超临界流体萃取制备脱沥青油与沥青微粒

A continuous three-stage supercritical fluid extraction (SFE) process with a capacity of 1.0kg.h^-1 was setup to extract petroleum residue by pentane to obtain more oil for further upgrading. A discharging system integrated to the bottom of the extractor was used to recover solvent as gas while asphalt was obtained as fine particles. The influence of operating conditions on the yield and quality of extracts, i.e., deasphalted oil (DAO) and resin, was studied in the range of temperature 150-220℃, pressure of 4.0-6.0 MPa and the mass ratio of solvent to oil feed (S/O) 2.5-5.0. The particle size distribution, apparent forms and the packing density, which vary with operating pressure, were measured. The particle structures were observed by SEM as well. With the modification to conventional processes, furnace can be eliminated for solvent recovery from asphalt phase, so as to reduce energy consumption.     

The use of environmentally sustainable bio-derived solvents in solvent extraction applications——A review

Replacement of volatile organic compounds (VOCs) by greener or more environmental y sustainable solvents is becoming increasingly important due to the increasing health and environmental concerns as wel as economic pressures associated with VOCs. Solvents that are derived from biomass, namely bio-derived solvents, are a type of green solvent that have attracted intensive investigations in recent years because of their advantages over con-ventional VOCs, such as low toxicity, biodegradability and renewability. This review aims to summarize the use of bio-derived solvents in solvent extraction applications, with special emphasis given to utilization of biodiesels and terpenes. Compared with the conventional VOCs, the overall performance of these bio-derived solvents is comparable in terms of extraction yields and selectivity for natural product extraction and no difference was found for metal extraction. To date most researchers have focused on laboratory scale thermodynamics studies. Future work is required to develop and test new bio-derived solvents and understand the kinetic performance as well as solvent extraction pilot plant studies.     

关于CO2有机溶剂体系液相体积膨胀的研究

The supercritical antisolvent （SAS） process has been developed in recent years for the tormation of nanoand micro-particles. It is necessary to study the liquid phase volume expansion （LPVE） and find the relationships between the operating conditions and the LPVE in order to develop a practical method for determining the operation conditions and selecting an organic solvent for SAS process. The PR equation of state with vdW-1 mixing rule is used to calculate the LPVE for CO2/toluene, CO2/acetone and CO2/ethyl acetate systems, and the results show that the LPVE for each CO2/organic solvent system decreases as the temperature increases. The relationship between the LPVE and the solubility of CO2 in the liquid phase for CO2/organic solvent systems is investigated, and the results show that the LPVE is determined directly by the solubility of CO2 in the liquid phase, xCO2, and can be related to xCO2 independently. No matter what system of CO2/organic solvent is and how different the temperature is, the LPVEs have little difference as long as the solubility of CO2 in the liquid phase, xCO2, keeps constant. The lower temperature is always favorable to the SAS process. The higher the solubility of CO2 in an organic solvent under certain operation condition, the more suitable it is to the SAS process.     

Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline,CO2 and Methanol

Methyl N-phenyl carbamate （MPC）, an important organic chemical, can be synthesized from aniline, CO2 and methanol. Catalyst Cu-Fe/ZrO2-SiO2 was first prepared and its catalytic performance for MPC synthesis was evaluated. Then the influence of solvent on the reaction path of MPC synthesis was investigated. It is found that the reaction intermediate is different with acetonitrile or methanol as a solvent. With acetonitrile as a solvent, the synthesis of MPC follows the reaction path with diphenyl urea as the intermediate, while with methanol as a solvent the reaction occurs via the reaction path with dimethyl carbonate as the intermediate. The catalytic mecha-nism of cooperative catalysis comprising metal sites, Lewis acid sites and Lewis base sites is proposed according to different reaction intermediates.     

聚醚与含氢硅油的硅氢加成反应的动力学研究

The hydrosilylation of polyhydrosiloxane and unsaturated allylic polyether terminated with ester group is processed with chloroplatinic acid as catalyst and ethyl acetate as solvent to exclude the mass transfer resistance in the system. The kinetic study is performed by means of Gel Permeation Chromatography. Within the experimental range （mass ratio of the whole reactants to solvent is 1：4, the tool ratio of Si-H bond to carbon-carbon double bond is 1： 1.3, the catalyst concentration from 1.0×10^-4mol·L^-1 （Pt） to 3.1×10^-4mol·L^-1 （Pt）, temperature between 338.15K and 350.35K）, a kinetic model of zero-th order reaction is built up and the evaluated model parameters are found to change linearly with the catalyst concentration.     

SOME THEORETICAL PROBLEMS OF ANIONIC POLYMERIZATION OF BUTADIENE——A Study on the Association Degree of n-BuLi and Polybutadienyl-Li

This paper determined the association degree of n-BuLi and polybutadinyllithium(PBLi)by UV spec-trometry and viscometry.The experimental results of UV spectrometric analysis showed that the associationdegree of n-BuLi as well as PBLi is dependent mainly on their concentration in solutions;there may be specieswith three and two degrees of association in cyclohexane solvent respectively for n-BuLi and PBLi,i.e.the asso-ciation degree for the former is equal to 2,4 and 6;and for the latter it equals to 2 and 4.Similarly,the experi-mental results obtained by viscometric measurement showed that the average association degree N of PBLiin cyclohexane changed from 2 to 4 with increasing of its concentration in solution and decreased with addi-tion of a small amount of polar additive into the above mentioned system.Furthermore,in pure polar solvent,such as dimethoxyethane(DME),tetrahydrofuran(THF)or dioxane(DOX),PBLi is completely dissociatedinto monomeric species;however,in pure diethyl ether,due to its weak polarity a part of associated species stillcan be found.Generally speaking,all of the above results were consistent with the results of kinetic studies in-vestigated by us before.     

工业PTA溶剂脱水过程动态模拟与分析

Dynamic model for dehydration process of industrial purified terephthalic acid solvent is investigated to understand and characterize the process.A temperature differential expression is presented,which ensures the equation to convergence and short computation time.The model is used to study the dynamic behavior of an azeotropic distillation column separating acetic acid and water using n-butyl acetate as the entrainer.Responses of the column to feed flow and aqueous reflux flow are simulated.The movement of temperature front is also simulated.The comparison between simulation and industrial values shows that the model and algorithm are effective.On the basis of simulation and analysis,control strategy,online optimization and so on can be implemented effectively in dehydration process of purified terephthalic acid solvent.     

通过官能团选择萃取精馏的溶剂

A method to select solvent for extractive distillation is proposed by UNIFAC group contribution. Solvent selectivity can be divided into two parts: the partial combinatorial solvent selectivity and the partial residual solvent selectivity. The properties of partial combinatorial and residual solvent selectivity are demonstrated. In most cases,the partial residual solvent selectivity is predominant. The candidate groups of solvent can be selected by group interaction parameter using UNIFAC group interaction parameter table as a guide.     

Solvent Selection for Extractive Distillation by the Universal Quasichemical Functional Group Activity Coefficient(UNIFAC) Group Contribution Method

A method to select solvent for extractive distillation is proposed by UNIFAC group contribution. Solvent selectivity can be divided into two parts: the partial combinatorial solvent selectivity and the partial residual solvent selectivity. The properties of partial combinatorial and residual solvent selectivity are demonstrated. In most cases, the partial residual solvent selectivity is predominant. The candidate groups of solvent can be selected by group interaction parameter using UNIFAC group interaction parameter table as a guide.     

离子液体在6号溶剂油改质中的应用

A new method of upgrading 6# solvent oils using different ionic liquids as catalysts in a continuous apparatus is studied in this paper. The results show that aromatics, olefins and small quantity of sulfurs can be removed simultaneously. Using complex ionic liquid modified with CuCl as catalyst, olefins are removed completely, the mass concentrations of aromatics and sulfurs in solvent oil are 0.36% and 0.0058%, respectively, and the bromic index is zero. The sulfur removal rate decreases gradually with increasing of running time. The refined 6# solvent oil is corresponded to the quality standards of GB16629-1996, which request that the mass concentrations of aro-matics, sulfurs and bromic index are 1%, 0.012% and 1000, respectively. The loss of solvent oil is less than 3%.     

超临界CO2萃取生姜油实验研究与数值模拟

利用自建的超临界流体萃取实验装置,以CO2为萃取剂,考察了萃取压力、温度、流体流量及原料颗粒度等因素对生姜油累积萃取率的影响,由此确定了较佳的萃取工艺条件。基于萃取器微分单元质量守恒原理,建立了数学模型,并利用直线推动力近似理论拟合了总传质推动力及平衡吸收常数,对实验结果进行了数值模拟。     

超临界二氧化碳萃取枸杞籽油的实验研究与数值模拟

建立了一套超临界流体萃取枸杞籽油的实验流程。以二氧化碳为萃取剂,考察了萃取压力、操作温度、二氧化碳流量及原料颗粒度等因素对枸杞籽油萃取率的影响。确定了较佳的萃取工艺条件:压力30MPa,温度313～318K,枸杞籽颗粒40～50目,二氧化碳流量0.3～0.4m3/h时枸杞籽油萃取率最高,可达15.5%。基于萃取器微分单元和固态颗粒微分单元质量守恒原理,建立了微分方程,利用直线推动力近似理论拟合总传质推动力及平衡吸收常数,化简方程,对部分实验结果进行数值模拟。     

超临界CO_2和微波辅助萃取当归挥发油

考察当归挥发油的不同提取方法。文中用超临界CO2流体萃取法和微波辅助萃取法研究萃取当归挥发油。实验表明:超临界CO2萃取最佳工艺条件为萃取压力25 MPa、分离釜Ⅰ解析温度55℃、萃取温度45℃,提取率约1.9%;微波辅助萃取最佳工艺条件为无水乙醇为提取溶剂,微波功率800 W、微波辐射时间150 s、液料质量比为4.71∶1,提取率约11.2%。微波辅助萃取法取得当归油的收率高于超临界CO2萃取法。微波辅助萃取法萃取当归挥发油收率高,但外观品质较超临界萃取的当归挥发油差。     

超临界流体萃取天然产物传质模型

为开发超临界流体萃取天然产物过程简单可靠的传质理论模型,对其传质机理进行了分析,由微分质量衡算方程经合理简化得到了动力学模型的解析解.定义了新准数B_z(可以确切地表征萃取过程的动态传质状况)和特征时间t_k,当t=t_k时,-dr_c/dt取得极小值,其原因可能是由内扩散传质阻力与内扩散传质推动力（浓度差）相竞争的结果.采用此数学模型计算了完全萃取时间t_ex、萃取收率Y随时间t的变化以及流体流率Q对萃取收率Y的影响,计算结果与文献中的实验数据吻合良好.本模型简单可靠,可用于超临界流体萃取天然产物过程的预测、分析、设计、模拟和优化.     

超临界CO_2萃取青皮挥发油的工艺研究

采用正交实验法对超临界CO2萃取中药青皮挥发油的最佳工艺条件进行优选。以挥发油得率为考察指标,探讨了萃取压力、萃取温度、萃取时间三因素在不同水平下对青皮挥发油得率的影响,并与水蒸气蒸馏法进行了比较。研究表明,萃取压力对挥发油得率有显著影响,萃取温度及时间影响不显著,各因素作用主次关系为:压力>温度>时间。优选得到的最佳工艺为:萃取压力25 MPa,萃取温度35℃,萃取时间1.5 h,得率为1.3197%,比水蒸气蒸馏法提高2.4倍,时间减少78.57%。超临界CO2萃取收率高、耗时短、品质好。     

ZrO2陶瓷注射成型超临界CO2流体脱脂动力学研究

用传统扩散方程建立了描述ZrO2陶瓷注射成型超临界流体脱脂过程的传质模型,研究分析了陶瓷注射成型超临界流体脱脂行为和脱脂的动力学过程。研究结果表明：有机粘合剂的溶解和扩散是陶瓷注射成型超临界脱脂过程关键因素,其中扩散为控制步骤。当脱脂时间足够长,模型计算曲线与实验结果吻合。通过实验数据,利用简单的理论模型可以得到相应的扩散系数。利用传质模型可以预测陶瓷注射成型超临界脱脂过程传质速率和萃取动力学。     

藜芦生物碱的提取技术研究

[目的]采用超临界CO2萃取法和改进碱性乙醇浸泡法提取藜芦生物碱。[方法]以藜芦生物碱含量、提取时间为指标,将超临界CO2萃取法和改进碱性乙醇浸泡法提取藜芦生物碱进行比较。[结果]在最佳工艺条件下,超临界CO2萃取碱化后的藜芦,其粗品提取率为3.13%,藜芦生物碱的质量分数可达(藜芦总碱/粗品)14.38%,萃取时间3 h;碱性乙醇溶液浸泡法藜芦粗碱收率为10.15%,藜芦生物碱质量分数为4.35%,时间72 h。[结论]与传统提取方法相比,超临界CO2萃取藜芦生物碱不但提取率高、时间短,而且粗碱中生物碱比例高、杂质少、浊度小,过程环保、高效。     

超临界CO2萃取胡椒油实验研究与数值模拟

建立了超临界流体萃取胡椒油实验装置,以CO2为萃取剂,考察了萃取压力、温度、CO2流量及原料颗粒大小等因素对胡椒油萃取率的影响,并由此确定了较佳的萃取工艺条件:压力22—26 MPa,温度313—323 K,胡椒颗粒度30—40目,CO2流量0.3—0.4 m3/h,胡椒油累积萃取率可达80%—90%。基于萃取器微分单元和固态原料颗粒微分单元质量守恒原理,建立了微分方程,利用直线推动力近似理论拟合总传质推动力及平衡吸收常数,化简方程,对实验结果进行了数值模拟。     

超临界CO_2萃取沙棘油的实验研究及数值模拟

本文利用超临界CO2萃取沙棘油,建立了一套实验流程,分别考察了萃取压力、萃取温度以及颗粒大小对萃取率的影响。同时根据萃取器单元的质量守恒建立了微分方程,并对一定萃取条件下的实验结果进行数值模拟。结果表明, 本文所建立的数值模型能较好地描述实际萃取行为。     

人工神经网络模拟超临界萃取米槁精油

为了更好地研究超临界CO2流体萃取米槁精油过程,文中对该过程萃取动力学进行了分析,建立了3层反向传导的人工神经网络模型。以MATLAB软件为平台,编制模型程序。以温度、压力、超临界CO2流体流率和原料平均粒径为输入,以收率为输出对网络进行训练。训练好的模型可用于萃取过程预测,与实验结果比较,预测平均误差小于5.0%。说明该模型可以对萃取过程进行模拟和预测。