模拟移动床色谱分离吴茱萸碱和吴茱萸次碱

doi:10.11949/0438-1157.20201919

摘要/Abstract

摘要：

以C18为固定相、甲醇/水=70/30（体积比）为流动相，利用三区带模拟移动床分离了两种生物碱，吴茱萸碱和吴茱萸次碱。通过前沿分析法测定了两种生物碱的吸附等温线，在实验浓度范围内符合线性吸附等温线，吴茱萸碱和吴茱萸次碱的亨利系数分别为3.11和5.25。利用经验公式估算了轴向扩散系数和有效传质系数。分别利用三角形理论和基于模型的优化方法对三区带模拟移动床的操作条件进行设计，在优化的条件下，最大进料流量为0.55 ml?min^-1，两种产品纯度均大于99%。通过异步切换策略，在不增加设备投资及保证产品纯度大于99%的前提下，将进料流量提高至0.62 ml?min^-1。

关键词: 模拟移动床, 色谱, 分离, 吴茱萸碱, 吴茱萸次碱, Varicol, 优化

Abstract:

Using C18 as the stationary phase and methanol/water=70/30 (volume ratio) as the mobile phase, the three-zone simulated moving bed was used to separate two alkaloids, evodiamine and rutaecarpine. The isotherms of the two alkaloids were determined by frontal analysis, which can be described by linear isotherms with the Henry coefficients of 3.11 for evodiamine and 5.25 for rutaecarpine. The axial diffusion coefficient and mass-transfer coefficients of the two alkaloids were estimated by empirical equations. The operation conditions were designed by triangle theory and optimization method based on the mathematical model. Through optimization, the maximum feed flow rate was 0.55 ml?min^-1. The experimental purities of two products were both higher than 99%. By asynchronous switching, the feed flow rate was increased to 0.62 ml?min^-1 without additional investment and product purity loss.

Key words: simulated moving bed, chromatography, separation, evodiamine, rutaecarpine, Varicol, optimization

中图分类号:

TQ 028.8

姚传义, 郑震玮, 涂志贤, 卢英华. 模拟移动床色谱分离吴茱萸碱和吴茱萸次碱[J]. 化工学报, 2021, 72(7): 3728-3737.

YAO Chuanyi, ZHENG Zhenwei, TU Zhixian, LU Yinghua. Separation of evodiamine and rutaecarpine with simulated moving bed chromatography[J]. CIESC Journal, 2021, 72(7): 3728-3737.

图/表 10

图1 吴茱萸碱和吴茱萸次碱的化学结构

Fig.1 Chemical structures of evodiamine and rutaecarpine

图2 Varicol过程实现平均构型[1,1.5,1.5,1]的异步切换策略

Fig.2 Asynchronous switching strategy in Varicol for achieving the average configuration of [1,1.5,1.5,1]

图3 C18制备柱上孔堵塞前后硫脲保留时间与Vc/Q之间的关系

Fig.3 Relationship between retention time of thiourea and Vc/Q on the C18 preparative column before and after pore blocking

图4 前沿分析法测定吴茱萸碱和吴茱萸次碱的吸附等温线

Fig.4 Adsorption isotherms of evodiamine and rutaecarpine by frontal analysis

图5 不同流量下的轴向扩散系数与有效传质系数

Fig.5 Axial diffusion coefficient and mass-transfer coefficients at different flow rates

图6 mⅡ - mⅢ平面内的操作点

Fig.6 Operation points in the mⅡ - mⅢ plane

表1 不同操作点的操作条件及产品纯度

Table 1 Operation conditions and product purities at different operation points

操作点	构型	切换周期/min	Q_I/(ml?min^-1)	Q_E/(ml?min^-1)	Q_F/(ml?min^-1)	P_E/%	P_R/%
P₁		22.5	2	0.55	0.5	99.5±0.2	94.4±0.2
P₂		22.5	2	0.60	0.5	99.4±0.3	95.8±0.2
P₃		22.5	2	0.65	0.5	99.1±0.2	95.9±0.1
P₄		22.5	2	0.70	0.5	98.9±0.2	96.0±0.2
P₅		22.5	2	0.75	0.5	98.2±0.3	96.1±0.3
P₆		24.48	2	0.78	0.55	99.6±0.3	99.4±0.2
P₇	[1.16, 1.16, 1.68]	23.75	2	0.80	0.62	99.6±0.2	99.7±0.1

表2 SMB及Varicol过程的最优操作条件

Table 2 Optimum operation conditions for the SMB and Varicol processes

过程	t_s/min	Q_F/(ml?min^-1)	Q_E/(ml?min^-1)	各区带流量/(ml?min^-1)			各区带柱子数目
过程	t_s/min	Q_F/(ml?min^-1)	Q_E/(ml?min^-1)	区带Ⅰ	区带Ⅱ	区带Ⅲ	区带Ⅰ	区带Ⅱ	区带Ⅲ
SMB	24.48	0.55	0.78	2.0	1.22	1.77	1	1	2
Varicol	23.75	0.62	0.80	2.0	1.20	1.82	1.16	1.16	1.68

图7 实现平均构型[1.16, 1.16, 1.68]的切换策略D—洗脱液; E—萃取液; F—进料; R—萃余液

Fig.7 Switching strategy for achieving the average configuration of [1.16, 1.16, 1.68]

图8 SMB及Varicol过程在切换周期中点时刻的柱内浓度分布曲线

Fig.8 Concentration profiles of SMB and Varicol processes at the mid-point of switching period

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