A rate-based method for dynamic analysis and optimal design of reactive extraction: n-Hexyl acetate esterification as an example

The dynamic analysis and optimal design of reactive extraction are challenging due to high nonlinearity of model equations and tough decision of judging criteria. In this work, a dynamic rate-based method is developed on g PROMS platform to get easy access to the solutions of reactive extraction with phase splitting. Based on rigorous criteria, dynamic analysis from initial state to final equilibrium(e.g., evolution of phase composition, mass transfer rate and reaction rate) and optimal design of operating conditions(e.g., extractant dosage and feed molar ratio) are achieved. To illustrate the method, the esterification of n-hexyl acetate is taken as an example. The approach proves to be reliable in the analysis and optimization of the exemplified system, which provides instructive reference for further process design and simulation of reactive extraction.

Preparation, Characterization and Catalytic Performance of La-SO_4^(2-)/SBA-15 in Esterification of Acetic Acid with n-Butanol

La-SO42-/SBA-15 was synthesized with various amounts of lanthanum via incipient-wetness impregnation. Characterization was done by X-ray diffraction（XRD）, transmission electron micrographs（TEM）, nitrogen adsorption, FTIR spectroscopic analysis, thermogravimetric analysis, and the total amount of acidity of catalyst was estimated by TPD of NH3. The results indicate that lanthanum has been incorporated into SBA-15 molecular sieve. The prepared materials（La-SO42-/SBA-15） keep the highly ordered mesoporous two-dimensional hexagonal structure and do not change the mesoporous channel structure of the support SBA-15. The catalyst showed best catalytic activity in the synthesis of n-butyl acetate. The optimum conditions of the esterification by orthogonal experiments were studied： the molar ratio of n-butanol to acetic acid 1：1.2, the amount of catalyst 7.5%, reaction time 80 min. The yield of n-butyl acetate could reach 93.2% under the optimum conditions. The catalyst was recyclable, cost effective and environmental friendly.

Preparation,Characterization of Dawson-type Heteropoly Acid Cerium（Ⅲ） Salt and Its Catalytic Performance on the Synthesis of n-Butyl Acetate

A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential thermal analyses(TG/DTA),Fourier transform infrared spectroscopy(FT-IR),X-ray powder diffraction(XRD),pyridine infrared spectroscopy(Py-IR) and scanning electron microscopy(SEM).Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol.The effects of various parameters such as molar ratio of n-butanol to acetic acid,reaction temperature,reaction time,and catalyst amount have been studied by single factor experiment.The results show that Ce2P2W18O62·16H2O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate.The optimum synthetic conditions were determined as follows︰molar ratio of n-butanol to acetic acid at 2.0︰1.0,mass of the catalyst being 1.44% of the total reaction mixture,reaction temperature of 120 ℃ and reaction time of 150 min.Under above conditions,the conversion of acetic acid was above 97.8%.The selectivity of n-butyl acetate based on acetic acid was,in all cases,nearly 100%.The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction.It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products.Compared with using sulfuric acid as catalyst,the present procedure with Ce2P2W18O62·16H2O is a green productive technology due to simple process,higher yield,catalyst recycling and no corrosion for the production facilities.

Reactive Distillation for Producing n-Butyl Acetate:Experiment and Simulation

In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model for separation were employed to study the RD process. The results obtained from the equilibrium stage model agreed well with the experiments. The effects of operating variables on the n-butanol conversion and n-butyl acetate purity were further investigated. The optimal column configuration for the production of n-butyl acetate was designed with 5 rectifying stages, 8 reaction stages and 13 stripping stages by the simulation study. According to the simulation results, n-butanol conversion and n-butyl acetate purity all reached greater than 96%.

Vapor-Liquid Equilibria for Dimethyl Carbonate-n-Butyl Acetate Binary System at 101.325kPa

The vapor-liquid equilibrium (VLE) data for the dimethyl carbonate-n-butyl acetate binary system were measured by an Ellis equilibrated distillator. The experimental data were checked for their thermodynamic consistency through statistical methods. The VLE data was correlated with Wilson and NRTL activity coefficient models and also with the calculation of the vapor phase fugacity coefficient by the modified Peng-Robinson equation of state.

Catalytic Esterification of Methyl Alcohol with Acetic Acid

Esterification of methyl alcohol with acetic acid catalysed by Amberlyst-15 (cation-exchange resin) was carried out in a batch reactor in the temperature ranging between 318-338 K, at atmospheric pressure. The reaction rate increased with increase in catalyst concentration and reaction temperature, but decreased with an increase in water concentration. Stirrer speed had virtually no effect on the rate under the experimental conditions. The rate data were correlated with a second-order kinetic model based on homogeneous reaction. The apparent activation energy was found to be 22.9kJ mol-1 for the formation of methyl acetate. The methyl acetate production was carried out as batch and continuous in a packed bed reactive distillation column with high purity methyl acetate produced.

Reactive dividing-wall column for the co-production of ethyl acetate and n-butyl acetate

Reactive dividing-wall column(RDWC) technology plays a critical role in the energy saving and high efficiency of chemical process.In this article, the process of co-producing ethyl acetate(EA) and n-butyl acetate(BA) with RDWC was studied.BA was not only the product, but also acted as entrainer to remove the water generated by the two esterification reactions.Experiments and simulations of the co-production process were carried out.It was found that the experimental results were in good agreement with the simulation results.Two kinds of RDWC structures(RDWC-FC and RDWC-RS) were proposed, and the co-production process operating parameters of the two types of RDWC were optimized by Aspen Plus respectively.The optimal operating parameters of the RDWC-FC were determined as follows: 0.6 of the reflux ratio of aqueous phase(RR), 0.66 of the vapor split(R_V) and 0.51 of the liquid split(R_L).And the optimal operating parameters of the RDWC-RS were shown as follows: RR was 0.295 and R_V was 0.61.Furthermore, the energy saving analysis of the co-production process was based on the annual output of 10000 tons of EA, compared with the traditional reaction distillation(RD) to prepare EA and BA, the reboiler duty of the RDWC-FC column could save 20.4%, TAC saving 23.6%; RDWC-RS reboiler energy consumption could save 17.0%, TAC 22.2%.

Cerium modified Y/SBA-15 composite molecular sieve catalyzed synthesis of n-butyl acetate

A novel Ce-Y/SBA-15 catalyst was prepared by modifying HY/SBA-15 microporous-mesoporous composite molecular sieve with cerium using the impregnation method. The characterization results from scanning electron microscopy/energy dispersive X-ray dispersive spectroscopy（SEM/EDS）, transmission electron microscopy（TEM）, and X-ray fluorescence（XRF） studies indicated that the Ce-modified catalyst maintained the microporous-mesoporous structure of Y/SBA-15. The Ce ions were found to be uniformly dispersed in the pores of the molecular sieve without aggregation. The results from pyrolysis coupled-Fourier transform infrared spectroscopy（Pyridine-FTIR） and temperature programmed desorption of ammonia（NH3-TPD） showed that the loading of cerium caused the hydroxyl group in the catalyst to display stronger Bronsted acidity. The efficiency of the modified Ce-Y/SBA-15 catalyst was evaluated by using it to catalyze the synthesis of n-butyl acetate. The optimal synthesis conditions were determined by orthogonal experiments. The highest esterification yield of 94.4% was obtained when the reaction time was 2.0 h, with acid/alcohol molar ratio of 1：1.2, and catalyst loading of 10 wt.%. The results in this study demonstrated that the loading of cerium and the structure of Y/SBA-15 microporous-mesoporous composite molecular sieve helped in improving the catalytic activity of this acidic catalyst.

Esterification of acetic acid with isobutanol catalyzed by ionic liquid n-sulfopropyl-3-methylpyridinium trifluoromethanesulfonate:Experimental and kinetic study

As an important organic,isobutyl acetate(IbAc)has been widely used in industries because of its good biodegradability,low surface tension,and other properties.The industrial production of IbAc is usually catalyzed by sulfuric acid.However,the use of sulfuric acid has the drawbacks of causing considerable corrosion to equipment and being difficult to be separated.In this work,n-sulfopropyl-3-methylpyridinium trifluoromethanesulfonate([HSO_(3)-PMPY][CF_(3)SO_(3)])Bronsted acidic ionic liquid(BAIL)was used as the catalyst and the catalytic activity,solubility,and corrosiveness were evaluated for the esterification of acetic acid with isobutanol.The reaction kinetics and chemical equilibrium were systemically studied.Compared to conventional acid catalysts,[HSO_(3)-PMPY][CF_(3)SO_(3)]showed higher catalytic activity,more excellent reusability,more favorable phase separation,and non-corrosiveness.Three kinetic equations based on ideal homogeneous(IH),non-ideal homogeneous(NIH),and modified nonideal homogeneous(NIH-M)models were established and correlated with the experimental data to determine the parameters and errors.The NIH-M model exhibited the best agreement with the experimental data,owing to its prediction considering the non-ideality and the self-catalysis effect of acetic acid in this system.Besides,the error of NIH-M model fitting was mainly caused by the difference in solubility between[HSO_(3)-PMPY][CF_(3)SO_(3)]with reactants and products in the reaction system.Furthermore,the applicability of the NIH-M model was investigated by simulating the esterification of acetic acid with three short-chain alcohols(ethanol,n-butanol,and isobutanol)catalyzed by BAILs.The NIH-M model displayed an acceptable simulation for this type of acetic acid esterification reaction catalyzed by BAILs at different ranges of the BAILs concentration and temperature.This study confirmed the industrial prospects of[HSO_(3)-PMPY][CF_(3)SO_(3)]in isobutyl acetate production and the applicability of the NIH-M kinetic model in the esterification of acetic acid.

ResearchonS202一／Zr02solidsuperacidinsynthesisofn—amylacetateundermicrowaveradiation

采用沉淀一浸渍法制得S2O62 8-／ZrO2固体超强酸，在微波辐射下催化合成乙酸正戊酯。通过单因素实验和正交实验优化了合成的反应条件；采用Hammett指示剂法、BET法、红外光谱、电子透镜技术和x_射线衍射对其进行了表征。实验结果表明，采用最佳制备条件下得到的催化剂在微波辐射下催化合成乙酸正戊酯的最优合成条件为：醇酸摩尔比1．9：1，反应温度135℃，反应时间25min，催化剂用量1．2g，功率500W，收率为97．8％。该工艺具有绿色、安全、操作简单和收率高等优点。

Residue curve maps of ethyl acetate synthesis reaction

The residue curve maps are considered as a powerful tool for the preliminary design of reactive distillation. The residue curve maps of ethyl acetate synthesis reaction were calculated based on the pseudo-homogeneous rate-based kinetic model and the NRTL activity coefficient model. The results show that the unstable node branch emerges from the ethyl acetate/water edge, moving toward the chemical equilibrium surface with the increase of Damkoeler value （D）, and the node reaches the ternary reactive azeotrope when D-∞ eventually. Conceptual design for the ethyl acetate synthesis of reactive distillation based on the residue curve maps is presented at last.

Investigation on catalytic distillation for ethyl acetate production with different catalytic packing structures

The catalytic packing is the core component of the catalytic distillation,and how the catalyst exists in the packing has significant influence on the process.To investigate the effect of catalyst packings on the catalytic distillation process,the classical ethyl acetate reactive distillation system was utilized,and a supported catalytic packing(SCP)was prepared in comparison with the conventional tea-bag catalytic packing(TBP).Laboratory scale experiments showed that the ethyl acetate conversion of the SCP was superior to the TBP at a low catalyst loading.The effects of reaction kinetics,mass transfer performance and actual catalytic efficiency of the packings on this process were regarded as reasons and studied by combining the experiments and numerical simulation.Results suggested that the relatively immediate“in-situ separation”caused by the rapid reaction kinetics and better mass transfer performance of SCP may be a main reason for the difference of the conversion.

A Novel Process Using Ion Exchange Resins for the Coproduction of Ethyl and Butyl Acetates

Before proposing an innovative process for the coproduction of ethyl and butyl acetates, the individual syntheses of ethyl acetate and butyl acetate by two different routes were first studied. These syntheses involved the reaction of ethanol or n-butanol with acetic acid or acetic anhydride in the presence of ion exchange resins: Amberlyst 15, Amberlyst 16, Amberlyst 36 and Dowex 50WX8. Kinetic and thermodynamic studies were performed with all resins. The lowest activation energy (Ea) value was obtained with Dowex 50WX8, which was identified as the best-performing resin, able to be reused at least in four runs without regeneration. The presence of water-azeotropes during the synthesis of ethyl acetate makes its purification difficult. A new strategy was adopted here, involving the use of ethanol and acetic anhydride as the starting material. In order to minimize acetic acid as co-product of this reaction, a novel two-step process for the coproduction of ethyl and butyl acetates was developed. The first step involves the production of ethyl acetate and its purification. Butyl acetate was produced in the second step: n-butanol was added to the mixture of acetic acid and the resin remaining after the first-step distillation. This process yields ethyl acetate and butyl acetate at high purity and shows an environmental benefit over the independent syntheses by green metrics calculation and life cycle assessment.

正交设计提高乙酸乙酯合成的产率和纯度

在乙酸乙酯合成的实验教学中,通常使用阿贝折射仪分析产物纯度,误差较大。在本研究中,采用气相色谱内标校正因子法和面积归一化法来测定乙酸乙酯的含量,我们发现内标校正因子法测量的结果准确度高,且操作简单。合成条件为:乙醇、乙酸摩尔比为1.5∶1,浓硫酸的添加量为2 mL。通过正交实验设计优化乙酸乙酯纯化过程,得到最佳纯化条件:20 mL饱和氯化钠溶液、40 mL 100%饱和氯化钙溶液(每次20 mL)、1.8 g无水硫酸镁。在此条件下提纯,我们将实验教学中普遍合成产率55%提高到80.70%,且纯度高达96.69%,实现了乙酸乙酯合成产率和纯度的双向提升。

正交法设计乙酸甲酯制备的教学实验

介绍了应用正交法设计乙酸甲酯制备教学实验的方法,分析了醇酸摩尔比、催化剂用量、分馏柱长度这三个因素对乙酸甲酯收率的影响,筛选出制备的最佳实验条件为醇酸摩尔比为1.3∶1,催化剂用量为1.5 mL,分馏柱长度30 cm,实现以较少的试验次数达到与全面试验相近的结果。在化学实验教学时,将实验操作训练与数据处理知识相结合,不仅提高了学生的学习兴趣,还让他们更好地理解实验设计思想,培养了他们分析问题和解决问题的实践能力和创新能力,取得了良好的教学效果。

不同链长烷基酸对纤维素纳米晶的改性研究

为了深入探究不同链长烷基酸对纤维素纳米晶(cellulose nanocrystals,CNC)疏水性以及热性能方面的影响,文中采用乙酸和硬脂酸两种不同链长的烷基酸对CNC进行酯化改性,分别得到乙酰化纳米纤维素(ANC)和硬脂酸改性纳米纤维素(MNC)两种改性产物,并对其疏水性及热性能进行测试表征。研究结果表明:水接触角从28.702°(CNC)分别提高到62.606°(ANC)和64.918°(MNC),改性产物的疏水性都有所提高;但是在热性能方面,ANC由于乙酰基的存在使得其热稳定性提高了47℃;而MNC因为硬脂酸长链烷基分子在高温下不稳定易断裂,所以其最大热分解温度相比CNC降低了34℃,热稳定性有所降低。所以乙酸作为短链烷基酸,既可以在一定程度上提高纤维素纳米晶的疏水性能,又能提高其热稳定性。本文研究结果可为后续与聚乳酸等疏水性聚合物共同制备增强型纳米复合材料提供性能方面的理论依据。

固载质子型离子液体催化酯化反应合成香蕉油——可回收固态催化剂的实验教学应用

酯化反应是大学有机合成实验课程中的重要训练项目。应用溶胶-凝胶法制备了N-甲基咪唑硫酸氢盐固载离子液体催化剂(Meim-HSO_(4)@SiO_(2)),Meim-HSO_(4)@SiO_(2)取代传统无机酸催化醋酸与异戊醇酯化反应。与无机酸相比,固态催化剂Meim-HSO_(4)@SiO_(2)取用更加方便,转化率提高22.1%,反应结束后只需抽滤、洗涤、烘干便可实现催化剂的回收再利用,成本缩减约37.5%。新设计为大学化学教学实验“香蕉油的制备与鉴定”提供了切实可行的催化剂选择新思路,符合绿色化学发展需求,有助于学生综合能力的提升和改进思维的培养。

Esterification of levulinic acid into n-butyl levulinate catalyzed by sulfonic acid-functionalized lignin-montmorillonite complex

In this study,sulfonic acid-functionalized lignin-montmorillonite complex(LMT-SO_(3)H)was pre-pared and employed as an efficient heterogeneous catalyst for the esterification of levulinic acid(LA)into n-butyl levulinate(BL).An intermediate pseudo-butyl levulinate(p-BL)was determined by distilled water treatment and nuclear magnetic resonance(NMR)analysis,and a possible mech-anism for the esterification of LA is proposed.The effects of various process parameters were studied and the results showed that the LMT-SO_(3)H catalyst had the excellent catalytic perfor-mance for esterification of the LA.Under optimum reaction conditions,the yield of BL was 99.3%and the conversion of LA was 99.8%.The LMT-SO_(3)H catalyst exhibited strong acidic sites and high stability even after seven cycles of usage.Furthermore,esterification of the LA with various alcohols over the LMT-SO_(3)H was further investigated.

乙酸正丙酯制备条件的优化研究

以乙酸和正丙醇为原料,以浓硫酸为催化剂合成乙酸正丙酯。通过优化催化剂用量、反应温度以及酯化反应时间3个条件,得到了纯度和产率较高的乙酸正丙酯。实验结果表明,当加入催化剂体积为1.5 mL,在100℃下反应时间为50 min时,乙酸正丙酯的精制收率可达到87.8%。

Dawson结构磷钨酸的制备、表征及催化绿色合成乙酸正丁酯工艺研究

制备了H6P2W18O62.13H2O催化剂,并通过FT-IR、UV-Vis、TG-DSC对催化剂进行表征.以乙酸正丁酯合成反应为探针考察催化剂的催化性能.研究了磷钨酸用量、醇酸比、反应时间和反应温度对反应的影响,并提出可能的催化机理.结果表明,最优的反应条件是:催化剂用量为0.72%(按反应体系总质量计算),醇酸比为2.0︰1.0,反应时间为2.0 h,反应温度为125℃,在此条件下酯化率可达96.83%.