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SCI和EI收录∣中国化工学会会刊
本期目录
2016年 第24卷 第11期 刊出日期:2016-11-28
    第25届中国过程控制会议专栏
    Research progress in ionic liquids catalyzed isobutane/butene alkylation
    Panxue Gan, Shengwei Tang
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1497-1504.  doi:10.1016/j.cjche.2016.03.005
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    The complicated reaction mechanismand the character of competitive reactions lead to a stringent requirement for the catalyst of C4 alkylation process. Due to their unique properties, ionic liquids (ILs) are thought to be new potential acid catalysts for C4 alkylation. An analysis of the regular and modified chloroaluminate ILs, novel Brønsted ILs and composite ILs used in isobutane/butene alkylation shows that the use of either ILs or ILs coupled with mineral acid as homogeneous catalysts can help to greatly adjust the acid strength. Bymodifying the structural parameters of the cations and anions of the ILs, the solubility of the reactants could also be adjusted, which in turn displays a positive effect on improving the activity of ILs. Immobilization of ILs is an effectiveway to modulate the surface adsorption/desorption properties and acid strength distribution of the solid acid catalysts. Such a process has a tremendous potential to reduce the deactivation of catalyst and enhance the activity of the solid acid catalyst. The development of novel acid catalysts for C4 alkylation is a comprehensive consideration of acid strength and its distribution, interfacial properties and transport characteristics.
    Lattice Boltzmann simulation of a laminar square jet in cross flows
    Guoneng Li, Youqu Zheng, Huawen Yang, Wenwen Guo, Yousheng Xu
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1505-1512.  doi:10.1016/j.cjche.2016.03.008
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    A three-dimensional, nineteen-velocity (D3Q19) Lattice BoltzmannMethod (LBM) modelwas developed to simulate the fluid flow of a laminar square jet in cross flows based on the single relaxation time algorithm. The code was validated by the mathematic solution of the Poiseuille flow in a square channel, and was further validated with a previouswell studied empirical correlation for the central trajectory of a jet in cross flows. The developed LBM model was found to be able to capture the dominant vortex, i.e. the Counter-rotating Vortex Pair (CVP) and the upright wake vortex. Results show that the incoming fluid in the cross flow channel was entrained into the leeside of the jet fluid, which contributes to the blending of the jet. That the spread width of the transverse jet decreaseswith the velocity ratio. A layer-organized entrainment pattern was found indicating that the incoming fluid at the lower position is firstly entrained into the leeside of the jet, and followed by the incoming fluid at the upper position.
    CO2/N2 separation using supported ionic liquid membranes with green and cost-effective[Choline] [Pro]/PEG200 mixtures
    Tengteng Fan, Wenlong Xie, Xiaoyan Ji, Chang Liu, Xin Feng, Xiaohua Lu
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1513-1521.  doi:10.1016/j.cjche.2016.03.006
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    The high price and toxicity of ionic liquids (ILs) have limited the design and application of supported ionic liquid membranes (SILMs) for CO2 separation in both academic and industrial fields. In this work,[Choline] [Pro]/polyethylene glycol 200 (PEG200) mixtures were selected to prepare novel SILMs because of their green and costeffective characterization, and the CO2/N2 separation with the prepared SILMs was investigated experimentally at temperatures from 308.15 to 343.15 K. The temperature effect on the permeability, solubility and diffusivity of CO2 was modeled with the Arrhenius equation. A competitive performance of the prepared SILMs was observed with high CO2 permeability ranged in 343.3-1798.6 barrer and high CO2/N2 selectivity from 7.9 to 34.8. It was also found that the CO2 permeability increased 3 times by decreasing the viscosity of liquids from 370 to 38 mPa·s. In addition, the inherent mechanism behind the significant permeability enhancement was revealed based on the diffusion-reaction theory, i.e. with the addition of PEG200, the overall resistance was substantially decreased and the SILMs process was switched from diffusion-control to reaction-control.
    Adsorption of 2-naphthalenesulfonic acid/sulfuric acid/sulfurous acid from aqueous solution by iron-impregnated weakly basic resin: Equilibrium and model
    Changhai Li, Dongmei Jia
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1522-1526.  doi:10.1016/j.cjche.2016.03.007
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    Commercial grade weakly basic resin D301 was impregnated with iron through a simple method using ferric chloride. Experiments for single, bisolute and trinary competitive adsorption were carried out to investigate the adsorption behavior of 2-naphthalenesulfonic acid (NSA), sulfuric acid and sulfurous acid from their solution at 298K onto the novel hybrid iron impregnated D301(Fe-D301). Adsorption affinity of NSA on Fe-D301 was found to be much higher than that of sulfuric acid, while adsorption affinity of sulfuric acid was slightly higher than that of sulfurous acid. The data of single-solute adsorption were fitted to the Langmuir model and the Freundlich adsorption model. The non-ideal competitive adsorbedmodel coupledwith the single-solute adsorption models were used to predict the bisolute and trinary-solute competitive adsorption equilibria. The NICM coupled with the Langmuir model yields the favorable representation of the bisolute and trinary-solute competitive adsorption behavior.
    Extended adsorption transport models for permeation of copper ions through nanocomposite chitosan/polyvinyl alcohol thin affinity membranes
    Ehsan Salehi, Leila Bakhtiari, Mahdi Askari
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1527-1532.  doi:10.1016/j.cjche.2016.04.013
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    Transport of copper ions through nanocomposite chitosan/polyvinyl alcohol thin adsorptive membranes has been mathematically investigated in the current study. Unsteady-state diffusive transport model was coupled with the Freundlich isotherm to predict the concentration of the ions in dialysis permeation operation. Pristine model was not successful in predicting the experimental data based upon its low coefficients of determination (0.1 < R2 < 0.65). Well-behaved polynomial and exponential functions were used to describe time-dependency of the inlet-concentration in the first extension of themodel with a little improvement in the model adjustment (0.4 < R2 < 0.69). Similar time-dependent functions were employed for tracking the ion diffusivity and then applied in combination with the optimized functions of inlet-concentration in the second extension of the model. A sensible enhancement was obtained in the adjustment of the second extended models as a result of this combination (0.73 < R2 < 0.93). APRE, AAPRE, RSME, RMSE, STD and R-square statistical analyses were performed to verify the agreement of the models with the experimental results. Concentration distribution versus time and location (inside the membrane) was obtained as 3D plots with the help of the optimized models. Modeling results emphasized on the transiency of diffusivity and feed-side concentration in dialysis permeation through chitosan membranes.
    Novel nanofiltration membranes with tunable permselectivity by polymer mediated phase separation in polyamide selective layer
    Zhuan Yi, Fa-dong Wu, Yong Zhou, Cong-jie Gao
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1533-1540.  doi:10.1016/j.cjche.2016.04.019
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    Microstructure in selective layer has played a decisive role in permselectivity of nanofiltration (NF) membranes, and nanomaterials were well-known additives that had been applied to mediate the microstructure and permeability of polyamide NF membranes. However, nanoadditives generally displayed a poor dispersion in membranes or in fabrication process. To solve this problem, we showed an interesting concept that novel NF membranes with hybrid selective layer consisting of flexible polyisobutylene (PIB) and rigid polyamide could be fabricated fromwell-defined interfacial polymerization. The hydrophobic polymer mediated phase separation andmicrodomains formation in polyamide layerwere found. The immiscibility between the rigid polyamide and flexible PIB as well as the resultant interface effect was interpreted as the reason for the polymer enhanced permselectivity, which was similar with the well-known thin film nanocomposite (TFN) membranes that nanoparticles incorporated contributed significantly to membrane permeability and rejection performance. Our results have demonstrated that novel NF membranes with enhanced performance can be prepared fromimmiscible polymers, which is a new area that has not been extensively studied before.
    An efficient methodology for utilization of K-feldspar and phosphogypsum with reduced energy consumption and CO2 emissions
    Zhixi Gan, Zheng Cui, Hairong Yue, Siyang Tang, Changjun Liu, Chun Li, Bin Liang, Heping Xie
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1541-1551.  doi:10.1016/j.cjche.2016.04.001
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    The issues of reducing CO2 emissions, sustainably utilizing naturalmineral resources, and dealing with industrial waste offer challenges for sustainable development in energy and the environment. We propose an efficient methodology via the co-reaction of K-feldspar and phosphogypsum for the extraction of soluble potassium salts and recovery of SO2 with reduced CO2 emission and energy consumption. The results of characterization and reactivity evaluation indicated that the partial melting of K-feldspar and phosphogypsum in the hightemperature co-reaction significantly facilitated the reduction of phosphogypsum to SO2 and the exchange of K+ (K-feldspar) with Ca2+ (CaSO4 in phosphogypsum). The reaction parameters were systematically investigated with the highest sulfur recovery ratio of ~60% and K extraction ratio of ~87.7%. This novel methodology possesses an energy consumption reduction of ~28% and CO2 emission reduction of ~55% comparing with the present typical commercial technologies for utilization of K-feldspar and the treatment of phosphogypsum.
    Hydrothermal synthesis of calcium sulfate whisker from flue gas desulfurization gypsum
    Chengjun Liu, Qing Zhao, Yeguang Wang, Peiyang Shi, Maofa Jiang
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1552-1560.  doi:10.1016/j.cjche.2016.04.024
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    Plenty of flue gas desulfurization (FGD) gypsum generated from coal-fired power plants for sulfur dioxide sequestration caused many environmental issues. Preparing calcium sulfate whisker (CSW) from FGD gypsum by hydrothermal synthesis is considered to be a promising approach to solve this troublesome problem and utilize calcium sulfate in a high-value-added way. The effects of particle size of FGD gypsum, slurry concentration, and additives on CSW were investigated in this work. The results indicated that fine particle size of FGD gypsum and moderately high slurry concentration were beneficial for crystal nucleation and growth. Three additives of magnesium chloride, citric acid, and sodium dodecyl benzene sulfonate (SDBS) were employed in this study. It was found that mean length and aspect ratio of CSW were both decreased by the usage of magnesium chloride, while a small quantity of citric acid or SDBS could improve the CSW morphology. When multi-additives of citric acid-SDBS were employed, the mean length and aspect ratio increased more than 20%. Moreover, surface morphology of CSW went better, and the particle size and crystal shape became more uniform.
    Application of Brönsted acid ionic liquids as green catalyst in the synthesis of 2-propanol with reactive distillation
    Jinbei Yang, Dongren Cai, Ting Zeng, Lihua Zhou, Ling Li, Ruoyu Hong, Ting Qiu
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1561-1569.  doi:10.1016/j.cjche.2016.04.025
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    Five Brönsted acidic ionic liquids (ILs)were prepared and characterized by FT-IR, 1H NMR and 13CNMR. Their catalytic activities for the synthesis of 2-propanol (IPOH) via transesterification of isopropyl acetate (IPAc) with methanol (MeOH) were investigated. Among all the tested ILs,[Ps-mim]HSO4 performed best and was used as catalyst for further studies. The reaction kinetics were carried out to correlate the parameters in a homogeneous second order kinetic model. It has been found that there is close agreement between the calculated and experimental values. The high-pressure batch reactive distillation experimental apparatus was set up in order to enhance the conversion of IPAc. A high conversion of IPAc of 99.4% was obtained under the optimal reaction conditions. The catalyst[Ps-mim]HSO4 can be recycled easily by a rotary evaporator and reusedwithout any further treatment. The catalyst had been repeatedly used for four times and no obvious changes in the structure of catalyst could be observed.
    Effects of porous oxide layer on performance of Pd-based monolithic catalysts for 2-ethylanthraquinone hydrogenation
    Xin Shi, Enxian Yuan, Guozhu Liu, Li Wang
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1570-1576.  doi:10.1016/j.cjche.2016.04.032
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    Pd/oxide/cordieritemonolithic catalysts (oxide=Al2O3, SiO2 and SiO2-Al2O3)were prepared by the impregnation method. The results of ICP, XRD, SEM-EDX, XPS and N2 adsorption-desorption measurements revealed that the Pd penetration depth increased with increasing the thickness of oxide layer, and the catalysts with Al2O3 layers had the larger pore size than those with SiO2 and SiO2-Al2O3 layers. Catalytic hydrogenation of 2-ethylanthraquinone (eAQ), a key step of the H2O2 production by the anthraquinone process, over the various monolithic catalysts (60℃, atmosphere pressure) showed that themonolithic catalystwith the moderate thickness of Al2O3 layer (about 6 μm) exhibited the highest conversion of eAQ (99.1%) and hydrogenation efficiency (10.0 g·L-1). This could be ascribed to the suitable Pd penetration depth and the larger pore size,which provides a balance between the distribution of Pd and accessibility of active sites by the reactants.
    Synthesis, characteristics of hierarchical EU-1 zeolite for xylene isomerization probe reaction
    Xiaofeng Li, Pengchao Ren, Yanting Zhang, Xiaozhen Liu, Xiaotao Sun, Meng Gao, Miaojuan Jia, Zhiping Lü, Tao Dou
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1577-1583.  doi:10.1016/j.cjche.2016.05.002
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    Introduced amethod of synthesizing hierarchical EU-1 zeolitewith organosilanes as additive, and studied the influences of following different kinds of organosilanes on the synthesis of hierarchical EU-1 zeolite:γ-glycidoxy propyl trimethoxy silane (GPTMS), N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxyl silane (APAEDMS), and N-(β-aminoethyl)-γ-aminopropyl dimethoxyl (ethyoxyl) silane (TMPED). The hierarchical EU-1 samples were characterized by XRD, SEM,N2 adsorption, FT-IR and NH3-TPD to analyze the crystallinity,morphology, surface area, pore size distribution and acidity. The results showed that hierarchical EU-1 zeolites were successfully synthesized; organosilanes have great influence on crystal morphology of EU-1 zeolites; the exterior surface area of hierarchical EU-1 zeolite, which synthesized with organosilanes (APAEDMS) adding into synthesis system, increased by 62.1% andmesopore volume increased by 129.1% comparedwith conventional EU-1 zeolites, thus can reduce the diffusional restriction markedly in catalytic reaction. The catalytic performance of hierarchical EU-1 zeolites were evaluated in m-xylene isomerization on fixed bed reactor. The catalytic data showed that the isomerization activity PX/X of the hierarchical EU-1 zeolites reached around 24.09% in theoretical thermodynamic equilibrium from 23.83%, and the selectivity of C8 aromatic hydrocarbon increased from 75.16% to 84.87%. The conversion of p-xylene increased from 16.30% to 18.41%.
    Design and control of methyl acetate-methanol separation via heat-integrated pressure-swing distillation
    Zhishan Zhang, Qingjun Zhang, Guijie Li, Meiling Liu, Jun Gao
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1584-1599.  doi:10.1016/j.cjche.2016.06.013
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    Design and control of pressure-swing distillation (PSD) with different heat integration modes for the separation of methyl acetate/methanol azeotrope are explored using Aspen Plus and Aspen Dynamics. First, an optimum steady-state separation configuration conditions are obtained via taking the total annual cost (TAC) or total reboiler heat duty as the objective functions. The results show that about 27.68% and 25.40% saving in TAC can be achieved by the PSD with full and partial heat integration compared to PSD without heat integration. Second, temperature control tray locations are obtained according to the sensitivity criterion and singular value decomposition (SVD) analysis and the single-end control structure is effective based on the feed composition sensitivity analysis. Finally, the comparison of dynamic controllability is made among various control structures for PSD with partial and full heat integration. It is shown that both control structures of composition/temperature cascade and pressure-compensated temperature have a good dynamic response performance for PSD with heat integration facing feed flowrate and composition disturbances. However, PSD with full heat integration performs the poor controllability despite of a little bit of economy.
    Solving chemical dynamic optimization problems with ranking-based differential evolution algorithms
    Xu Chen, Wenli Du, Feng Qian
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1600-1608.  doi:10.1016/j.cjche.2016.04.044
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    Dynamic optimization problems (DOPs) described by differential equations are often encountered in chemical engineering. Deterministic techniques based on mathematic programming become invalid when the models are non-differentiable or explicit mathematical descriptions do not exist. Recently, evolutionary algorithms are gaining popularity for DOPs as they can be used as robust alternativeswhen the deterministic techniques are invalid. In this article, a technology named ranking-based mutation operator (RMO) is presented to enhance the previous differential evolution (DE) algorithms to solve DOPs using control vector parameterization. In the RMO, better individuals have higher probabilities to produce offspring, which is helpful for the performance enhancement of DE algorithms. Three DE-RMO algorithms are designed by incorporating the RMO. The three DE-RMO algorithms and their three original DE algorithms are applied to solve four constrained DOPs from the literature. Our simulation results indicate that DE-RMO algorithms exhibit better performance than previous non-ranking DE algorithms and other four evolutionary algorithms.
    An analysis of an ethanol-based, whole-crop refinery system in China
    Zhiqiang Zhang, Shanying Hu, Dingjiang Chen, Bing Zhu
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1609-1618.  doi:10.1016/j.cjche.2016.05.036
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    Bio-fuel can be used to help transition froma petroleum-based society to a bio-based society. Ever since the China Development and Reform Commission suspended the approval of crop processing programs, second-generation bio-ethanol research and industrialization processes have attracted significant attention. In 2020, bio-ethanol production is predicted to reach 10 million tons. Currently, there are a few domestic enterprises that have established different scaled pilot or demonstration bases for cellulosic ethanol, which reduce the cost of ethanol by continuously improving pretreatment and hydrolysis techniques. In the next three years, these enterprises will realize large-scale commercial production. Given the practical problems in cellulosic ethanol plant construction and operation (e.g., marketing price variation and difficulties in feedstock collection), this paper began with the concept of a "whole-crop refinery" and presented a solution to the integration of industry and agriculture as well as multi-crop refining. This paper then took the whole-crop refining system of corn as an example and presented an analysis of the logistics, energy flow, and economical efficiency of the system. The results demonstrated that the integrated system could properly reduce the required fixed investments in production equipment, shared utilities, and wastewater treatment facilities, as well as reduction of energy consumption. Although the proposed system has several problems, it brings the long-term goal of large-scale commercial application closer than ever.
    COSMO-RS: An ionic liquid prescreening tool for gas hydrate mitigation
    Cornelius B. Bavoh, Bhajan Lal, Omar Nashed, Muhammad S. Khan, Lau K. Keong, Mohd. Azmi Bustam
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1619-1624.  doi:10.1016/j.cjche.2016.07.014
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    Recently ionic liquids (ILs) are introduced as novel dual function gas hydrate inhibitors. However, no desired gas hydrate inhibition has been reported due to poor IL selection and/or tuning method. Trial & error as well as selection based on existing literature are the methods currently employed for selecting and/or tuning ILs. These methods are probabilistic, time consuming, expensive and may not result in selecting high performance ILs for gas hydrate mitigation. In this work, COSMO-RS is considered as a prescreening tool of ILs for gas hydrate mitigation by predicting the hydrogen bonding energies (EHB) of studied IL inhibitors and comparing the predicted EHB to the depression temperature (?) and induction time. Results showthat, predicted EHB and chain length of ILs strongly relate and significantly affect the gas hydrate inhibition depression temperature but correlate moderately (R=0.70) with average induction time in literature. It is deduced fromthe results that, ? increaseswith increasing IL EHB and/or decreases with increasing chain length. However, the cation-anion pairing of ILs also affects IL gas hydrate inhibition performance. Furthermore, a visual and better understanding of IL/water behavior for gas hydrate inhibition in terms of hydrogen bond donor and acceptor interaction analysis is also presented by determining the sigma profile and sigma potential of studied IL cations and anions used for gas hydrate mitigation for easy IL selection.
    Droplets diameter distribution using maximum entropy formulation combined with a new energy-based sub-model
    Seyed Mostafa Hosseinalipour, Hadiseh Karimaei, Ehsan Movahednejad
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1625-1630.  doi:10.1016/j.cjche.2016.03.004
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    The maximum entropy principle (MEP) is one of the firstmethods which have been used to predict droplet size and velocity distributions of liquid sprays. Thismethod needs amean droplets diameter as an input to predict the droplet size distribution. This paper presents a newsub-model based on the deterministic aspects of liquid atomization process independent of the experimental data to provide the mean droplets diameter for using in the maximum entropy formulation (MEF). For this purpose, a theoretical model based on the approach of energy conservation law entitled energy-based model (EBM) is presented. Based on this approach, atomization occurs due to the kinetic energy loss. Prediction of the combinedmodel (MEF/EBM) is in good agreement with the available experimental data. The energy-basedmodel can be used as a fast and reliable enoughmodel to obtain a good estimation of the mean droplets diameter of a spray and the combined model (MEF/EBM) can be used to well predict the droplet size distribution at the primary breakup.
    Simultaneous hybrid modeling of a nosiheptide fermentation process using particle swarm optimization
    Qiangda Yang, Hongbo Gao, Weijun Zhang, Huimin Li
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1631-1639.  doi:10.1016/j.cjche.2016.08.013
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    Hybrid modeling approaches have recently been investigated as an attractive alternative to model fermentation processes. Normally, these approaches require estimation data to train the empirical model part of a hybrid model. This may result in decreasing the generalization ability of the derived hybridmodel. Therefore, a simultaneous hybridmodeling approach is presented in this paper. It transforms the training of the empiricalmodel part into a dynamic system parameter identification problem, and thus allows training the empiricalmodel partwith only measured data. An adaptive escaping particle swarm optimization (AEPSO) algorithm with escaping and adaptive inertia weight adjustment strategies is constructed to solve the resulting parameter identification problem, and thereby accomplish the training of the empirical model part. The uniform design method is used to determine the empirical model structure. The proposed simultaneous hybrid modeling approach has been used in a lab-scale nosiheptide batch fermentation process. The results show that it is effective and leads to a more consistent model with better generalization ability when compared to existing ones. The performance of AEPSO is also demonstrated.
    Jatropha curcas L. oil extracted by switchable solvent N, N-dimethylcyclohexylamine for biodiesel production
    Shanjin Zeng, Chuandong Tao, Richard Parnas, Wei Jiang, Bin Liang, Yingying Liu, Houfang Lu
    Chinese Journal of Chemical Engineering. 2016, 24(11):  1640-1646.  doi:10.1016/j.cjche.2016.04.023
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    Biodiesel, which is a renewable and environmentally friendly fuel, has been studied widely to help remedy increasing environmental problems. One of the key processes of biodiesel production is oil extraction fromoilseed materials. Switchable solvents can reversibly change from molecular to ionic solvents under atmospheric CO2, and can be used for oil extraction. N, N-dimethylcyclohexylamine (DMCHA), a switchable solvent, was used to extract oil from Jatropha curcas L. oil seeds to produce biodiesel. The appropriate extraction conditions were:1:2 ratio of seedmass to DMCHA volume, 0.3-1mmparticle size, 200 r·min-1 agitation speed, 60min extraction time, and 30℃ extraction temperature. The extraction ratio was about 83%. This solvent extracted the oil more efficiently than hexane, and ismuch less volatile. By bubbling CO2 under 1 atmand 25℃ for 5 h, the oilwas separated, and DMCHA was recovered after releasing CO2 by bubbling N2 under 1 atmand 60℃ for 2 h. The residual solvent content in oil was about 1.7%. Selectivity of DMCHA was evaluated by detecting the protein and sugar content in oil. Using the oil with residual solvent to conduct transesterification process, the oil conversion ratio was approximately 99.5%.