numerical simulation

中图分类号:

TQ 028

王文雅, 张玮, 楼小玲, 钟若菲, 陈冰冰, 贠军贤. 纳米纤维素嵌合型晶胶微球的多微管成形与模拟[J]. 化工学报, 2024, 75(5): 2060-2071.

Wenya WANG, Wei ZHANG, Xiaoling LOU, Ruofei ZHONG, Bingbing CHEN, Junxian YUN. Multi-microtubes formation and simulation of nanocellulose-embedded cryogel microspheres[J]. CIESC Journal, 2024, 75(5): 2060-2071.

图/表 19

图1 多微管反应器的几何模型

Fig.1 Geometric model of multi-microtube reactor

图2 计算域1,4—velocity inlet; 2,5—wall; 3,6—pressure outlet

Fig.2 Computational region

表1 流体的物性参数

Table 1 Physical parameters of fluid

Phase	$ρ$ /（g·cm^-3）	$μ$ /（mPa·s）	$σ$ /（mN·m^-1）
1% monomer solution	1.0178	2.08	48.7
3% monomer solution	1.0206	2.41	49.0
5% monomer solution	1.0237	3.16	49.6
air	1.225	1.7894×10^-2

表1 流体的物性参数

Table 1 Physical parameters of fluid

Phase	$ρ$ /（g·cm^-3）	$μ$ /（mPa·s）	$σ$ /（mN·m^-1）
1% monomer solution	1.0178	2.08	48.7
3% monomer solution	1.0206	2.41	49.0
5% monomer solution	1.0237	3.16	49.6
air	1.225	1.7894×10^-2

图3 网格无关性验证

Fig.3 Grid independence verification

图4 放大模拟的几何模型

Fig.4 Geometric model of magnification simulation

图5 放大模拟的计算域1,2,5,6—symmetry; 3,7—velocity inlet; 4,8—pressure outlet

Fig.5 Computational region of magnification simulation

图6 纤维素含量1%的液滴形态变化

Fig.6 Morphological changes of droplets with cellulose content of 1%

表2 实验得到的SF值随液滴下落高度的变化

Table 2 Change of experimental SF value with falling height

Distance from nozzle/mm	SF
5.17—6.12	0.029
6.50—7.45	0.071
7.75—8.23	0.040
9.47—15.82	0.159
16.27—17.22	0.025

图7 纤维素含量1%的液滴形态模拟图

Fig.7 Simulation diagram of droplets with 1% cellulose content

表3 模拟得到的SF值随液滴下落高度的变化

Table 3 Change of simulated SF value with falling height

Distance from nozzle/mm	SF
4.51—5.40	0.027
6.18—7.33	0.116
7.65—8.03	0.014
8.80—14.56	0.083
15.92—19.49	0.002

图8 不同时刻液滴轴向速度变化

Fig.8 Axial velocity variation of droplets at different time

图9 颈缩线断裂时的速度云图

Fig.9 Velocity cloud diagram when necking line breaks

图10 不同纤维素含量下实验与模拟得到的液滴直径

Fig.10 Droplet diameter obtained by experiment and simulation under different cellulose content

图11 不同纤维素含量下实验与模拟得到的液滴颈缩线长度

Fig.11 Length of droplet necking line obtained by experiment and simulation under different cellulose contents

图12 放大模拟得到的液滴形态变化图

Fig.12 Droplet shape change diagram obtained by magnification simulation

图13 液滴直径分布

Fig.13 Droplet diameter distribution

图14 纤维素嵌合型晶胶微球的宏观形态和粒径分布

Fig.14 Macroscopic morphology and particle size distribution of cellulose chimeric cryogel microspheres

图15 纤维素嵌合型晶胶微球的内部微观结构

Fig.15 Internal microstructure of cellulose-embedded cryogel microspheres

表4 晶胶微球的孔隙率

Table 4 Porosity of crystal microspheres

质量比 [细菌纤维素∶(HEMA+PEGDA)]	有效孔隙率/ %（质量）	绝干孔隙率/ %（质量）
1∶100	83.41	90.80
3∶100	81.43	88.57
5∶100	80.35	87.65

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纳米纤维素嵌合型晶胶微球的多微管成形与模拟

Multi-microtubes formation and simulation of nanocellulose-embedded cryogel microspheres

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