陶瓷膜分离技术及其在生物制造领域的应用进展

doi:10.16085/j.issn.1000-6613.2023-1042

化工进展 ›› 2024, Vol. 43 ›› Issue (8): 4550-4561.DOI: 10.16085/j.issn.1000-6613.2023-1042

• 生物与医药化工 • 上一篇

陶瓷膜分离技术及其在生物制造领域的应用进展

张锐¹(), 江静¹, 徐鸿飞¹, 杨盛凯¹, 李亚红¹, 周靖原¹, 曾坚贤¹(), 黄小平¹, 刘鹏飞¹, 张明明², 李志强³

^1.湖南科技大学化学化工学院，湖南湘潭 411201
^2.湖南科技大学国有资产与实验室管理处，湖南湘潭 411201
^3.湖南恒辉膜科技有限公司，湖南长沙 410205

收稿日期:2023-06-25 修回日期:2023-12-11 出版日期:2024-08-15 发布日期:2024-09-02
通讯作者: 曾坚贤
作者简介:张锐（1987—），男，博士，研究方向为生物化工及膜分离技术。E-mail: 245945581@qq.com。
基金资助:
湖南省自然科学基金(2022JJ30238);湖南省教育厅重点科学研究项目(21A0291);大学生创新创业训练计划(S202310534060)

Progress of ceramic membrane separation technology and its application in bio-manufacturing field

ZHANG Rui¹(), JIANG Jing¹, XU Hongfei¹, YANG Shengkai¹, LI Yahong¹, ZHOU Jingyuan¹, ZENG Jianxian¹(), HUANG Xiaoping¹, LIU Pengfei¹, ZHANG Mingming², LI Zhiqiang³

^1.College of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, Hunan, China
^2.Office of Asset Management and Laboratory Management, Hunan University of Science and Technology, Xiangtan 411201, Hunan, China
^3.Hunan Evershine Membrane Technology Co. , Ltd. , Changsha 410205, Hunan, China

Received:2023-06-25 Revised:2023-12-11 Online:2024-08-15 Published:2024-09-02
Contact: ZENG Jianxian

摘要/Abstract

摘要：

陶瓷膜分离技术因具有高通量、抗污性能好、易清洗、生命周期长等优点而得到广泛应用。然而，受限于对陶瓷膜的特点、优势和用途等方面的认知，该技术在飞速发展的生物制造领域应用相对有限。本文首先介绍了陶瓷膜分离技术及分类，简述了陶瓷膜的优势以及陶瓷膜组件和国内外生产厂家。此外，重点综述了生物制药、生物基材料、生物能源、大宗发酵产品和发酵食品饮料等生物制造领域的产品特点以及陶瓷膜的应用实例，并根据发酵液的分离目的，从膜的材料、结构、孔径、操作和清洗方法等方面分析了陶瓷膜的选择策略。最后，指出了低成本和高分离精度的陶瓷膜研发是拓宽其在生物制造领域应用的重要方向，同时，进一步积累陶瓷膜在生物制造领域的应用案例和数据，提高产品质量和膜的使用寿命，降低成本，将促进陶瓷膜技术在快速发展的生物制造领域更加广泛的应用，落实“双碳”战略目标。

关键词: 生物分离, 膜, 发酵, 陶瓷, 生物制造

Abstract:

Ceramic membrane separation technology is widely used due to the advantages of high flux, good anti-fouling performance, easy cleaning, and long lifespan. However, the limited understanding of the characteristics, advantages and uses of ceramic membrane has greatly restricted the application of this technology in the fast-developing field of bio-manufacturing industry in the past years. This paper introduced the ceramic membrane separation technology and classification, and described the advantages of ceramic membranes and domestic and foreign manufacturers. The bio-product characteristics and application examples of ceramic membrane in bio-manufacturing fields including biopharmaceuticals, bio-based materials, bioenergy, bulk fermented products and fermented food and beverage were reviewed systematically. The selection strategies for ceramic membranes application were analyzed from the aspects of membrane material, configuration, pore size, operation and cleaning method according to the separation purpose of fermentation liquid. The article pointed out that the development of ceramic membrane with low cost and high separation accuracy was an important direction to expand its application in bio-manufacturing field. Meanwhile, further accumulating ceramic membrane application cases and data in bio-manufacturing fields in future researches, improving product quality and membrane lifespan, and reducing the cost would promote more extensive application of the ceramic membrane technology in the fast-developing bio-manufacturing industry, and the implement of the carbon peaking and carbon neutrality goals.

Key words: bioseparation, membranes, fermentation, ceramics, bio-manufacturing

中图分类号:

TQ028

张锐, 江静, 徐鸿飞, 杨盛凯, 李亚红, 周靖原, 曾坚贤, 黄小平, 刘鹏飞, 张明明, 李志强. 陶瓷膜分离技术及其在生物制造领域的应用进展[J]. 化工进展, 2024, 43(8): 4550-4561.

ZHANG Rui, JIANG Jing, XU Hongfei, YANG Shengkai, LI Yahong, ZHOU Jingyuan, ZENG Jianxian, HUANG Xiaoping, LIU Pengfei, ZHANG Mingming, LI Zhiqiang. Progress of ceramic membrane separation technology and its application in bio-manufacturing field[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4550-4561.

图/表 12

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材料	亲水性	渗透性	抗污性	耐化学腐蚀性	机械强度	经济性
Al₂O₃	+	++	+++++	+++	++++	+++++
TiO₂	++	++	+++	+++	++++	++++
ZrO₂	++++	+++	++	++++	+++++	+++
SiC	+++++	+++++	+	+++++	+++++	++

材料	亲水性	渗透性	抗污性	耐化学腐蚀性	机械强度	经济性
Al₂O₃	+	++	+++++	+++	++++	+++++
TiO₂	++	++	+++	+++	++++	++++
ZrO₂	++++	+++	++	++++	+++++	+++
SiC	+++++	+++++	+	+++++	+++++	++

参数	微滤（MF）	超滤（UF）	纳滤（NF）
孔径类型	大孔	介孔	微孔
过滤精度	>50nm	2~50nm/1~500kDa	<2nm/200~800Da
操作压力/MPa	<0.2	0.1~1	0.5~3.5
典型应用	微生物分离或细胞碎片过滤；多聚体净化；酶制剂澄清；RO/NF预处理	细菌病毒截留；抗生素澄清；酶制剂浓缩；蛋白质浓缩；糖类色素去除；蛋白质、肽的分离、分级与浓缩；酱油过滤	抗生素浓缩；脱色；BOD/COD脱除；有机酸的回收和浓缩；脱盐

参数	微滤（MF）	超滤（UF）	纳滤（NF）
孔径类型	大孔	介孔	微孔
过滤精度	>50nm	2~50nm/1~500kDa	<2nm/200~800Da
操作压力/MPa	<0.2	0.1~1	0.5~3.5
典型应用	微生物分离或细胞碎片过滤；多聚体净化；酶制剂澄清；RO/NF预处理	细菌病毒截留；抗生素澄清；酶制剂浓缩；蛋白质浓缩；糖类色素去除；蛋白质、肽的分离、分级与浓缩；酱油过滤	抗生素浓缩；脱色；BOD/COD脱除；有机酸的回收和浓缩；脱盐

膜类型	聚合物膜	陶瓷膜
优点	成本低（约100元/平米）；选择性好；容易制备	耐酸、耐碱、耐高温、耐有机溶剂；机械强度大、稳定性好、通量大、占用空间小、能耗低；抗污染性能好；孔径分布窄，分离时无须相变，分离效率高；可靠性高和生命周期长（15~20年）
缺点	抗污染性能低；不耐强化学腐蚀；有限的“工作温度和压力”；生命周期短暂（1~3年）	生产工艺复杂，烧结后产品性能差异化大；价格较高（450~600CNY/m²）；产品脆性大

陶瓷膜分离技术及其在生物制造领域的应用进展

Progress of ceramic membrane separation technology and its application in bio-manufacturing field

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构型	污染趋势	装填密度	滞留体积	易于清洗	能源消耗
平板	中	中	低	好	中
管式	低	低	高	优秀	高
中空纤维	高	高	低	一般	低
板框式	中	中	低	好	中
卷式	中/高	中/高	低	一般	低

公司	国家	膜材料	膜元件	公司网站
久吾高科	中国	Al₂O₃、ZrO₂	管式	http://www.jiuwu.com/
山东工业陶瓷研究设计院	中国	Al₂O₃、SiC	管式，平板	http://www.zcfilter.com/
国初科技	中国	Al₂O₃、TiO₂、ZrO₂	管式	http://www.guochukeji.com/
合肥世杰	中国	Al₂O₃、ZrO₂、TiO₂	管式	http://www.sjm-filter.com.cn/
TAMI	法国	ZrO₂、TiO₂	管式	https://www.tami-industries.com/
Pall	美国	Al₂O₃ 、ZrO₂、TiO₂	管式	https://www.pall.com/
Inopor	德国	Al₂O₃、ZrO₂、TiO₂、SiO₂	管式，平板	https://www.inopor.com/de/
Hydroair	意大利	Al₂O₃	管式	https://www.gmmpfaudler.com/
Mantec	意大利	ceramic membrane (NA)	管式，平板	https://mantectechnicalceramics.com/
Delemil	美国	ceramic membrane (NA)	管式	http://cn.delemil.cn/
Meidensha	日本	α-Al₂O₃、ZrO₂	平板	https://www.meidensha.co.jp/
NGK Insulators,Ltd.	日本	Al₂O₃、TiO₂	管式	https://www.ngk.co.jp/
Delemil	美国	ceramic membrane (NA)	管式	http://cn.delemil.cn/
Ceraflo	新加坡	Al₂O₃、ZrO₂、TiO₂	平板	http://www.ceraflo.cn/
Tritech	新加坡	Al₂O₃、ZrO₂、TiO₂	中空纤维	http://www.tritechgrp.cn/
LiqTech	丹麦	SiC	管式，平板	https://liqtech.com/
Cembrane	丹麦	SiC	平板	https://www.cembrane.com/
Novasep	法国	ceramic membrane (NA)	管式	http://www.novasep.com.cn/
PWNT	荷兰	ceramic membrane (NA)	管状	https://pwntechnologies.com/
ItN-Nanovation	德国	Al₂O₃	平板	http://www.itn-nanovation.com/

组分	分子量/Da	尺寸/nm
酵母和真菌	—	10³~10⁴
细菌	—	300~10⁴
胶体	—	100~10³
病毒	—	30~300
蛋白质、多糖、酶	10⁴~10⁶	2~10
抗体	300~10³	0.6~1.2
抗生素	300~1200	0.6~1.3
单糖	200~400	0.8~1.0
有机酸	100~500	0.4~0.8
氨基酸	70~200	0.3~0.8
无机离子	10~100	0.2~0.4

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