陶瓷膜用于杜仲叶提取液澄清的分离特性与膜污染机制研究

doi:10.11949/0438-1157.20221347

化工学报 ›› 2023, Vol. 74 ›› Issue (3): 1113-1125.DOI: 10.11949/0438-1157.20221347

陶瓷膜用于杜仲叶提取液澄清的分离特性与膜污染机制研究

王思琪¹(), 顾天宇¹, 陈献富¹, 王通², 李佳², 柯威², 李小锋³, 范益群¹()

^1.南京工业大学化工学院，材料化学工程国家重点实验室，江苏南京 210009
^2.南京膜材料产业技术研究院有限公司，江苏南京 211800
^3.江西普正制药股份有限公司，江西吉安 343199

收稿日期:2022-10-12 修回日期:2023-01-26 出版日期:2023-03-05 发布日期:2023-04-19
通讯作者: 范益群
作者简介:王思琪(1998—)，女，硕士研究生，wsq1365180706@163.com
基金资助:
国家自然科学基金项目(21921006);江西省科技厅“揭榜挂帅”项目(20213AAG02022)

Study on separation characteristics and membrane fouling mechanism of ceramic membrane for clarification of Eucommia ulmoides leaves extract

Siqi WANG¹(), Tianyu GU¹, Xianfu CHEN¹, Tong WANG², Jia LI², Wei KE², Xiaofeng LI³, Yiqun FAN¹()

^1.State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu, China
^2.Nanjing Membrane Materials Industry Technology Research Institute Co. , Ltd. , Nanjing 211800, Jiangsu, China
^3.Jiangxi Puzheng Pharmaceutical Co. , Ltd. , Ji’an 343199, Jiangxi, China

Received:2022-10-12 Revised:2023-01-26 Online:2023-03-05 Published:2023-04-19
Contact: Yiqun FAN

摘要/Abstract

摘要：

杜仲是我国特有的珍稀中药材树种且资源丰富，其树叶富含绿原酸和黄酮类化合物等活性物质。然而，杜仲叶提取液中杜仲胶、蛋白、多糖等杂质含量较高，缺乏活性物质的高效分离技术。陶瓷膜具有分离效率高、抗污染性能好等优势，已在植物提取液的澄清过程中广泛应用。开发杜仲叶提取液的陶瓷膜法高效澄清技术具有重要应用价值。本文从膜材料和膜过程两个层面展开研究，对陶瓷膜孔径进行了优选，系统考察了操作压力、膜面流速与温度对陶瓷膜澄清过程的影响，并结合Hermia模型对膜污染机制进行了分析。结果表明，平均孔径为100 nm的陶瓷微滤膜具有较高的浊度去除率、活性成分透过率和渗透通量，适合杜仲叶提取液的澄清过程。在优化的操作条件下，陶瓷微滤膜的稳定通量约为58 L·m^-2·h^-1，绿原酸与黄酮的总透过率为75.3%，浊度截留率接近100%，清洗后膜通量恢复率达85%以上。陶瓷膜分离技术在杜仲叶提取液澄清过程中展现了良好的应用前景。

关键词: 膜, 分离, 澄清, 陶瓷膜, 杜仲叶, 膜污染

Abstract:

Eucommia ulmoides is a rare Chinese herbal medicine tree specie unique to China and is affluent in resources. Its leaves are rich in active substances such as chlorogenic acid and flavonoids. However, the content of gutta percha, protein, polysaccharide and other impurities in the extract of Eucommia ulmoides leaves is high. There is a lack of efficient separation technology for active substances. Ceramic membrane has been widely used in the clarification process of plant extract due to its advantages of high separation efficiency and good anti-pollution performance. At present, there are few reports on the application of ceramic membrane in the separation of Eucommia ulmoides leaf extract. It is of great application value to develop an efficient clarification technology of Eucommia ulmoides leaf extract by ceramic membrane. In this paper, the research was carried out from two aspects of membrane material and membrane process. The pore size of ceramic membrane was optimized. The effects of operating pressure, membrane surface velocity and temperature on the clarification process of ceramic membrane were systematically investigated. The membrane fouling mechanism was analyzed by Hermia model. The results showed that the ceramic microfiltration membrane with an average pore size of 100 nm had higher turbidity removal rate, active component transmittance and permeation flux, which was suitable for the clarification process of Eucommia ulmoides leaves extract. Under the optimized operating conditions, the stable flux of ceramic microfiltration membrane was about 58 L·m^-2·h^-1, the total transmittance of chlorogenic acid and flavonid was 75.3%, the turbidity removal rate was nearly 100%, and the flux recovery rate was over 85% after cleaning. Ceramic membrane separation technology has shown a good application prospect in the clarification process of Eucommia ulmoides leaves extract.

Key words: membrane, separation, clarification, ceramic membrane, Eucommia ulmoides leaf, membrane fouling

中图分类号:

TQ 028.8

王思琪, 顾天宇, 陈献富, 王通, 李佳, 柯威, 李小锋, 范益群. 陶瓷膜用于杜仲叶提取液澄清的分离特性与膜污染机制研究[J]. 化工学报, 2023, 74(3): 1113-1125.

Siqi WANG, Tianyu GU, Xianfu CHEN, Tong WANG, Jia LI, Wei KE, Xiaofeng LI, Yiqun FAN. Study on separation characteristics and membrane fouling mechanism of ceramic membrane for clarification of Eucommia ulmoides leaves extract[J]. CIESC Journal, 2023, 74(3): 1113-1125.

图/表 15

表1 实验仪器

Table 1 Experimental materials and instruments

仪器	型号	生产厂家
紫外可见光分光光度计	UV-2600i	岛津仪器(苏州)有限公司
液相色谱仪	LC-20AT	日本岛津公司
浊度计	WZS-188	上海仪电科学仪器股份有限公司
凝胶色谱仪	Waters1515	Waters(美国)
冷场发射扫描电镜	S-4800	Hitachi(日本)
Zeta电位分析仪	Nano-ZS90	Malvern(英国)
白光干涉仪	VK-X1000	Keyence(日本)

图1 错流过滤装置示意图

Fig.1 Schematic diagram of the cross-flow filtration device

表2 膜污染孔阻塞模型方程

Table 2 Pore blocking model equations

污染模型	n	方程
完全孔阻塞	2	$J = J * + J 0 - J * e - k c t$
标准孔阻塞	1.5	$J = J 0 1 + J 0 1 / 2 k s t 2$
中间孔阻塞	1	$J = J 0 J * e k i J * t J * + J 0 e k i J * t - 1$
滤饼层阻塞	0	$t = 1 k l J * 2 l n J J 0 - J * J 0 J - J * - J * 1 J - 1 J 0$

表2 膜污染孔阻塞模型方程

Table 2 Pore blocking model equations

污染模型	n	方程
完全孔阻塞	2	$J = J * + J 0 - J * e - k c t$
标准孔阻塞	1.5	$J = J 0 1 + J 0 1 / 2 k s t 2$
中间孔阻塞	1	$J = J 0 J * e k i J * t J * + J 0 e k i J * t - 1$
滤饼层阻塞	0	$t = 1 k l J * 2 l n J J 0 - J * J 0 J - J * - J * 1 J - 1 J 0$

图2 陶瓷膜的电镜表面微观形貌

Fig.2 Surface FESEM images of ceramic membranes

图3 陶瓷膜的电镜断面微观形貌

Fig.3 Cross-section FESEM images of ceramic membranes

图4 陶瓷膜的表面粗糙度（Sa）

Fig.4 Roughness （Sa） of ceramic membranes

图5 孔径分布结果

Fig.5 Pore size distribution results

图6 Ⅰ~Ⅳ号膜的渗透性能

Fig.6 Separation performances of membrane Ⅰ—Ⅳ

图7 不同压力下的渗透性能

Fig.7 Separation performances at different operating pressures

图8 不同操作压力下的Hermia模型对渗透通量的模拟

Fig.8 Simulation of permeation flux by Hermia model at different operating pressures

表3 不同操作压力下的污染模型相关系数R2和污染指数k

Table 3 Correlation coefficient R2 and pollution index k of pollution model at different operating pressure

Fouling model	0.10 MPa		0.20 MPa		0.25 MPa		0.30 MPa
Fouling model	R²	k	R²	k	R²	k	R²	k
complete blocking	0.9586	7.280×10^-2	0.9827	3.280×10^-1	0.9630	3.546×10^-1	0.9989	4.784×10^-1
standard blocking	0.9645	6.167×10^-3	0.5289	8.237×10^-3	0.6802	1.067×10^-3	0.6641	1.353×10^-2
intermediate blocking	0.9963	9.040×10^-4	0.9934	2.969×10^-3	0.9766	2.991×10^-3	0.9994	5.135×10^-3
cake layer	0.8892	1.203×10^-5	0.8770	2.512×10^-5	0.9258	1.524×10^-5	0.4676	4.495×10^-5

图9 不同膜面流速下的渗透性能

Fig.9 Separation performances at different membrane surface velocities

表4 不同膜面流速下的污染模型相关系数 R2 和污染指数 k

Table 4 Correlation coefficient R2 and pollution index k of pollution model at different membrane surface velocities

Fouling models	2 m·s^-1		3 m·s^-1		4 m·s^-1		5 m·s^-1
Fouling models	R²	k	R²	k	R²	k	R²	k
complete blocking	0.9480	2.016×10^-1	0.9827	3.280×10^-1	0.9621	3.816×10^-2	0.8065	9.167×10^-2
standard blocking	0.8646	1.215×10^-2	0.5289	8.237×10^-3	0.9754	2.416×10^-3	0.5496	2.643×10^-3
intermediate blocking	0.9875	2.990×10^-3	0.9934	2.969×10^-3	0.9603	2.947×10^-4	0.9052	5.706×10^-4
cake layer	0.9528	2.370×10^-5	0.8770	2.012×10^-5	0.9628	1.767×10^-6	0.9747	3.427×10^-6

图10 不同温度下的渗透性能

Fig.10 Separation performances at different temperatures

表5 不同温度下的污染模型相关系数 R2 和污染指数 k

Table 5 Correlation coefficient R2 and pollution index k of pollution model at different temperatures

Fouling models	20˚C		30˚C		40˚C		50˚C
Fouling models	R²	k	R²	k	R²	k	R²	k
complete blocking	0.9401	2.629×10^-1	0.9827	3.280×10^-1	0.9005	6.547×10^-2	0.7565	5.062×10^-2
standard blocking	0.6005	3.430×10^-6	0.5289	8.237×10^-3	0.8977	3.465×10^-3	0.8471	3.068×10^-3
intermediate blocking	0.9728	3.033×10^-3	0.9934	2.969×10^-3	0.9727	4.133×10^-4	0.8922	2.543×10^-4
cake layer	0.8452	2.640×10^-5	0.8770	2.512×10^-5	0.8929	2.880×10^-6	0.8985	1.070×10^-6

参考文献 39

1	Huang H J, Ramaswamy S, Tschirner U W, et al. A review of separation technologies in current and future biorefineries[J]. Separation and Purification Technology, 2008, 62(1): 1-21.
2	国家药典委员会. 中华人民共和国药典-二部: 2020年版[M]. 北京: 中国医药科技出版社, 2020.
	State Pharmacopoeia Committee. People's Republic of China (PRC) Pharmacopoeia—part Ⅱ: 2020 edition[M]. Beijing: China Pharmaceutical Science and Technology Press, 2020: 172.
3	Huang L C, Lyu Q, Zheng W Y, et al. Traditional application and modern pharmacological research of Eucommia ulmoides Oliv[J]. Chinese Medicine, 2021, 16(1): 73.
4	Pandey K B, Rizvi S I. Plant polyphenols as dietary antioxidants in human health and disease[J]. Oxidative Medicine and Cellular Longevity, 2009, 2(5): 270-278.
5	Zhang Q, Su Y Q, Zhang J F. Seasonal difference in antioxidant capacity and active compounds contents of Eucommia ulmoides oliver leaf[J]. Molecules, 2013, 18(2): 1857-1868.
6	Xu D H, Yu C L, Wang J J, et al. Ultrafiltration strategy combined with nanoLC-MS/MS based proteomics for monitoring potential residual proteins in TCMIs[J]. Journal of Chromatography B, 2021, 1178: 122818.
7	Shao F L, Xu J T, Zhang J Y, et al. Study on the influencing factors of natural pectin's flocculation: their sources, modification, and optimization[J]. Water Environment Research, 2021, 93(10): 2261-2273.
8	郭立玮, 邢卫红, 朱华旭, 等. 中药膜技术的"绿色制造"特征、国家战略需求及其关键科学问题与应对策略[J]. 中草药, 2017, 48(16): 3267-3279.
	Guo L W, Xing W H, Zhu H X, et al. "Green manufacture" characteristics and national strategic demand of Chinese material medica membrane technology and its key scientific problems and countermeasures[J]. Chinese Traditional and Herbal Drugs, 2017, 48(16): 3267-3279.
9	Jha A K, Sit N. Extraction of bioactive compounds from plant materials using combination of various novel methods: a review[J]. Trends in Food Science & Technology, 2022, 119: 579-591.
10	Tchabo W, Ma Y K, Engmann F N, et al. Ultrasound-assisted enzymatic extraction (UAEE) of phytochemical compounds from mulberry (Morus nigra) must and optimization study using response surface methodology[J]. Industrial Crops and Products, 2015, 63: 214-225.
11	Jiang T, Ghosh R, Charcosset C. Extraction, purification and applications of curcumin from plant materials—a comprehensive review[J]. Trends in Food Science & Technology, 2021, 112: 419-430.
12	Horosanskaia E, Yuan L N, Seidel-Morgenstern A, et al. Purification of curcumin from ternary extract—similar mixtures of curcuminoids in a single crystallization step[J]. Crystals, 2020, 10(3): 206.
13	Sjölin M, Thuvander J, Wallberg O, et al. Purification of sucrose in sugar beet molasses by utilizing ceramic nanofiltration and ultrafiltration membranes[J]. Membranes, 2019, 10(1): 5.
14	Castro-Muñoz R, Yáñez-Fernández J, Fíla V. Phenolic compounds recovered from agro-food by-products using membrane technologies: an overview[J]. Food Chemistry, 2016, 213: 753-762.
15	Martín J, Díaz-Montaña E J, Asuero A G. Recovery of anthocyanins using membrane technologies: a review[J]. Critical Reviews in Analytical Chemistry, 2018, 48(3): 143-175.
16	Wang K, Li W X, Fan Y Q, et al. Integrated membrane process for the purification of lactic acid from a fermentation broth neutralized with sodium hydroxide[J]. Industrial & Engineering Chemistry Research, 2013, 52(6): 2412-2417.
17	Laorko A, Li Z Y, Tongchitpakdee S, et al. Effect of membrane property and operating conditions on phytochemical properties and permeate flux during clarification of pineapple juice[J]. Journal of Food Engineering, 2010, 100(3): 514-521.
18	Zhu Z Z, Guan Q Y, Koubaa M, et al. Preparation of highly clarified anthocyanin-enriched purple sweet potato juices by membrane filtration and optimization of their sensorial properties[J]. Journal of Food Processing and Preservation, 2017, 41(3): e12929.
19	Castro-Muñoz R, Yáñez-Fernández J. Valorization of Nixtamalization wastewaters (Nejayote) by integrated membrane process[J]. Food and Bioproducts Processing, 2015, 95: 7-18.
20	Russo C. A new membrane process for the selective fractionation and total recovery of polyphenols, water and organic substances from vegetation waters (VW)[J]. Journal of Membrane Science, 2007, 288(1/2): 239-246.
21	Urošević T, Povrenović D, Vukosavljević P, et al. Recent developments in microfiltration and ultrafiltration of fruit juices[J]. Food and Bioproducts Processing, 2017, 106: 147-161.
22	杨祖金, 江燕斌, 葛发欢, 等. 超滤膜技术分离杜仲叶绿原酸的研究[J]. 中药材, 2008, 31(4): 585-588.
	Yang Z J, Jiang Y B, Ge F H, et al. Study on isolation of chlorogenic acid from Eucommia ulmoides leaves by ultrafiltration technique[J]. Journal of Chinese Medicinal Materials, 2008, 31(4): 585-588.
23	Lu Y W, Chen T, Chen X F, et al. Fabrication of TiO₂-doped ZrO₂ nanofiltration membranes by using a modified colloidal sol-gel process and its application in simulative radioactive effluent[J]. Journal of Membrane Science, 2016, 514: 476-486.
24	Zou D, Xu J R, Chen X F, et al. A novel thermal spraying technique to fabricate fly ash/alumina composite membranes for oily emulsion and spent tin wastewater treatment[J]. Separation and Purification Technology, 2019, 219: 127-136.
25	钟文蔚, 郑东阳, 邹洪荟, 等. 基于中药液、固体物料指标成分含量相关性的膜工艺评估方法创新研究: 以杜仲叶水提液为例[J]. 中草药, 2021, 52(11): 3234-3238.
	Zhong W W, Zheng D Y, Zou H H, et al. A novel approach for evaluating the concentrations of indicative components in liquid and solid in the pharmaceutical process of TCM manufacturing using membrane based clarification—example given in the water extracts of Eucommiae Folium[J]. Chinese Traditional and Herbal Drugs, 2021, 52(11): 3234-3238.
26	Field R W, Wu D, Howell J A, et al. Critical flux concept for microfiltration fouling[J]. Journal of Membrane Science, 1995, 100(3): 259-272.
27	Lu D W, Zhang T, Ma J. Ceramic membrane fouling during ultrafiltration of oil/water emulsions: roles played by stabilization surfactants of oil droplets[J]. Environmental Science & Technology, 2015, 49(7): 4235-4244.
28	Sayehi M, Sahnoun R D, Fakhfakh S, et al. Effect of elaboration parameters of a membrane ceramic on the filtration process efficacy[J]. Ceramics International, 2018, 44(5): 5202-5208.
29	Chen X F, Qi T, Zhang Y, et al. Facile pore size tuning and characterization of nanoporous ceramic membranes for the purification of polysaccharide[J]. Journal of Membrane Science, 2020, 597: 117631.
30	Akamatsu K, Kagami Y, Nakao S I. Effect of BSA and sodium alginate adsorption on decline of filtrate flux through polyethylene microfiltration membranes[J]. Journal of Membrane Science, 2020, 594: 117469.
31	Marshall A D, Munro P A, Trägårdh G. The effect of protein fouling in microfiltration and ultrafiltration on permeate flux, protein retention and selectivity: a literature review[J]. Desalination, 1993, 91(1): 65-108.
32	Vincent Vela M C, Álvarez Blanco S, Lora García J, et al. Analysis of membrane pore blocking models adapted to crossflow ultrafiltration in the ultrafiltration of PEG[J]. Chemical Engineering Journal, 2009, 149(1/2/3): 232-241.
33	Corbatón-Báguena M J, Álvarez-Blanco S, Vincent-Vela M C. Fouling mechanisms of ultrafiltration membranes fouled with whey model solutions[J]. Desalination, 2015, 360: 87-96.
34	滕达, 李铁林, 李昂, 等. 单通道陶瓷膜管低压透水性能实验分析[J]. 化工学报, 2020, 71(S1): 261-271.
	Teng D, Li T L, Li A, et al. Experimental analysis of low pressure water permeability of single channel ceramic membrane tube[J]. CIESC Journal, 2020, 71(S1): 261-271.
35	Cui Z L, Peng W B, Fan Y Q, et al. Effect of cross-flow velocity on the critical flux of ceramic membrane filtration as a pre-treatment for seawater desalination[J]. Chinese Journal of Chemical Engineering, 2013, 21(4): 341-347.
36	Niu B H, Yang L, Meng S J, et al. Time-dependent analysis of polysaccharide fouling by Hermia models: reveal the structure of fouling layer[J]. Separation and Purification Technology, 2022, 302: 122093.
37	Qi T, Chen X F, Shi W D, et al. Fouling behavior of nanoporous ceramic membranes in the filtration of oligosaccharides at different temperatures[J]. Separation and Purification Technology, 2021, 278: 119589.
38	France T C, Bot F, Kelly A L, et al. The influence of temperature on filtration performance and fouling during cold microfiltration of skim milk[J]. Separation and Purification Technology, 2021, 262: 118256.
39	Alper N, Onsekizoglu P, Acar J. Effects of various clarification treatments on phenolic compounds and organic acid compositions of pomegranate (Punica granatum L.) juice[J]. Journal of Food Processing and Preservation, 2011, 35(3): 313-319.

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陶瓷膜用于杜仲叶提取液澄清的分离特性与膜污染机制研究

Study on separation characteristics and membrane fouling mechanism of ceramic membrane for clarification of Eucommia ulmoides leaves extract

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