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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Pilot-scale validation and process design of reactive distillation with HY@SiC structured catalytic packing for dimethyl maleate production

Zhengkun Hou,Qiuyan Ding,Hongbin Wang,Yilai Jiao,Peng Jin,Hong Li,Xin Gao

In reactive distillation processes constrained by the efficiency of vapor–liquid mass transfer, reducing the physical dimensions of simultaneous reaction and separation operations can significantly enhance overall process efficiency. To achieve this, HY@SiC, a structured catalytic packing was developed, allowing for concurrent catalytic reactions and vapor–liquid mass transfer on its surface. This innovative catalytic packing was employed in a pilot reactive distillation column to experimentally investigate the production of dimethyl maleate via reactive distillation, marking the first validation of its performance. Additionally, a reactive distillation model incorporating HY@SiC structured catalytic packing was established. Ultimately, a new double-column reactive distillation process for producing dimethyl maleate was proposed, with plans for optimization aimed at minimizing total annual cost, which was 4.08 × 10 5  $/y, utilizing a sequential iterative algorithm as the core focus for design improvements, while achieving DMM yield and purity levels of 99.42 % and 99.0 wt%, respectively.

CAS / MDL: 67-56-1 108-31-6
研究领域: 化学工程 · 工艺设计 · 催化 · 反应精馏
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Chemical Engineering and Processing-Process Intensification · 2020 · IF 3.731

Intensification of 2-Methyl-1,3-Dioxolane hydrolysis for recovery of ethylene glycol through reactive distillation: Kinetics and process design

Xingang Li,Yan Wu,Hong Li,Guomin Yuan,Hao Chen,Xin Gao

Chemical Looping technology, which consist of aldolization and hydrolysis processes, is proved as a potential and effectively method to separate ethylene glycol (EG) in the coal-based EG production process. However, the problem of acetal hydrolysis is that this reaction is hindered by the boiling points ranking and the chemical equilibrium limitations, which is not the most favorable. In this paper, a potentially sustainable reactive distillation (RD) process is presented for intensification of hydrolysis of 2-Methyl-1,3-Dioxolane (2MD). To accurate design the RD process, the hydrolysis kinetics was measured and a regressed pseudo homogeneous model showed good agreement with experiments. Furthermore, an applicable reactive distillation model was proposed to analyzing the effect of pressure, feed ratio, feed position, reflux ratio, number of reaction plates, rectification plates and stripping plates on the energy consumption and 2MD conversion. Results show that the designed RD process will shift the conventional hydrolysis process towards completion with a 2MD conversion higher than 99.9 %, even without high excess water. The obtained results could give a guide for the pilot scale of recovery EG in coal-based EG production process.

CAS / MDL: 67-68-5
研究领域: 化学工程 · 过程强化
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2019 · IF 3.375

Esterification of Methacrylic Acid with Methanol: Process Optimization, Kinetic Modeling, and Reactive Distillation

Ran Ran,Jie Li,Gang Wang,Zengxi Li,Chunshan Li

The esterification of methacrylic acid with methanol catalyzed by NKC-9 resin (a cation-exchange resin with sulfonate groups) was conducted in a stainless stirred batch reactor. The effects of catalyst loading, initial molar ratio of reactants, temperature, and pressure on this esterification reaction were investigated. A kinetic model based on the Langmuir–Hinshelwood mechanism was developed in which methacrylic acid and methanol were considered to be uniformly adsorbed on the surface of catalysts. Model parameters, including reaction equilibrium constants, activation energy, enthalpy change, entropy change, and rate constants, were solved. The accuracy of the model was validated by means of both experimental proofs and standard deviation between the predicted and experimental data. Finally, the reactive distillation process was proposed for continuous synthesis and separation of methyl methacrylate.

CAS / MDL: 79-41-4
研究领域: 化学工程 · 催化科学
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Journal of Cleaner Production · 2024 · IF 9.7

A green synthesis route of cyclohexanol via transesterification reaction intensified by reactive distillation technology

Zhengkun Hou,Xueli Geng,Qiuyan Ding,Hong Li,Yaocong Guo,Ting Qiu,Chen Yang,Qinglian Wang,Xin Gao

With the increasing demand of cyclohexanol in nylon industry, it is significant to develop a safe, green and economical process to produce cyclohexanol. For this purpose, a novel reactive distillation process through cyclohexyl acetate transesterification with methanol was proposed in this work. The NKC-9 catalyst was preferred to establish the reaction kinetic model based on pseudo-homogeneous model. Seven reactive distillation experiments with pilot-scale for cyclohexanol synthesis were explored to prove feasibility of reactive distillation processes and accuracy of model by comparing simulated results, which ensured the establishment of the process simulation. Furthermore, three reactive distillation processes of cyclohexanol production were designed and optimized by the sequential iterative algorithm based on minimum total annual cost. After optimization of pressure and recycled stream flow, a novel double column of reactive and pressure-swing hybrid distillation process showed the minimized total annual cost per ton product, which was 170.90 $/kg. Finally, total annual cost of transesterification, hydrolysis and hydrogenation processes were compared, and transesterification process demonstrated economic advantage. This work would provide a guidance for cyclohexanol green production by reactive distillation through cyclohexyl acetate transesterification, while a whole, economical and atomic economical reactive distillation process of cyclohexanol production could be established in the future.

CAS / MDL: 7440-70-2 67-56-1
研究领域: 化学工程 · 绿色化学
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Reaction Chemistry & Engineering · 2024 · IF 3.4

Efficient synthesis of glycerol carbonate over a commercially available 4A molecular sieve via an integrated vacuum reactive distillation process

Jiayin Huang,Anwei Wang,Chunsheng Zhao,Yu Fan,Shanshan Cao,Zheng Tian,Weiyou Zhou

Various heterogeneous catalysts have been investigated in the transesterification of glycerol with ethylene carbonate to glycerol carbonate in a batch reactor, and a commercially available 4A molecular sieve exhibited relatively high catalytic performance for its surface strong basic and acidic sites. Further, an integrated vacuum reactive distillation process was developed for the transesterification in the presence of the 4A molecular sieve. The produced ethylene glycol could be efficiently removed from the reaction system to overcome the equilibrium, and excellent glycerol conversion (99%) and glycerol carbonate selectivity (>99%) were obtained under the optimal reaction conditions. The recycling and the scale-up experiments demonstrate the excellent practical potential of the present process, thus providing an efficient reaction process for the preparation of glycerol carbonate.

研究领域: 化学工程 · 催化材料
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CHEMICAL ENGINEERING & TECHNOLOGY · 2020 ·Vol. 43 ·期 12 ·2359-2364 · IF 1.543

Stable Organic Titanium Catalysts and Reactive Distillation Used for the Transesterification of Dimethyl Carbonate with Phenol

Weihua Shen,Qing Ge,Kaijie Gu,Yingying Nie,Linyu Jiao,Zhiqing Zhu,Yunjin Fang

The transesterification of dimethyl carbonate with phenol to methyl phenyl carbonate (MPC) was investigated on novel catalysts such as titanium diisopropoxide bis(ethyl acetoacetate) and titanium dibutoxide bis(ethyl acetoacetate) in a closed batch reactor at 185–206 °C under high pressure. The produced methanol could be removed efficiently by reactive distillation in order to overcome the equilibrium. The prepared catalysts have higher resistance to water than titanium alkoxides. Phenol conversion as high as 86.4 % with an MPC selectivity of 99.4 % was achieved under optimal reaction conditions within 9 h. Most of the catalytic activity was retained after repeated use for ten times.

CAS / MDL: 546-68-9
研究领域: 化学工程 · 催化化学
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JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY · 2019 ·Vol. 94 ·期 10 ·3292-3304 · IF 2.659

A combination of low-temperature reactive and extractive distillation for methoxy-2-propyl acetate synthesis and separation process: simulations and experiments

Baohe Wang,Xinlei Cai,Liang Lu,Jing Ma

BACKGROUND Esterification of methoxy propanol (MP) and acetic acid (HAC) to methoxy-2-propyl acetate (MPA) is a typical reversible reaction. The yield of MPA is low owing to the limitation of chemical equilibrium. In the present study, with the goal of increasing the reaction conversion and preventing the NKC-9 cation exchange resin catalyst from deactivation at high temperature, a process combining low-temperature reactive and extractive distillation with cyclohexane (C 6 H 12 ) as entrainer was investigated by process simulations and experiment methods. RESULTS The intrinsic kinetic parameters were obtained by catalyst activity evaluation in a batch reactor. Binary interaction parameters of thermodynamic models were determined by the measurement and fitting of vapor–liquid equilibrium data. The effects of different operating parameters on the reaction conversion and column performance were examined in detail, and a production process of MPA with an annual output of 56 000 tons was suggested. The results showed that the purity of MPA reached nearly 100% after further purification following reactive distillation, and the reaction temperature was controlled in the range 75–80 °C, which allowed long-term operation thermal stability of the catalyst. CONCLUSION The developed low-temperature reactive distillation method ensured a long life of the ion exchange resin catalyst, which should provide insights into further advances of MPA industrial production. © 2019 Society of Chemical Industry

研究领域: 化学工程 · 工业催化
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2019 · IF 3.375

Ethylene Glycol Recovery from 2-Ethyl-1,3-dioxolane Hydrolysis via Reactive Distillation: Pilot-Scale Experiments and Process Analysis

Xingang Li,Rui Wang,Yutao Yan,Runnan Zhao,Hong Li,Xin Gao

EG is an important industrial raw material, and the hydrolysis of 2-ethyl-1,3-dioxolane (2ED) to re-obtain EG is a very important step to recover EG from an EG and 1,2-BDO azeotropic mixture via a reversible-reaction-assisted intensification process. The applicability of reactive distillation for 2ED hydrolysis in the presence of KRD-002 ion exchange is studied by experiments and simulations. The reaction kinetics were investigated, and the kinetic parameters were derived. Thermodynamic aspects of the reaction system were discussed, and the NRTL model was built. Pilot-plant reactive distillation experiments were performed using the structured catalytic packing unit (SCPI) with several operating condition variations (reflux ratio (RR), feed mole ratio (FMR), and feed-in style). The experimental results are in good agreement with the simulation results, which prove that the equilibrium stage model can describe the hydrolysis experiments quantitatively. The simulation was subsequently used to determine the influence of important design factors and laid the foundation for industrial application.

CAS / MDL: 75-07-0
研究领域: 化学工程 · 工业催化
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Process design and optimization of enzymatic reaction distillation

Jun Liang,Zhixi Zhang,Qiang Zhang,Yaqian Bian,Kunlong Yi,Wenbin Zhou,Weiyi Su,Yuqi Hu,Xiong Yu,Honghai Wang

Driven by global environmental awareness, biocatalysts are playing an increasingly important role in industrial chemistry . Enzymatic reactive distillation (ERD) combines the high efficiency of enzymatic reaction and distillation separation to reduce the limiting effects of reaction equilibrium, product inhibition, and the difficulty of product recovery due to its thermodynamic constraints. The lipase CALB was immobilized and coated on the θ-ring by sol-gel method. The synthesis of n-butyl acetate by transesterification reaction was selected as the model reaction in the ERD process, and a laboratory scale column was constructed. The Rate-based RadFrac model in Aspen Plus was used to describe the ERD. The results showed that the enzyme-loaded packing showed high long-term stability after 120 days in the reaction system. The deviation of the ERD experiment and simulation results was less than 10 %, which verifies the reliability of simulation. After the parameter sensitivity optimization on the simulation, compared with the batch reactor, the ERD process increased the reactant conversion from 60 % to 94.74 %. This study established a complete process from enzyme immobilization to ERD process, which provided a theoretical basis for the establishment and optimization of ERD process.

研究领域: 生物化学工程 · 工业化学 · 过程工程
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2017 · IF 2.843

Feasibility Study of Reactive Distillation for the Production of Propylene Glycol Monomethyl Ether Acetate through Transesterification

Xiaoda Wang,Qinglian Wang,Changshen Ye,Xiaolian Dong,Ting Qiu

This paper aims to present the feasibility of conducting the transesterification of propylene glycol ether (PM) with methyl acetate (MeAc) in a reactive distillation (RD) column to improve the reaction conversion. The essential thermodynamic and reaction kinetic data of the reaction system were measured for the feasibility study. There is only one azeotrope, MeAc–MeOH, in the reaction system, and the NRTL model could describe well the thermodynamic behavior of this system. The transesterification of PM with MeAc is an endothermic reaction with activation energy E = 55.704 kJ·mol–1. The feasibility was analyzed by residue curve maps (RCM), showing that full conversion of PM could be realized by RD with a mole ratio of MeAc–PM larger than 2.882. The intensification effect was experimentally verified in a batch RD column. Finally, some important parameters are given through the conceptual design to develop a continuous RD column for the transesterification of PM with MeAc.

研究领域: 化学工程 · 反应动力学
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CHEMICAL ENGINEERING RESEARCH & DESIGN · 2022 · IF 4.119

Reactive distillation for sustainable synthesis of bio-ethyl lactate: Kinetics, pilot-scale experiments and process analysis

Qiuyan Ding,Hong Li,Zhanpeng Liang,Rui Zuo,Songzhe Huang,Xingang Li,Yilai Jiao,Xin Gao

Bio-ethyl lactate (EL), an alternative green solvent to the traditional petroleum-based solvent, has a distinct advantage in the chemical industry. However, to solve the problem of high energy consumption and low yield in the production of EL is the premise of large-scale production and application. This work proposes an economical and energy-efficient reactive distillation (RD) process through excess lactic acid (LA). As the primary data of RD process design, the kinetics of esterification reaction between LA and EL were investigated using the ion exchange resins KRD001 catalyst. Besides, the developed RD model has been validated utilizing five pilot-scale RD experimental data for process design. Furthermore, the proposed process is optimized with the objective of the minimum heat duty per kilogram product (HDP) of EL, taking into account energy consumption, reaction conversion, economic and environmental impacts. The proposed process has obvious economic and environmental advantages, which can cause a reduction of 52.25% for the total annual cost per kilogram product ( T A C K ) of EL and 4.63% for the gas emissions compared with the excess ethanol (EtOH) process. This provides guidance and reference for the green technology development and production of EL.

CAS / MDL: 5398-29-8
研究领域: 化学工程 · 环境科学 · 可持续发展
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Investigation of sustainable reactive distillation process to produce malonic acid from dimethyl malonate

Qiuyan Ding,Zhengkun Hou,Xueli Geng,Guiyu Gao,Wenwei Dong,Hong Li,Yaohong Wang,Xibo Chen,Xin Gao

The new energy battery is currently a hot research topic, leading to an increase in the demand for malonic acid (MA) as a raw material. The objective of the present work is to find a potential reactive distillation (RD) process to solve the problem of low conversion and high energy consumption in hydrolytic system. In the meantime, the RD technology still faces the problem of how to distribute water in the RD column. Aiming at the problem, four different RD processes are proposed: RD combined water separation process (RDWS), RD combined with MA concentration process (RDMC), RD combined methanol separation process (RDMS), and single RD process (SRD). Beforehand, reaction kinetic of dimethyl malonate (DM) hydrolysis was investigated using the ion exchange resin catalysts, and the developed RD model was verified via pilot-scale RD experiments. Finally, the proposed RD process is analyzed from the aspects of economic and environmental and compared with the traditional reaction + distillation (R + D) process. Consequently, the proposed SRD process is a better economy-saving and environment-friendly technology, and has certain directive significance for the industrial production of MA.

CAS / MDL: 7664-38-2
研究领域: 化学工程 · 能源材料
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