Research Progress in Reactive Distillation: Xin Zhang, Ping He, Hao Li
Research Progress in Reactive Distillation: Xin Zhang, Ping He, Hao Li
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DOI: https://doi.org/10.61187/ast.v1i1.3
Abstract: As a special distillation process, reactive distillation technology has been widely used in the petrochemical field due to its
outstanding advantages such as high efficiency and energy saving. It has been paid more and more attention from researchers in the field
of chemical process enhancement since the 1920s. With the progress of social development level, resource conservation and
environmental friendliness have become the general trend. In order to pursue the maximization of energy utilization and higher economic
benefits, scientific researchers have developed a variety of new reactive distillation processes suitable for various occasions considering
the advantages and limitations of traditional reactive distillation technology. The biggest difference from traditional reactive distillation is
that the new processes have the characteristics of saving equipment investment, low reaction energy consumption, improving mass
transfer, heat transfer efficiency and energy utilization rate. In order to fully understand and apply the technology, this paper describes the
process flow of traditional and new reactive distillation technologies in detail, and focuses on analyzing and summarizing the latest
developments in the industrial application of reactive distillation technologies in various fields. Finally, it points out that reactive
distillation technologies issues that need attention and future development directions.
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difficult for computers to simulate and design [8]. From the for process intensification [25-27]. For example, ethanol and
perspective of volatility, volatilities between reactants and dimethyl carbonate (DMC) are used as reactants and
products cannot cross each other, that is, all reactants are a transesterification method is adopted in the synthesis reaction
whole, and all products are another whole. Volatilities of of methyl ethyl carbonate (EMC). The three-tower process of
components between these two wholes cannot cross each traditional reactive distillation will result in unnecessary
other. Reaction and separation conditions are the key points of production increase of DEC, with no place to sell and low
this technique, but they contradict each other in some cases economic value. Although increasing the ratio of DMC can
and it is difficult to achieve the best combination. The make more EMC converted into target products, it is not
introduction of in situ separation in the reaction zone leads to worth the loss because it violates the principle of saving
complex interactions among gas-liquid equilibrium, mass energy. The divided wall reaction distillation takes advantage
transfer rate, diffusion and chemical kinetics, which poses of its unique advantages such as less land area, high
great challenges to the design and synthesis of the system conversion rate and good selectivity, so as to solve this
[18]. problem well. Compared with the traditional reaction
rectification column, the inner structure of the adjacent
3. Application of new reactive distillation column is more complicated. In order to avoid the generation
technology of the by-product DEC, the inner column is separated
vertically by a partition from the top to the middle of the
After long-term exploration and research, new reactive column, and the upper and lower reaction sections on the left
distillation technologies such as adjacency reactive side of the partition are respectively transesterification and
distillation [19], "backpack" reactive distillation [20], anti-disproportionation reaction. The EMC yield was
membrane percolation [21], microwave reactive distillation improved greatly by purifying the EMC on the right side of
[22], hypergravity reactive distillation [23], can better avoid the separator. At the top of the tower, both sides of the
some limitations of traditional reactive distillation to improve separator are provided with condensers, and the lower end of
the coupling degree of matter and energy between reaction the separator is a common distillation section of the reaction
and separation operations, improve the efficiency of mass and zone and the purification zone. Methanol and DMC azeotrope
heat transfer and energy utilization, and broaden the scope of are produced from the top of the tower on the left side of the
application. partition, EMC products are produced from the top of the
tower on the right side of the partition, and the tower reactor
3.1 Dividing wall reactive distillation process DEC is circulated to the reaction zone on the left side of the
partition [19]. Two condensers and a reboiler allow the
In recent years, a large number of researchers focusing on rectification process of adjacent reactions, as shown in Fig. 2.
chemical process intensification have discovered that the It greatly saves the load of the reboiler and condenser, reduces
advantages of dividing wall column (DWC) and traditional the equipment investment and operating costs due to the use
reaction distillation technology can complement each other. of one less tower than the traditional three-tower process. In
With this idea in mind, they integrated dividing wall addition, the simulation analysis revealed that the technology
distillation and reactive distillation, and adjacent reactive can effectively suppress the degree of back-mixing and make
distillation is born and applied to several reaction systems the reaction proceed smoothly, which plays a positive role in
[24]. DWC replaces two columns with one, reducing reducing energy consumption and improving the conversion
installation space by 35-45% and providing an excellent path rate and product purity.
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Figueiredo et al. [43] used PVA membrane containing strong and the focus should be on dynamic modeling and process
acidic cation exchange resin with large pore to conduct control to solve complex and uncertain problems such as mass
pervaporation experiment in the autocatalytic reaction, which and heat transfer in the tower, combining reaction distillation
could increase the yield of ethyl acetate to 60%. In addition, with advanced computer simulation software is the future
the formation of azeotropes during the process does not limit development trend. The reaction section plays a significant
the application of membrane separation technology, because role in the reactive distillation process. Therefore, it is
the membrane separation technology is based on the principle imperative to select solid catalysts with excellent activity and
of selective transmission of raw material side components long life, as well as filler internals with good structure and
through the membrane, rather than gas-liquid equilibrium. performance, so scientists and technological workers should
Mitkowski et al. [44] used membrane separation technology focus on the development of catalysts and fillers to optimize
in the batch reactive distillation process and completed the the existing reaction distillation process. Reactive distillation
computer-aided design well. Buchaly et al. [45] used and other new unit coupling technologies are the fresh blood
membrane separation reactive distillation in the injected into the chemical intensive separation process, which
heterogeneous catalytic synthesis of n-propyl ester, and has the outstanding advantages of high selectivity and low
simulated and optimized the corresponding non-equilibrium footprint cost, and promotes the development of "green
stage model. distillation". Therefore, the combined mechanism of reactive
separation and coupling is a technical challenge for the future
3.4 Microwave reaction distillation development of chemical process intensification. It is
believed that reaction distillation in the future of the chemical
Microwave can provide energy to the reaction system, but it industry will have a broad development space with the
does not strengthen all the reaction distillation system. Gao et theoretical basis of reaction distillation technology, design
al. [46] developed the stripping microwave reactive application and equipment development related to the field of
distillation process based on the study of the gas-liquid research continues to deepen.
balance between microwave and non-microwave microwave
effects. Microwave reactive distillation process for the References
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