Study on the Intensification of Reaction Kinetics and Reactive Distillation for the Esterification of N-Butyl Acetate Using [HSO₃-BMIM][HSO₄] as a High-Efficiency Ionic Liquid Catalyst

Abstract

An ionic liquid (IL) catalyst 1-sulfobutyl-3-methylimidazolium hydrogen sulfate, [HSO 3 -BMIM][HSO 4 ], was used to produce nbutyl acetate (BuAc) via esterification. A novel modified nonideal homogeneous kinetic model was developed by self-catalysis theory. A new reactive distillation (RD) process using [HSO 3 -BMIM][HSO 4 ] to produce BuAc was intensified using Aspen simulation taking advantage of phase splitting to increase the ester purity. Various design parameters like reactant feed location, reflux ratio, reactant feed molar ratio, flow ratio of products to materials, and condenser pressure were optimized. Fitting results indicated that modified models presented exact prediction results for the [HSO 3 -BMIM][HSO 4 ]-catalyzed esterification compared with the unmodified model because the former introduced a revisional term for the self-catalysis of HAc, which revealed the mechanism of self-catalysis and interaction between ILs and reactants. The BuAc purity was increased from 91.05 to 95.02 wt % by the RD process intensification. [HSO 3 -BMIM][HSO 4 ] showed a higher acid conversion (75%) than commercial ILs and resins. The ester yield was higher when using [HSO 3 -BMIM][HSO 4 ] as the catalyst than resin A (80.89 wt %) in the intensified RD process. This research provides a novel modified method for the kinetic model in the IL-catalyzed reaction where the modified model exhibited a high accuracy and is useful for improving the production efficiency and controlling the catalyst dosage in the chemical engineering process design. The intensified RD process shows a flexible design for IL application, which is helpful for designing industrial scale-up.

Optimization of Poly(ethylene terephthalate) Fiber Degradation by Response Surface Methodology Using an Amino Acid Ionic Liquid Catalyst

“…A reasonable experimental design is given by the software, the required data are obtained through the experiment, and a multiple quadratic regression equation is used to fit the functional relationship between the factors and the response values. The analysis of the regression equation is used to find the best process parameters. , In this experiment, the optimal reaction conditions for the catalytic degradation reaction of PET fibers were designed and optimized. Using the conversion of PET fibers and the yield of monomeric BHET as the response variables, four factors were found to have a significant influence on the catalytic degradation process of polyester fibers through single-factor experiments: temperature (X1), time (X2), catalyst dosage (X3), and EG dosage (X4).…”

“…As a green and mild medium that has emerged in recent years, , ionic liquids (ILs) have demonstrated excellent catalytic properties in the field of catalysis. , This is because ILs are in the liquid state at room temperature and can better participate in reactions as homogeneous catalysts, , thus improving the catalytic efficiency of reactions. Meanwhile, due to the advantages of designable and adjustable structures, ILs are expected to replace traditional metal catalysts through the interaction of anions and cations, solving a series of problems caused by metal residues.…”

Mild Catalytic Mechanism of the Mannich Reaction for Synthesizing Methylacrolein by sec-Amine Short-Chain Aliphatic Acid Ionic Liquid Catalysts

“…Moreover, they used [HSO 3 -Bmim][HSO 4 ] IL catalysts to produce n-butyl acetate by esterification and provided a novel modified method for the kinetic model of the IL-catalyzed reaction, which is useful for improving the production efficiency and controlling the catalyst dosage in the chemical engineering design process. 24 In the synthesis of significant chemical feedstock methylacrolein (MAL), the sec-amine IL-catalyzed Mannich reaction has advantages of mild reaction conditions compared with other Mannich reactions. Zhong et al reported the Mannich reaction catalyzed by 330 resin containing functional groups.…”

“…With the increasing pursuit of greener and more sustainable chemistry in recent years, the significant contribution of ionic liquids (ILs) to organic synthesis by improving the reaction environment and reaction rate has become indispensable. − ILs not only exhibit an outstanding performance as an extractive agent or solvent , but also play an important role in creating mild reaction conditions by dramatically decreasing the reaction energy barrier such as in cycloaddition, − desulfurization, − and esterification , reactions.…”

“…[Bmim]­Cl/ZnCl 2 exhibited greater affinity for N compounds due to the nucleophilic behavior of cationic species and promoted this reaction. Moreover, they used [HSO 3 -Bmim]­[HSO 4 ] IL catalysts to produce n -butyl acetate by esterification and provided a novel modified method for the kinetic model of the IL-catalyzed reaction, which is useful for improving the production efficiency and controlling the catalyst dosage in the chemical engineering design process …”