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Design and Optimization of a Process for the Production of Methyl Methacrylate Via Direct Methylation

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Design and Optimization of a Process for the Production of Methyl Methacrylate Via Direct Methylation processes Article Design and Optimization of a Process for the Production of Methyl Methacrylate via Direct Methylation Taotao Liang 1,2, Xiaogang Guo 2,3,*, Abdulmoseen Segun Giwa 1,4, Jianwei Shi 3, Yujin Li 3, Yan Wei 3, Xiaojuan Wang 5, Xuansong Cao 3, Xiaofeng Tang 3 and Jialun Du 3 1 Green Intelligence Environmental School, Yangtze Normal University, Chongqing 408003, China; [email protected] (T.L.); [email protected] (A.S.G.) 2 Faculty of Materials and Energy, Southwest University, Chongqing 400715, China 3 College of Chemistry and Chemical Engineering, Yangtze Normal University, Chongqing 408003, China; [email protected] (J.S.); [email protected] (Y.L.); [email protected] (Y.W.); [email protected] (X.C.); [email protected] (X.T.); [email protected] (J.D.) 4 State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China 5 College of chemistry and bioengineering, Guilin University of Technology, Guilin 541004, China; [email protected] * Correspondence: [email protected]; Tel.: +86-023-72782170 Received: 25 April 2019; Accepted: 6 June 2019; Published: 18 June 2019 Abstract: Methyl methacrylate (MMA) plays a vital role in national productions with broad application. Herein, the production of MMA is realized by the improved eco-friendly direct methylation method using Aspen Plus software. Three novel kinds of energy-saving measures were proposed in this study, including the recycle streams of an aqueous solution, methacrolein (MAL), and methanol, the deployment of double-effect distillation instead of a normal one, and the design of a promising heat-exchange network. Moreover, MMA with a purity of 99.9% is obtained via the design of a MAL absorber column with an optimal stage number of 11 and a facile chloroform recovery process by using the RadFrac model. Thus, the proposed green process with energy-conservation superiority is the vital clue for developing MMA, and provides a reference for the production of MMA-ramifications with excellent prospects. Keywords: MMA; double-effect distillation; energy conservation; MAL; purity 1. Introduction Methyl methacrylate (MMA), an essential chemical raw material, has drawn growing interest in the fields of poly(methyl methacrylate) (PMMA), functional coatings, lubricant additives, ion exchange resins, construction materials, lighting equipment, etc., due to excellent transparency and weather resistance [1–6]. It is worth mentioning that the production of MMA needs to grow quickly and steadily due to the increasing demand for MMA in the world [7–10]. Thus, it is necessary to develop a green process for preparing MMA efficiently. In fact, several processes for obtaining MMA have been developed up to now, including the C2-method (ethylene carbonylation, etc.) [11], C3-method (acetone cyanohydrin (ACH), etc.) [12], and C4-method (isobutylene direct methylation method (IDMM), methacrylonitrile process, etc.) [13,14], which are clearly seen in Figure1. Based on the mentioned methods, lots of researchers have devoted efforts to exploring MMA production processes, notably including a separate process of a mixture of methyl methacrylate, methanol and water. For example, Wu et al. studied the optimization Processes 2019, 7, 377; doi:10.3390/pr7060377 www.mdpi.com/journal/processes Processes 2019, 7, x FOR PEER REVIEW 2 of 13 Processes 2019, 7, 377 2 of 12 mixture of methyl methacrylate, methanol and water. For example, Wu et al. studied the optimization design and dynamic control of the simplified separation process for MMA by using a design and dynamic control of the simplified separation process for MMA by using a one-column one-column flowsheet with a middle decanter, which can cut operating costs by 35.9% compared to flowsheet with a middle decanter, which can cut operating costs by 35.9% compared to the industrial the industrial three-column design. Large disturbances of the feed composition can be effectively three-column design. Large disturbances of the feed composition can be effectively controlled [15]. controlled [15]. Chang et al. studied an alternative design for separating mixtures (including methyl Chang et al. studied an alternative design for separating mixtures (including methyl methacrylate, methacrylate, methanol, and water) using a distillation column, a stripper and a decanter. methanol, and water) using a distillation column, a stripper and a decanter. Compared with the Compared with the traditional design process, the operating cost of during this improved design traditional design process, the operating cost of during this improved design significantly reduced significantly reduced to 25.9%. In addition, based on open/closed-loop sensitivity testing, the overall to 25.9%. In addition, based on open/closed-loop sensitivity testing, the overall design turns out to design turns out to ensures the product of MMA with a high degree of purification [16]. The azeotropicensures the distillation product of and MMA ionic with liquid a high eco-envi degreeronmental of purification separation [16]. The of azeotropicmethacrolein distillation (MAL) was and investigatedionic liquid eco-environmentalby Yan et al. to obtain separation MMA, of methacroleinand results indicated (MAL) was that investigated used green by process Yan et al. had to obtain MMA, and results indicated that used green process had significant economic and green-degree significant economic and green-degree advantages [14]. Compared with related reports, C4-IDMM hasadvantages gradually [14 been]. Compared regarded with as relateda promising reports, green C4-IDMM technique, has gradually due to the been low-cost regarded equipment, as a promising short reactiongreen technique, path, and due sufficient to the low-cost raw materials, equipment, and so short on [12,13,17], reaction path, though and ther suffiecient are no raw large-scale materials, uses and inso industry. on [12,13 ,17However,], though it thereis still are a nochallenge large-scale to develop uses in industry.the production However, process it is of still MMA a challenge based on to develop the production process of MMA based on C4-IDMM economically. The method used in our C4-IDMM economically. The method used in our study is based on the improved direct methylation ofstudy isobutylene is based onmethod the improved proposed direct by the methylation Asahi Kasei of isobutyleneCorporation. method There proposedis no MAA by step the Asahiduring Kasei this process,Corporation. which There effectively is no MAA avoids step side during reactions this process, such as whichMAA epolymerization,ffectively avoids simplifies side reactions the process such as flow,MAA and polymerization, reduces energy simplifies consumption, the process thereby flow, gr andeatly reduces reducing energy operating consumption, costs and thereby investment greatly costsreducing and operatingmaking it costsmore andcompetitive investment costs and making it more competitive. FigureFigure 1. ComparisonComparison diagram diagram of of different different production processes of methyl methacrylate (MMA). Thus, the focus of this report is on the facile design of an MMA synthesis route by using a direct isobutylene methylation method method to to reduce the energy consumption.consumption. Moreover, ASPEN simulation software, an an effective effective and and common common tool, tool, is used is used for forprocess process simulation simulation and anddata dataanalysis analysis at the atsame the time.same time. 2. Simulation Simulation and and Experimental Experimental Methods 2.1. Main Main Reaction Reaction Equation The production process-C 44-IDMM-IDMM of of MMA MMA in in this this study study is is based based on on the the Asahi Asahi direct direct method, method, also called direct methylation as follows. Firstly, Firstly, the oxidation of isobutylene (Aladdin Industrial Corporation, Shanghai,Shanghai, China)China) produces produces methylacrolein, methylacrolein, which which acts acts with with air inair the in liquid the liquid phase. phase. Then, Then,the product the product of the previousof the previous step undergoes step undergoes the one-step the one-step esterification esterification oxidation oxidation reaction reaction with excess with excessmethanol methanol (Aladdin (Aladdin Industrial Industrial Corporation, Corporation, Shanghai, Shanghai, China) toChina) obtain to MMA, obtain where MMA, the where catalyst the is catalystPd (Aladdin is Pd Industrial(Aladdin Corporation,Industrial Corporation, Shanghai, China),Shanghai, and China), the carrier and the is CaCO carrier3 (Aladdin is CaCO3 Industrial (Aladdin IndustrialCorporation, Corporation, Shanghai, China)Shanghai, or ZnO China) (Aladdin or ZnO Industrial (Aladdin Corporation, Industrial Shanghai, Corporation, China), Shanghai, and the Processes 2019, 7, x FOR PEER REVIEW 3 of 13 ProcessesProcesses2019 2019, 7, 377, 7, x FOR PEER REVIEW 3 of3 12of 13 China), and the activity and stability of the whole reaction is improved by adding metal elements of China),Pb, Bi andor Zn the, etc. activity [18,19 and]. The stability synthetic of the route whole is shown reaction clearly is improved in the following by adding Equation metal elements (1): of activityPb, Bi and or Zn, stability etc. [18,19]. of the The whole synthetic reaction route is improved is shown byclearly adding in the metal following elements Equation of Pb, (1): Bi or Zn, etc. [18,19]. The synthetic route is shown clearly in the following
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