大型液相色谱分离甘露醇和山梨醇的热力学及动力学参数辨识

本文研究了液相色谱分离过程的吸附平衡常数、传质系数参数的估值模型，用色谱技术和以惰性物示踪的扰动应答实验技术测定甘露醇和山梨醇在钙型吸附剂上的吸附相平衡常数和总传质系数以及床层中的轴向扩展系数，结果表明：吸附平衡常数和吸附剂的选择性随温度的升高而下降；液固相间的总传质系数随温度的升高而增大；轴向扩散系数随流速的增大而增大，参数灵敏度分析的结果表明，相平衡关系，尤其是吸附选择性，对色谱分离的影响有较     

液相色谱技术测定葡萄糖果糖在Ca型吸附剂上相平衡常数和总传质系数

]考虑轴向扩散的影响,导出液相色谱技术测定吸附相平衡常数和总数传质系数参数估值模型,测定葡萄糖果糖吸附相平衡常数和总传质系数,研究流速、温度对这些参数的影响。获得理论计算与色谱分离实验流出曲线相吻合结果。     

大型液相色谱分离过程FAD－SMT数学模型及其数值解

 提出大型液相色谱分离过程ＦＡＤ－ＳＭＴ数学模型，把色谱分离连续性方程转变为对流扩散方程和常微分方程组，并提出模型的数值方法，分析了数值解的稳定条件和收敛条件以及空间和时间步长的选取。实验结果表明，ＦＡＤ－ＳＭＴ数学模型计算的液相色谱分离葡萄糖、果糖和分离甘露醇、山梨醇理论与实验流出曲线相吻合。灵敏度分析结果表明：相平衡常数比轴向扩散系数和总传质系数对色谱分离有较大的影响。     

大型液相色谱分离过程FAD－SMT数学模型及其数值解

提出大型液相色谱分离过程ＦＡＤ－ＳＭＴ数学模型，把色谱分离连续性方程转变为对流扩散方程和常微分方程组，并提出模型的数值方法，分析了数值解的稳定条件和收敛条件以及空间和时间步长的选取。实验结果表明，ＦＡＤ－ＳＭＴ数学模型计算的液相色谱分离葡萄糖、果糖和分离甘露醇、山梨醇理论与实验流出曲线相吻合。灵敏度分析结果表明：相平衡常数比轴向扩散系数和总传质系数对色谱分离有较大的影响。     

吸附剂性能和操作参数对液相色谱流出峰不对称性的影响

色谱流出峰的拖尾现象普遍存在于制备和大型色谱分离过程中,它直接影响分离的产率和回收率．本文提出采用色谱流出峰形的不对称偏差度来表征色谱流出峰的拖尾程度;并基于液相制备色谱分离过程FAD－SMT模型及吸附速率理论,通过计算机模拟,定量分析了吸附剂性能和操作参数对色谱流出峰形不对称性的影响。结果表明：不仅是吸附剂的热力学和动力学性能（包括吸附相平衡关系、液固两相间的传质阻力）;而且柱的设计和吸附剂的装填状况（包括轴向扩散系数）,以及色谱分离的操作条件（进料时间、浓度和流速等）都直接影响色谱流出峰形的不对称性。随着吸附相平衡等温线的非线性程度增大,或者总传质系数的减小,色谱流出峰形的不对称偏差度明显增大;吸附剂吸附容量的减小也将引起色谱流出峰形的不对称偏差度的增加;色谱流出峰形的不对称偏差度与进科体积、浓度和流体线速,以及轴向扩散系数的增大成正比。     

色谱法测定氧和氮在13X分子筛上的吸附平衡常数及传质系数

以H_2作载气,在微机辅助下用色谱法测定O_2和N_2在13X分子筛填充柱上的吸附平衡常数和传质系数。提出用计算量小的矩量法求吸附平衡常数,再由时域拟合单参数估算总传质系数。由实验结果及理论分析发现,该体系中,轴向扩散对总传质阻力贡献最大,并得轴向扩散系数与操作条件的关联式     

连续旋转环状色谱的数学模型参数分析

连续旋转环状色谱用数学模型模拟时,模拟结果的精确度和所采用参数的“灵敏”程度有关。为此,探讨了相平衡常数、相间传质系数、弥散返混系数等对色谱峰质量浓度最高点位置角度（保留值）、分离度、峰宽和产率等参数的灵敏度并对它们逐一进行了分析。认为相平衡关系对分离效果最为敏感。筛选吸附量大、选择性好的吸附剂是改进操作效果的最佳途径。     

采用浅床技术测定亚铁氰化钛钾交换Cs+的传质特性

采用浅床技术分别研究了料液浓度、操作温度以及料液流速对用亚铁氰化钛钾无机离子交换剂从硝酸铯溶液中交换Cs+的总传质系数的影响.结果表明,随着料液浓度的上升,总传质系数变化不大,仅在q(交换剂相Cs+浓度)较高时呈微弱的下降趋势.在实验范围内,随着操作温度的升高,总传质系数相应升高.料液流速对亚铁氰化钛钾交换Cs+的总传质系数的影响最大,其影响分为两个阶段当q＜0.25mmol/ml时,对一定的料液流速,总传质系数随着q值增加而较快下降;对一定的q值,总传质系数随着料液流速增加而增加.当q≥0.25mmol/ml时,时一定的料液流速,总传质系数随着q值增加缓慢下降;对一定的q值,不同料液流速下的总传质系数几乎没有区别.总之,当q值较小时,传质过程由液膜扩散和交换剂粒内扩散共同控制;当q值较大时,液膜扩散阻力相对于交换剂粒内扩散阻力要小得多,传质过程由交换剂粒内扩散控制.     

富里衰分析法计算固定床吸附柱的轴向返混系数

在柠蒙酸吸附分离柱的放大过程中，分离柱放大后的轴向返混系数是了解其放大效应的重要参数之一。本文以０，１６％ＫＣｌ溶液为示踪剂，用扰动－应答技术测取基模参数，并以富里衰分析法拟合。     

富里哀分析法估算固定床吸附柱的轴向返混系数

在柠檬酸吸附分离柱的放大过程中，分离柱放大后的轴向返混系数是了解其放大效应的重要参数之一。本文以０．１６％ＫＣｌ溶液为示踪剂，用扰动──应答技术测取其模型参数，并以富里哀分析法拟合。在频率因子ω＝０．０２～０．１的范围内抓幅比Ｍ·Ｒ．成平行直线，即振幅比Ｍ·Ｒ．不变，故取ω＝０．０４，根据式Ｉｎ（Ｍ·Ｒ．）＝（ｐｅ／２）［１－（１＋ａ２）１／４ｃｏｓａ］求出不同柱高，柱径和流速下的轴向返混系数，并列表比较。     

Axial dispersion coefficient in high-speed counter-current chromatography

Experimental measurements of axial dispersion coefficients in high-speed counter-current chromatography have been carried out in the single-phase and two-phase modes. Axial dispersion coefficients were calculated from the residence time distribution curve (or the elution profile). The experimental data obtained were used to develop a model involving Peclet number Pe, Reynolds number and the ratio of flow velocity u to linear angular velocity u_θ for predicting the axial dispersion coefficient. Furthermore, the models obtained from the single-phase and two-phase modes were compared, and a counterintuitive phenomenon was found in that the effects of the flow rate and the rotation speed on the axial dispersion coefficients are inconsistent: the axial dispersion coefficient decreases with the rotation speed and increases with the flow rate in the single-phase mode, but increases with rotation speed and decreases slightly with the flow rate in the two-phase mode.     

Determination of the lumped mass transfer rate coefficient by frontal analysis

The validity of measurements of the lumped mass transfer rate coefficient (k_m,L) is studied on the basis of experimental data acquired under Langmuir isotherm conditions, in reversed-phase liquid chromatography. Two different methods were used, the perturbation method and frontal analysis. Accurate values of k_m,L can be properly obtained by the perturbation method because, with this method, the chromatographic processes take place under locally linear isotherm conditions. Values of k_m,L can also be derived from the breakthrough curves obtained in frontal analysis. Because the contribution of axial dispersion to band broadening was larger than that of the mass transfer resistances, the apparent axial dispersion coefficient (D_a) was first derived from the breakthrough curve by applying the equilibrium–dispersive model. Then, the value of k_m,L was calculated from D_a. The values of k_m,L determined by the two methods were in close agreement in the range of nondimensional Langmuir equilibrium constants (r=1/[1+K_LC₀]) between 0.32 and 0.85, irrespective of the mobile phase flow velocity. Thus, frontal analysis can be used for kinetic studies of the mass transfer in chromatographic columns.     

Characterization of a novel continuous supermacroporous monolithic cryogel embedded with nanoparticles for protein chromatography

A novel continuous supermacroporous monolithic cryogel embedded with nanometer-size particles was prepared by the radical cryogenic co-polymerization of acrylamide (AAm), N,N'-methylene-bis-acrylamide (MBAAm), allyl glycidyl ether (AGE) and the dispersed surfactant-stabilized Fe3O4 nanoparticles under the freezing-temperature variation condition in a glass column. This special separation matrix has interconnected supermacropores with pore size of 10-50 microm, which permit the free-passage of microbial cells or cell debris in the culture fluids and then is interest in downstream processes. The axial liquid dispersion coefficients of the new continuous supermacroporous monolithic bed at different liquid flow rates were obtained by measuring residence time distributions (RTDs) using tracer pulse-response method. The experimental results showed that the axial liquid dispersion within the bed was weak in a wide water flow rate of 0.5-15 cm/min. The axial dispersion coefficient was found to be increased exponentially with the increase of liquid flow rate. Chromatographic process of bovine serum albumin (BSA) in the cryogel monolithic bed was carried out to reveal the protein breakthrough and elution characteristics. Compared with other reported cryogel beds in literature, the protein adsorption capacity of the present cryogel bed was improved due to the embedded nano-sized solid adsorbents in the gel matrix. Microstructure morphology of the embedded nanoparticles in the cryogel and the gel matrix structure were also analyzed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) in this paper.     

Sorption of phenols from water in column systems using surfactant-modified montmorillonite

The sorption of phenol, m-nitrophenol (m-NP), and o-cresol from water onto montmorillonite modified with cetyltrimethylammonium bromide (CTAB) in a column was studied. The sorption isotherms were fitted by the Langmuir equation. Column experiments were performed at 25 degrees C to determine the breakthrough curves at different flow rates, feed sorbate concentrations, and bed lengths. It was shown that the proposed constant-pattern wave approach with the Langmuir model could well describe the breakthrough curves. The time required when the effluent concentration reached half of the feed concentration (t(1/2)) decreased with increasing feed flow rate, but the mass transfer coefficient (KLa) increased. In addition, an increase in feed sorbate concentration led to a decrease of both values of t(1/2) and KLa. The effect of axial dispersion on breakthrough dynamics in these sorption systems was finally discussed.     

Phenomenological study on heat and mass coupling mechanism of waxy crude oil pipeline transport process

Based on the phase equilibrium model of the paraffin wax precipitation in the process of oil pipeline transportation, theory and method of non-equilibrium thermodynamics were applied to obtain the linear phenomenological equations for the cross-interaction of heat and mass transfer during pipeline transport, which were derived from the irreversible entropy production rate equation. Then, the analysis of the irreversible heat flow and the mass flow were carried out, and the mathematical expressions of the phenomenological coefficient of liquid phase, the phenomenological coefficient of solid phase flow, and the heat flow phenomenological coefficient were obtained. Taking a waxy crude oil transportation pipeline in Daqing Oilfield as an example, based on the analysis of liquid–solid phase equilibrium, the irreversible linear phenomenological mechanism of heat and mass coupling in waxy crude oil pipeline transportation was analyzed in detail from three levels: phenomenological coefficients which reflect characteristic of the effect of force on flow in heat and mass transfer; thermodynamic forces which trigger heat and mass transfer; transmitted heat and mass flow density, providing a theoretical basis for the further study of the wax deposition in the process of pipeline transportation.     

Influence of suspended solid particles on gas-liquid mass transfer coefficient in a system stirred by double impellers

The aim of the research work was to investigate the effect of the presence and concentration of solid particles on the gas-liquid volumetric mass transfer coefficient in a mechanically stirred gas-solid-liquid system. Experimental studies were conducted in a tall vessel of the diameter of 0.288 m, equipped with two designs of double stirrers. Three high-speed stirrers were used: A 315, Smith turbine, and Rushton turbine. The following operating parameters were changed: gas flow rate, stirrer speed, and solid concentration. The volumetric mass transfer coefficient was determined using the dynamic gassing-out method. In the range of the measurements conducted, this coefficient was strongly affected by both the presence and the concentration of particles in the system. Generally, a low concentration of particles in the system, equal to 0.5 mass %, caused an increase of the volumetric mass transfer coefficient values for both stirrer configurations compared to a system without solids whilst more particles (2.5 mass %) caused a decrease of this coefficient. It could be supposed that an increase of slurry viscosity affected the decrease of the volumetric mass transfer coefficient at higher solid concentration. An empirical correlation was proposed for volumetric mass transfer coefficient prediction. Its parameters were fitted using experimental data. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

T形微通道中气泡分散流的传质性能

在T形微通道中,以错流剪切的分散方式实现了微米级分散气泡的制备,并以NaOH水溶液吸收CO2为对象,考察了气．液微分散体系的分散规律和传质性能．通过考察两相流速对气泡分散尺寸的影响,建立了预测气泡形成尺寸的数学模型．根据气泡的初始分散尺寸、流动阶段的体积变化以及传质完成后的尺寸,首次测定和区分了气泡形成阶段和运动阶段的传质量,建立了原位测定气泡分散流传质系数札的方法,并考察了两相流量对札的影响．结果表明,由于微通道中气泡的形成时间很短,形成阶段的传质量在总传质量中所占的比例很低．气泡分散流的传质系数主要受液相流量的影响,气相流量的影响基本可以忽略．基于实验结果,建立了计算传质系数鼠的无因次准数关联,计算结果与实验结果符合良好．     

Experimental study of extraction fraction and mass transfer coefficient in a microchannel using butyl acetate/acetic acid/water chemical system

The droplet flow regime in microchannels can increase the mass transfer and chemical reactions considerably. In this work, the mass transfer of immiscible fluids of water as the solvent and butyl acetate containing 5 vol% of acetic acid as the feed is experimentally studied in a vertical flow inside a microchannel with the inner diameter of 8 mm. Effect of total flow velocity, Re number and volumetric flux ratio of two phases (Q_aq/Q_or) on the extraction fraction of acetic acid, mass transfer coefficient and droplet size were investigated. Based on the experiments, increasing the flux ratio can shift the flow regime from the plug to the droplet. Compared to the plug flow, the extraction fraction increased by 2–3 times in the droplet regime, depending on the total velocity, while the average diameter of the droplets decreased. Moreover, with the increase in the total velocity, the extraction fraction is reduced by 22%. However, in the case of the plug flow, the extraction fraction does not change appreciably with the increase in the total flow velocity. The mass transfer coefficient was found to increase monotonously with increasing Re number and an enhancement of 133% was achieved in the droplet flow regime.     

THE DETERMINATION OF ADSORPTION ISOTHERMS AND SOLID DIFFUSION COEFFICIENTS OF MANNITOL AND SORBITOL BY LIQUID CHROMATOGRAPHY TECHNIQUE

The parameter identification model is proposed for determining the linear adsorption isotherms and the solid diffusion coefficients by using adsorption chromatorgaphy.Axial dispersion coefficients is firstly determined by pulse-respond experiment technique with an inert substance as tracer,then the elution curves of chromatography separating the isomer mannitol and sorbitol are determined by the chromatographic measuring technique,and pinally the adsorption isotherms and the solid diffusion coefficients of mannitol and sorbitol on Ca^2+ resins are estimated by using this model.The results show that the axial dispersion coefficients increase with fluid velocity increasing,The adsorption equilibrium constants decrease with temperature rising;and the solid diffusion coefficients increase with temperature rising.The theoretical elution curves are good agreement with the experimental elution curves of the liquid adsorption chromatography separating the mannitol and the sorbitol.The model provides a simple and reliable procedure to estimate the kinetic and thermodynamic parmeters of the adsorption.