Application of Bronsted acid ionic liquids as green catalyst in the synthesis of 2-propanol with reactive distillation

Five Br?nsted acidic ionic liquids(ILs) were prepared and characterized by FT-IR,~1H NMR and ^(13)C NMR. Their catalytic activities for the synthesis of 2-propanol(IPOH) via transesterification of isopropyl acetate(IPAc) with methanol(Me OH) were investigated. Among all the tested ILs, [Ps-mim]HSO_4 performed best and was used as catalyst for further studies. The reaction kinetics were carried out to correlate the parameters in a homogeneous second order kinetic model. It has been found that there is close agreement between the calculated and experimental values. The high-pressure batch reactive distillation experimental apparatus was set up in order to enhance the conversion of IPAc. A high conversion of IPAc of 99.4% was obtained under the optimal reaction conditions. The catalyst [Ps-mim]HSO_4 can be recycled easily by a rotary evaporator and reused without any further treatment. The catalyst had been repeatedly used for four times and no obvious changes in the structure of catalyst could be observed.

Simulation and design of a heat-integrated double-effect reactive distillation process for propylene glycol methyl ether production

A double-effect reactive distillation(DERD)process was proposed for the production of propylene glycol methyl ether from propylene oxide and methanol to overcome the shortcoming of low selectivity and high-energy consumption in the tubular plug-flow reactor.A single-column reactive distillation(RD)process was conducted under optimized operating conditions based on sensitivity analysis as a reference.The results demonstrated that the proposed DERD process is able to achieve more than 95%selectivity of the desired product.After that,a design approach of the DERD process with an objective of the minimum operating cost was proposed to achieve further energy savings in the RD process.The proposed DERD configuration can provide a large energy-savings by totally utilization of the overhead vapor steam in the high-pressure RD column.A comparison of the single-column RD process revealed that the proposed DERD process can reduce the operating cost and the total annual cost of 25.3%and 30.7%,respectively,even though the total capital cost of DERD process is larger than that of the RD process.

Supported catalytic packing prepared from ceramic packing for reactive distillation of ethyl acetate

In this work,a strategy of"etching-modification filling-graft copolymerization"was proposed to load the acidic ionic polyionic liquid on the smooth ceramic surface.In this way,commercial ceramic Raschig rings were successfully transformed into the supported catalytic packing for the reactive distillation,and were further evaluated with esterification reaction of ethyl acetate by means of the fully mixed reactor,the ultrasonic destruction,the cyclic catalysis reaction and the lab-scale distillation column experiment.This catalyst coating has good adhesion with the substrate.It can withstand 24 h of ultrasound damage and shows good stability in three cycle catalytic experiments.This kind of coated catalyst has better catalytic activity than the commercial Amberlyst 15 dry.In the lab-scale reaction distillation,the supported catalyst Raschig ring can achieve a higher conversion in comparison with the tea bag catalytic packing of Amberlyst 15 dry under some conditions.

Reinforced temperature control of a reactive double dividing-wall distillation column

The mass and thermal coupling makes the control of the reactive double dividing-wall distillation column(R-DDWDC) an especially challenging issue with a highly interactive nature. With reference to the separation of an ideal endothermic quaternary reversible reaction with the most unfavorable ranking of relative volatilities(A + B ■ C + D with α_(A)>α_(C)>α_(D)>α_(B)), the operation rationality of the R-DDWDC is studied in this contribution. The four-point single temperature control system leads to great steady-state discrepancies in the compositions of products C and D and the reason stems essentially from the failure in keeping strictly the stoichiometric ratio between reactants A and B. A temperature plus temperature cascade control scheme is then employed to reinforce the stoichiometric ratio control and helps to secure a substantial abatement in the steady-state discrepancies. A temperature difference plus temperature cascade control scheme is finally synthesized and leads even to better performance than the most effective double temperature difference control scheme. These outcomes reveal not only the operation feasibility of the R-DDWDC but also the general significance of the proposed temperature difference plus temperature cascade control scheme to the inferential control of any other complicated distillation columns.

Novel eco-efficient reactive distillation process for dimethyl carbonate production by indirect alcoholysis of urea

Dimethyl carbonate is an eco-friendly essential chemical that can be sustainably produced from CO_(2),which is available from carbon capture activities or can even be captured from the air.The rapid increase in dimethyl carbonate demand is driven by the fast growth of polycarbonates,solvent,pharmaceutical,and lithium-ion battery industries.Dimethyl carbonate can be produced from CO_(2)through various chemical pathways,but the most convenient route reported is the indirect alcoholysis of urea.Previous research used techniques such as heat integration and reactive distillation to reduce the energy use and costs,but the use of an excess of methanol in the trans-esterification step led to an energy intensive extractive distillation required to break the dimethyl carbonate-methanol azeotrope.This work shows that the production of dimethyl carbonate by indirect alcoholysis of urea can be improved by using an excess of propylene carbonate(instead of an excess of methanol),a neat feat that we showed it requires only 2.64 kW·h·kg^(-1) dimethyl carbonate in a reaction-separation-recycle process,and a reactive distillation column that effectively replaces two conventional distillation columns and the reactor for dimethyl carbonate synthesis.Therefore,less equipment is required,the methanol-dimethyl carbonate azeotrope does not need to be recycled,and the overall savings are higher.Moreover,we propose the use of a reactive distillation column in a heat integrated process to obtain high purity dimethyl carbonate(>99.8 wt-%).The energy requirement is reduced by heat integration to just 1.25 kW·h·kg^(-1) dimethyl carbonate,which is about 52%lower than the reaction-separation-recycle process.To benefit from the energy savings,the dynamics and control of the process are provided for10%changes in the nominal rate of 32 ktpy dimethyl carbonate,and for uncertainties in reaction kinetics.

Design and optimization of reactive distillation: a review

Reactive distillation process,a representative process intensification technology,has been widely applied in the chemical industry.However,due to the strong interaction between reaction and separation,the extension of reactive distillation technology is restricted by the difficulties in process analysis and design.To overcome this problem,the design and optimization of reactive distillation have been widely studied and illustrated for plenty of reactive mixtures over the past three decades.These design and optimization methods of the reactive distillation process are classified into three categories:graphical,optimization-based,and evolutionary/heuristic methods.The primary objective of this article is to provide an up-to-date review of the existing design and optimization methods.Desired and output information,advantages and limitations of each method are stated,the modification and development for original methodologies are also reviewed.Perspectives on future research on the design and optimization of reactive distillation method are proposed for further research.

Evolutionary Algorithms for Controller Tuning of Tert-Amyl-Methyl-Ether Reactive Distillation

Efficient tuning of the coefficients used by proportional-integral-derivative(PID)controllers enhances their performance.For highly non-linear systems,optimization algorithms are required to make the PID controllers more responsive to disturbances.The production of tert-amyl-methyl-ether(TAME),an essential additive for gasoline,in reactive distillation columns integrates highly non-linear reaction and separation processes.On the other hand,TAME distillation is an azeotrope distillation process,therefore non-linearity of this process is more complex than that of conventional distillation.PID-controller tuning methods applying a genetic algorithm(GA)and a particle swarm optimization(PSO)algorithm are compared using a dynamic simulation that integrates the optimization algorithms with the HYSYS process simulator.The PID controller response trends are analyzed following the introduction of a significant disturbance to the TAME reactive distillation column(i.e.,a ten percent change in the methanol feed temperature).The PSO PID controller tuning method that minimizes the integral of the absolute error(IAE)as its objective function significantly outperforms the GA tuning method.The novel PID-tuning methodology developed has more extensive application potential.

Application of the Chemical-Looping Concept for Azoetrope Separation

The need for the separation of azeotropic mixtures for the production of high-end chemicals and resource recovery has spurred significant research into the development of new separation methods in the chemical industry.In this paper,a green and sustainable method for azeotrope separation is proposed based on a chemical-looping concept with the help of reversible-reaction-assisted distillation.The central concept in the chemical-looping separation(CLS)method is the selection of a reactant that can react with the azeotrope components and can also be recycled by the reverse reaction to close the loop and achieve cyclic azeotrope separation.This paper aims to provide an informative perspective on the fundamental theory and applications of the CLS method based on the separation principle,reactant selection,and case analysis,for example,the separation of alkenes,alkane,aromatics,and polyol products.In summary,we provide guidance and references for chemical separation process intensification in product refining and separation from azeotropic systems for the development of a more sustainable chemical industry.

Experimental results for the vapor-liquid equilibria of 0(formaldehyde+1,3,5-trioxane+methanol+salt+water)systems and comparison with predictions

The salt effect on the vaporliquid phase equilibrium(VLE)of solvent mixtures is of significant interest in the industrial production of 1,3,5trioxane.Experimental data for the VLE of quinary systems(formaldehyde+1,3,5trioxane+methanol+salt+water)and their ternary subsystems(formaldehyde+salt+water),(1,3,5trioxane+salt+water),and(methanol+salt+water)were systematic measured under atmospheric pressure.The salts considered included KBr,NaNO_(3),and CaCl_(2).The extended UNIFAC model was used to describe the VLE of the saltcontaining reactive mixtures.The model parameters were determined from the experimental VLE data of ternary systems or obtained from the literature,and then were used to predict the VLE of systems(1,3,5trioxane+KBr+water),(methanol+KBr+water),(formaldehyde+KBr+water),and(formaldehyde+1,3,5trioxane+methanol+salt+water)with salt=KBr,NaNO_(3),and CaCl_(2).The predicted results showed good agreements with the measured results.Furthermore,the model was used to uncover the salt effect on the VLE of these multisolvent reactive systems.