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

doi:10.11949/0438-1157.20221347

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 15

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)

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

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	$t = 1 k l J * 2 l n J J 0 - J * J 0 J - J * - J * 1 J - 1 J 0$

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	$t = 1 k l J * 2 l n J J 0 - J * J 0 J - J * - J * 1 J - 1 J 0$

Fig.2 Surface FESEM images of ceramic membranes

Fig.3 Cross-section FESEM images of ceramic membranes

Fig.4 Roughness （Sa） of ceramic membranes

Fig.5 Pore size distribution results

Fig.6 Separation performances of membrane Ⅰ—Ⅳ

Fig.7 Separation performances at different operating pressures

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

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

Fig.9 Separation performances at different membrane surface velocities

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

Fig.10 Separation performances at different temperatures

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

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