Novel Eco-Efficient Process for Methyl Methacrylate Production

Abstract

Methyl methacrylate is an essential chemical used as raw material for the production of other methacrylates and poly-methyl methacrylate. There are various chemistry routes, available or not on the industrial scale, to produce methyl methacrylate. These routes use the same or different raw materials and present common chemistry and processing steps. Many of these routes though, have as a final step the esterification of methacrylic acid with methanol to obtain methyl methacrylate. However, there is no complete process described in the literature for this final esterification step. This paper is the first to propose a solid-based catalytic process for methyl methacrylate production starting from methyl methacrylate and methanol, in a continuous reaction–separation–recycle system. In this specific case, this system is more suitable than reactive distillation due to the unfavorable ranking of boiling points and also due to the presence of several potentially hindering azeotropes. This work also provides an original framework for simulation of other methyl methacrylate processes, by deriving detailed equilibrium and kinetic parameters based on literature experimental data. Rigorous process simulations are carried out in Aspen Plus and Aspen Plus Dynamics for the design and control of the new process. The flowsheet consists mainly of a fixed-bed tubular reactor followed by a sequence of three distillation columns coupled with a decanter. The results show that the process is technically feasible, cost-effective in terms of total annualized costs, and with excellent sustainability metrics, requiring only 2.05 MJ/kg of methyl methacrylate produced.

Methyl Methacrylate Production Processes: A Comparative Analysis of Alternatives Using the Life Cycle Assessment Methodology

“…Although the LCI data sources included catalyst compositions and amounts, it was difficult to estimate the quantity of catalyst required for scaling up these processes. Moraru et al modeled the esterification of MAA to MMA to produce 2324 kg of MMA. The catalyst requirement for this process was used as the basis for the computation of the quantity of catalyst in conjunction with an established peer-reviewed catalyst modeling procedure .…”

“…MAA is one of the products identified in the AL-MMA process, and it is a carboxylic acid which can esterify with MeOH to produce MMA. The process for producing MMA from MAA was modeled according to the work of Moraru et al, 74 as shown in Table S4, and it was incorporated into the system to improve the efficiency of the whole system. Further details are collected in Supporting Information.…”

Unraveling the Coking and Deactivation Behavior of Al–Cs/SiO2 Catalyst in the Aldol Condensation of Methyl Propionate with Formaldehyde

“…As an indispensable chemical raw material, methyl methacrylate (MMA) is mainly used in the production of poly­(methyl methacrylate). − The traditional acetone cyanohydrin (ACH) route using methanol (MeOH), acetone, sulfuric acid, and hydrocyanic acid as raw materials is the earliest and most widely used route in industrialization, which suffers from equipment corrosion and environmental pollution. , The C4 route uses isobutene as the main raw material, with the advantage of fewer byproducts and the disadvantage of cost dependence on the oil market . One-step reaction of methyl propionate (MP) with formaldehyde (FA) to synthesize MMA, in which reactants can be derived from coal-based chemicals instead of petroleum-based resources, has stimulated the interest of researchers in the past years, considering its abundant raw materials, simple process, and environmental sustainability (Scheme ).…”

Acid Promoter-Modified Cs/Al2O3 Catalyst for Methyl Methacrylate Production by Aldol Condensation of Methyl Propionate with Formaldehyde

“…MMA is a high-value raw material that is crucial for producing plastic modifiers, adhesion agents, and coatings. There is still a growing demand for MMA due to its unique properties, such as transparency and wear resistance. − Tremendous research has recently been published for the synthesis of MMA, and the aldol condensation of MP and FA has garnered a lot of interest since they are rich coal materials and environmentally benign. − Unfortunately, the low yield and limited catalytic lifetime of available catalysts have been major limitations to the vital process.…”