Pseudo-homogeneous Model Research Articles

Kinetic and mechanistic studies on the synthesis of dimethyl carbonate reaction using deep eutectic solvents as catalysts

Dimethyl carbonate (DMC) is extensively utilized in various industries due to its exceptional physical and chemical properties, functioning as an additive in gasoline and an electrolyte solvent in lithium batteries. Among several production methods, the transesterification of propylene carbonate (PC) with methanol (MeOH) is the most efficient and environmentally friendly. This study synthesized various deep eutectic solvents (DESs) using choline chloride (ChCl) as the hydrogen bond acceptor (HBA) and monoethanolamine (MEA) as the hydrogen bond donor (HBD) in molar ratios of 1: n (n = 5, 6, 7, 8). The DESs’ structures were analyzed using Fourier Transform Infrared (FT-IR) spectroscopy, and their melting points were determined via differential scanning calorimetry (DSC). The density, viscosity, and surface tension of the DESs were measured over a temperature range from 318.15 K to 358.15 K. The catalytic effects of four different DESs on PC transesterification with MeOH were investigated, revealing that ChCl-6MEA was the most effective catalyst, prompting its selection for further experiments. Subsequent investigations examined the effects of temperature, MeOH quantity, and catalyst dosage on PC conversion and DMC yield. Additionally, this study explored chemical equilibrium and reaction kinetics through experimental and theoretical approaches. Activity-based chemical equilibrium constants, derived from experimental data, and the van’t Hoff equation elucidated their temperature dependency. A pseudo-homogeneous (PH) model characterized the non-ideal thermodynamic behavior of the liquid phase in reaction kinetics analysis. The Arrhenius equation was employed to delineate the impact of temperature variations on reaction rate constants. Finally, the proposed reaction mechanism for ChCl-6MEA catalyzed transesterification was elucidated and verified through quantum chemistry (QC) calculations.

Kinetic modeling of microwave-assisted esterification for biofuel additive production: conversion of levulinic acid with pentanol using Dowex® 50WX8 catalyst

This study explores the esterification of levulinic acid with 1-pentanol, employing Dowex® 50WX8 as a catalyst under microwave irradiation. Key parameters such as the pentanol/acid molar ratio, temperature, and catalyst loading were evaluated and utilized for kinetic modeling. The kinetic behavior of the reaction was investigated using a dual-model approach: a pseudo-homogeneous model to account for the microwave effect and catalytic contributions modeled through LHHW and Eley–Rideal mechanisms. The best model was chosen based on statistical results obtained from Markov Chain Monte Carlo (MCMC) analysis, which involved an LHHW model with the surface reaction as the limiting step, resulting in an activation energy of 50.6 kJ mol−1 for the catalytic synthesis of pentyl levulinate. The role of the alcohol in the esterification route was explained, and catalytic stability was confirmed, with the catalyst maintaining activity over multiple cycles. The absence of mass transfer limitations was proved using the Weisz–Prater criterion. A plausible reaction pathway was proposed for the levulinic acid esterification over the 50WX8 catalyst.Graphical abstract

Thermodynamic and kinetic study on the catalysis of tributyl aconitate by Amberlyst-15 in a cyclic fixed-bed reactor

Abstract Tributyl aconitate is a new type of alternative plasticizer to phthalates. Amberlyst-15 was used to catalyze the esterification of aconitic acid and n-butanol for the preparation of tributyl aconitate in a cyclic fixed-bed reactor. The influence of the reaction conditions on the conversion was investigated. The results showed that the conversion of aconitic acid increased significantly with the rise of temperature and catalyst loading. The reaction conditions were optimized as: temperature: 115 °C; initial mass ratio of AA and n-butanol: 1:4; catalyst loading: 25 %; reaction absolute pressure: 85 kPa; volume flow rate: 30 mL min−1. Thermodynamics and kinetics of the reaction was studied. The non-ideality of the reaction system was rectified using the UNIFAC group contribution method. The kinetic process was simulated using the pseudo-homogeneous (PH) model, Eley-Rideal (E-R) model, and Langmuir-Hinshelwood-Hougen-Watson (LHHW) model. The results revealed that the E-R model exhibited superior suitability in simulating the kinetic process.

An integrated approach for parameter estimation of a propyl propionate synthesis model

This paper introduces an innovative approach to the ProPro synthesis process, aiming to improve the modeling and parameter estimation by integrating and optimizing existing methodologies. It combines well-established models available in the literature with a hybrid solution approach, emphasizing computational efficiency. Additionally, it assesses and enhance the modeling results by calculating confidence regions and uncertainties in both kinetic and thermodynamic modeling. To this end, a batch reactor with Amberlyst 46 catalyst is modeled. The parameter estimation approach combines Particles Swarm Optimization and Gradient Method to estimate both thermodynamic and kinetic parameters, sequentially and simultaneously. Confidence regions and uncertainties are determined for the sequential approach, guiding the search space for the simultaneous estimation. By utilizing PSO, the parameters are estimated, and their confidence regions are determined, providing a comprehensive understanding of their uncertainty. The uncertainty is propagated through the model predictions of the batch reactor, allowing for a comprehensive analysis of the system's behavior. The results demonstrate a good agreement between the model predictions and experimental data, with the expanded uncertainty adequately reflecting the statistical variability of the experimental observations. Furthermore, the heterogeneous Langmuir-Hinshelwood model yields improved representation of the experimental data in both transient and steady states compared to the pseudo-homogeneous model. The Root Mean Square Deviation (RMSD) for parameter estimation shows significant improvement compared to literature values. The simultaneous parameter estimation approach exhibits the best fit performance for the model predictions, confirming its effectiveness in accurately representing the system.

Solketal Production Using Eco-Friendly Reduced Graphene Oxide as the Catalyst

In this study, two materials based on reduced graphene oxide (rGOH or rGOE) were synthesized through the Hummers methodology and a more sustainable electrochemical method. These materials were extensively characterized and tested as catalysts in solketal production. Both rGOH and rGOE demonstrated significant catalytic activity, achieving 66.18% and 63.97% conversion rates, respectively. The catalytic activity of the synthesized materials was 30 times more efficient than the homogeneous catalyst p-Toluenesulfonic acid. Pseudo-homogeneous and heterogeneous kinetic models were employed to gain further insights into the glycerol ketalization reaction with acetone. The pseudo-homogeneous model suggested that the direct rate constant was lower than the reverse rate constant. In this sense, a reversible bimolecular reaction was proposed. The heterogeneous kinetic models revealed that in the Langmuir-Hinshelwood-Hougen-Watson mechanism, the controlling step of the reaction was the glycerol-acetone surface reaction on the catalyst. In contrast, in the Eley-Rideal mechanism, the reaction was controlled by the adsorbed glycerol on the reaction surface reacting with the available acetone in the bulk fluid. In the reusability tests, the rGOE catalyst demonstrated superior performance over five consecutive cycles, maintaining the highest activity without needing post-reaction washing or treatment.

Kinetics of esterification of acetic acid with n‐butanol over different homogeneous acid catalysts

AbstractThe esterification reaction of n‐butanol and acetic acid has been performed in batch reactor in the presence of different homogeneous acid catalyst, namely sulfuric acid, nitric acid, and para toluene sulfonic acid (p‐TSA). The objective of present research work is to investigate kinetic behavior of esterification reaction over the temperature range of 60°C–80°C. The effect of reaction parameter such as catalyst loading varied from 1% to 5% v/v and acid to alcohol molar ratio of 1:1, 1:3, and 1:5 has been observed. A pseudo homogeneous kinetic model has been applied. Kinetic parameters such as equilibrium constant, reaction rate constant, enthalpy, activation energy, and entropy were calculated by the experimental data for different acid catalyst system. It was observed that sulfuric acid gives higher conversion 73% than p‐TSA 68.5% and nitric acid 66.25% at temperature of 80°C, 1:1 molar ratio and 3% catalyst concentration. The activation energy was estimated 36448.49, 23324.31 and 19060.156 J/mol K for three different catalyst sulfuric acid, nitric acid and p‐TSA respectively. The enthalpy and entropy of the esterification reaction of acetic acid with n‐butanol over three different catalysts has been calculated (Enthalpy: 25.788 KJ/mol, 12.256 KJ/mol, 28.320 KJ/mol, Entropy: 88.1 J/mol K, 45.298 J/mol K, 91.44 J/mol K) and found enthalpy is having positive value that shows reaction is endothermic.

Optimal operation of a large-scale packed bed chemical-looping combustion process using nonlinear model predictive control

In this work, a nonlinear model predictive control (NMPC) scheme is presented for chemical-looping combustion (CLC) in a large-scale packed bed reactor. For NMPC, the plant is represented by a multiscale model comprised of mass and energy balances for both the reactor and particles, with states dependent on their location within both the spatial and temporal domains. A kinetic scheme was chosen from existing literature such that it can accurately predict the process behaviour obtained from multiple sets of literature data, attained using reactors of different sizes operating under different inlet flowrates and temperatures. The multiscale model was used to simulate the plant behaviour, while a pseudo-homogeneous model was used as the internal NMPC model to reduce computational costs for implementation of feedback control. For the pseudo-homogeneous model, it was verified that the gradients within the particles could be assumed to be negligible, and the number of states is decreased by about 87% by focusing on the reactor behaviour. The resulting NMPC scheme is implemented for packed bed CLC and was performed for both the oxidation and reduction stages of CLC. For NMPC of the oxidation stage, manipulating both the inlet air and inert gas fluxes allowed the outlet gas temperature to track a given setpoint. In this case, the oxidation stage generated energy for three times as long as the case when a constant inlet air flux is used. When NMPC was implemented for the reduction stage, improved CO2 selectivity could be achieved by manipulating the inlet fuel flowrate. This improved the CO2 and H2O purity of the outlet stream by over 20% and thus improved the carbon capture effectiveness of the process.

Mathematical Modeling of CO<sub>2</sub> Reforming of Methane with Reverse Water Gas Shift Reaction

Synthesis gas is the cornerstone of many chemical processes for manufacturing a broad range of petrochemical products. In this work, a mathematical model was developed for investigation of the CO2 reforming of methane in a catalytic packed bed reactor. To simulate the reformer, a pseudo homogenous two-dimensional mathematical model was developed and the resulting nonlinear second order partial differential equations were solved using the finite difference method. It was assumed that equilibrium reverse water gas shift reaction always takes place in the reactor to adjust H2/CO ratio (≤1). The effect of operating conditions, including bulk density, porosity, inlet gas and wall temperature, reactor diameter, total molar flow of gas and inlet CH4/CO2 ratio on the reactor performance were investigated. Finally, the study investigated the effect of H2/CO ratio on the outlet synthesis gas product at the range of 0.7–1. The validity of the model was investigated and the deviation between the model results and the experimental data was acceptable.

Kinetics of acetic acid and isoamyl alcohol liquid esterification over Amberlyst-70

This work is a kinetic study on liquid phase esterification between acetic acid and isoamyl alcohol using Amberlyst-70 as catalyst. There are not scientific papers with fitted kinetic models for this esterification system using this catalyst. Experiments were carried out in a laboratory batch reactor at controlled temperature conditions. Molar feed ratio (between 2 and 0.5), temperature (between 353.15 K and 383.15 K) and catalyst load (between 0.5 wt% and 2.0 wt%) were the manipulated experimental conditions. Measured composition profiles were used to fit the parameters for three versions of the pseudohomogeneous model (PHM) that differ in their activity model. At the end, a PHM model based on molar fractions is recommended to explain composition changes due to the esterification reaction. Calculated values for activation energy and chemical equilibrium constant are E = 43 kJ/mol and KE = 5.22, respectively. In accordance with the Weisz-Prater criterion, intraparticle mass transport effects were appreciable in experimental kinetic tests due mainly to the particle size used (0.363 mm). In order to take into account diffusional effects, the effectiveness factor was calculated using the Maxwell-Stephan equations. Therefore, adjusted models are the intrinsic kinetics and they can be used to simulate and design reactors and reactive distillation operations.

Novel intensified process for di-isopropyl ether production from isopropanol etherification using reactive distillation technology

The preparation of di-isopropyl ether (DIPE), as an important chemical solvent, by isopropanol (IPA) etherification is limited by chemical equilibrium and azeotropic formation in its production processes. A novel sustainable etherification process based on reactive distillation (RD) coupled with extractive distillation is proposed. The reaction of IPA etherification was carried out by cation exchange resin NKC-9 in a 250 mL autoclave and fitted by a pseudo-homogeneous model. According to the reaction kinetic, the IPA etherification RD model was established. To confirm the viability of RD and the accuracy of the model, pilot-scale RD experiments for generating DIPE were investigated. Based on the established model matching the pilot scale experiments, the operating conditions of the etherification RD column were optimized by sensitivity analysis. The simulation results show that the conversion of IPA in the RD column can be increased from 18.2 % to 77.9 % compared with autoclave and the yield of DIPE in the whole process flowsheet can reach 99.9 %, which demonstrates that combining reactive distillation with extractive distillation technology is a feasible and advantageous solution for DIPE production.

Analysis of the Effectiveness Factor in a Fixed-Bed Tubular Reactor System: Catalytic Dehydrogenation of Cyclohexanol

The modeling and simulation of the catalytic dehydrogenation process of cyclohexanol in a fixed-bed catalytic reactor is presented, leading to finding the relationship between the effectiveness factor, the Thiele modulus, and the Weisz–Prater modulus of the catalyst particles with respect to their axial and radial position, for which the external conditions of concentration and temperature around each particle were previously obtained by applying the material and energy balances in the catalyst bed considering a two-dimensional pseudo-homogeneous model with radial diffusion. Subsequently, the material balances are established in terms of the molar flux density and conversion, the energy balance in terms of the heat flux density, Fick’s law, Fourier’s law, and the differential form of the effectiveness factor non-isothermal for each particle chosen based on the proposed meshing. The Thiele modulus calculated for most of the points is between 0.8 and 0.25, with a tendency towards the lower limit, and the theoretical values established as the limit for the Thiele modulus fluctuate between 0.4<Th<4. Therefore, the effectiveness factor analyzed is between 1 and 1/Th; this indicates that both the reaction speed as well as the diffusion speed within the particle have an influence on the intraparticle process, which is confirmed by the calculation of the Weisz–Prater modulus whose values are not <<1 nor >>1. The results obtained are subjected to a statistical test leading to analyzing whether there are significant differences both in the Thiele modulus, as well as in the effectiveness factor with respect to the radius and length of the reactor. It has been determined that there are no significant differences between the effectiveness factor with respect to the radius of the reactor; however, according to the analysis of variance, there are significant differences in the effectiveness factor with respect to length and, likewise, there are significant differences in the Thiele modulus and the Weisz–Prater modulus with respect to radius and length.

Features of triamyl citrate synthesis

Objectives. To find an effective way for obtaining triamyl citrate, an environmentally friendly, biodegradable citric acid ester used as a plasticizer for PVC-based polymer compositions.Methods. The possibilities of heterogeneous catalysis were analyzed using the case study of three commercial samples of macroporous sulfocationites (Amberlyst™ 15, Amberlyst™ 70, and TULSION® 66). Homogeneous catalysis was studied using the example of orthophosphoric acid (H3PO4), while self-catalysis was investigated during esterification of citric acid with amyl alcohol (ROH). The syntheses were carried out under identical conditions: T = 110 °C, the ratio of CA:ROH = 1:5 (mol) amount of catalyst 1 wt % on the reaction mass in a thermostatically controlled reactor of ideal mixing with continuous distillation of the resulting water.Results. It was found that in all variants (even under self-catalysis conditions), the conversion of citric acid in 180 min reached 94–99%. Triamyl citrate was formed after 9 h with a yield of 90% only when using a homogeneous catalyst (H3PO4) and in the presence of a heterogeneous catalyst sample (Amberlyst ™ 15).Conclusions. The revealed differences in the reactivity of the studied sulfocationites (Amberlyst™ 15, Amberlyst ™ 70, and TULSION® 66) confirm the well-known theoretical positions, according to which the kinetic pseudo-homogeneous model of the esterification process of hydroxy acids in excess of aliphatic alcohols is based on the law of acting masses and depends on the specific surface area of the catalyst, which for Amberlyst ™ 15 is of the greatest importance as compared to Amberlyst ™ 70 and TULSION® 66 (m2/g): 53:36:35, respectively.

Kinetic modelling and simulations studies for propanoic acid esterification process

The esterification of propanoic acid with n-butanol to produce n-butyl propionate and water in the influence of an Amberlite catalyst was investigated using a batch reactor. The catalyst was chosen based on its ability to perform in this reaction. The temperature of the reaction runs between 363.15 K and 403.15 K, while the propanoic acid to n-butanol molar ratio is around 1:1 and 1:4. The selection of the catalyst loading is dependent on the volume of the reaction mixture. The catalyst dosage was kept within a 1%–3% by weight range. The kinetics of conversion have been researched in relation to the reaction temperature, mole ratio, catalyst size, stirrer speed, and catalyst quantity. The catalyst dosage and reaction temperature, according to the study, have a substantial influence on how soon the system achieves equilibrium. The pseudo homogeneous kinetic model is developed and tested against experimental results. Under the specified conditions, model predictions and empirical observations accord well. Arrhenius equation was used for calculation of rate constants and energy of activation. The forward reaction's frequency factor & activation energy are 18.554 L/mol.min and 30350 J/mol, correspondingly. Since the equilibrium constant increases as the temperature rises, the reaction is endothermic.

Model-based design of a segmented reactor for the flexible operation of the methanation of CO2

As the share of renewable energies is growing, chemical plants need to adapt to the current energy availability. This is highly relevant for power-to-gas plants, where large amounts of electricity are used for hydrogen and subsequent synthetic natural gas production. A high plant flexibility allows adjusting the plant load according to the availability of feed streams. This raises the question how the methanation process can meet the high flexibility of the upstream electrolytic hydrogen production. As a possible solution, we propose a segmented, adiabatic fixed-bed reactor for the enhancement of the load range for CO2 methanation. A 1D pseudo-homogenous model is presented to investigate the reactor regarding its main thermal effects. Our findings prove the feasibility of the concept and illustrate its main features: a larger operating window and shorter start-up times compared to a conventional unit. Furthermore, unlimited standby at high temperature levels is possible, if at least one segment is actively operated.

Numerical simulation on flow and reaction characteristics for catalytic region in helium-heated steam reformer coupled with HTR-10

In this paper, one dimension steady-state and pseudo-homogeneous model of the hydrogen production reformer in the steam methane reforming (SMR) process using the high temperature gas-cooled test reactor of 10 MW (HTR-10) as heat source (HTR-10/SMR) is simulated based on the semi-coupled solution method using matlab2016b. Firstly, The axial variations of hydrogen production performance including temperature (T2), methane conversion rate (XCH4), carbon monoxide conversion rate (XCO) and hydrogen production per mole methane (YH2/CH4 or total hydrogen production (YtH2)) as well as thermal efficiency (η) are investigated. Then, it is noted that YH2/CH4 decreases from 2.92 mol H2/mol CH4 to 2.53 mol H2/mol CH4. However, YtH2 increases from 2.33 kmol/h to 3.23 kmol/h with the increase of the inlet process gas flow rate (F2inlet) from 4 kmol/h to 6 kmol/h. Finally, YtH2 increases with steam to carbon ratio (S) when S < 4 and decreases when S > 4. The maximum value of YtH2 with 3.03 kmol/h is obtained at S = 4. Especially, XCH4, XCO, YH2/CH4 and η are in the range of 70.54%–90.78%, 38.56%–54.30%, 2.50–3.07 mol/mol CH4 and 54.55%–64.57%, respectively, when T3_inlet is in the range of 850–950 °C. The effect of the process gas temperature and pressure on the system performance can be neglected.

Theoretical and experimental investigation of the influence of intraphase diffusion on the oxidation of toluene over manganese-based oxide

ABSTRACT The influence of intraphase diffusion on the oxidation of toluene over manganese-based oxide, MnFeOx, under isothermal conditions was investigated. The one-dimensional (1D) heterogeneous model was developed to explain the experimental results. The model can be applied under certain operating conditions, i.e. conditions with negligible resistance to external mass transfer. The article describes the numerical solution of the equations of the proposed model. The relevance of the 1D heterogeneous model compared to the 1D pseudohomogeneous model was also emphasized. Validation of the proposed models was carried out by comparing with experimentally measured results. Both models were found to describe the experimental system studied quite well, with the 1D heterogeneous model providing better insight into the relationship between the rate of chemical reaction and the rate of intraphase diffusion.

Transesterification reactive extractive distillation process using ionic liquids as entrainers: From molecular insights to process integration

In this work, the transesterification reactive distillation coupled with extractive distillation process for n-propanol (PROH) and methyl acetate (MEAC) was developed based on pseudo homogeneous kinetic parameter model using ionic liquids (ILs) as entrainers. The COSMO-RS model was used for screening ILs entrainers. Here, 1-ethyl-3-methylimidazolium acetate [EMIM][AC] was selected as a potential entrainer due to its excellent solvent capacity and selectivity. Further, the COSMO-RS model was performed to calculate the polarization charge density (σ-profile) of methanol (MEOH), methyl acetate and [EMIM][AC], and to explore the molecular polarity. Based on quantum chemistry (QC) theory, the interaction energy between different molecular pairs is calculated. Independent gradient model (IGM) analysis identifies the interaction types of molecular pairs from the perspective of visualization. Owing to the strong hydrogen bond between anion [AC]− and MEOH, the extractive distillation process performance was significantly improved. Based on Aspen Plus platform, the effects of the theoretical stage number, reflux ratio, feed position and entrainer dosage on the cost and energy consumption of the new process was investigated. Based on the sensitivity analysis method, the operating conditions were optimized. Compared to the conventional process, the new reactive distillation coupled with extraction distillation process has higher energy efficiency and lower economic cost. The new process can save the total annual cost of about 3.42 × 105 $/year.

Intensified synthesis of glycerol monocaprylin using ionic liquids by temperature-responsive esterification

• [N 1,1,1,1 ][H 2 PO 4 ] is screened by COSMO-RS for selective synthesis of glycerol monocaprylin. • Dual effects of IL as solvent and catalyst are verified by analysis and experiments. • The esterification process with [N 1,1,1,1 ][H 2 PO 4 ] shows a temperature-responsive behavior. • The esterification conditions are optimized to obtain high GMC yield. • The esterification kinetics are correlated with the pseudo-homogeneous model. The selective conversion of glycerol (GL), a surplus by-product in biodiesel production, is deemed as a promising way to produce high value products. Glycerol monocaprylin (GMC), one of the widely utilized industrial chemicals, can be synthesized by esterification of GL with caprylic acid (CA). In this work, the intensified synthesis of GMC is proposed using ionic liquid (IL) as dual solvent and catalyst. The IL namely tetramethylammonium dihydrogen phosphate ([N 1,1,1,1 ][H 2 PO 4 ]) is screened out from 414 acidic IL candidates by calculating the infinite dilution capacity of GL and CA in ILs based on COSMO-RS model. The dual effects of [N 1,1,1,1 ][H 2 PO 4 ] are verified by σ -profile/ σ -potential analysis and experiments. The good solubility of [N 1,1,1,1 ][H 2 PO 4 ] for GL and CA makes the esterification system homogenous during reaction at high temperature, whereas phase splitting occurs after cooling down. Such a temperature-responsive behavior can greatly improve the GMC selectivity and benefit product separation and IL recycling. The reaction conditions are optimized to achieve 87.7% CA conversion and 78.4% GMC yield. The pseudo-homogeneous model is adopted to successfully describe the esterification kinetics with RMSD of 0.0349. Moreover, the recycling tests of [N 1,1,1,1 ][H 2 PO 4 ] are also performed, and the IL can keep its initial catalytic performance after four successive cycles.

Hidrólisis ácida de hemicelulosa de Ipomoea arborecens: Cinética de producción de xilosa

In this paper the composition change of Ipomoea arborescens was evaluated under acid hydrolysis pretreatment, and the kinetic parameters of this reaction were determined. The goal was to evaluate the effects of particle size in the reaction rate of hemicellulose hydrolysis, and to find the concentration of sulfuric acid in which the reaction mechanism favors hemicellulose hydrolysis of Ipomoea arborescens particles. Once the best conditions were found, Ipomoea arborescens particles were hydrolyzed at different temperatures. A pseudo-homogenous model was adopted to describe hemicellulose hydrolysis. The empirical formula of hemicellulose was determined experimentally to have 21 molecules of xylose, 5 molecules of glucose and 1 molecule of galactose. The mathematical model of hemicellulose hydrolysis is successful to describe the experimental results when the temperature is between 120 and 160°C.

Reactive Distillation of Glycolic Acid Using Heterogeneous Catalysts: Experimental Studies and Process Simulation.

The glycerol oxidation reaction was developed leading to selective catalysts and optimum conditions for the production of carboxylic acids such as glycolic acid. However, carboxylic acids are produced in highly diluted mixtures, challenging the recovery and purification, and resulting in high production costs, polymerization, and thermal degradation of some of the products. The protection of the acid function by esterification reaction is one of the most promising alternatives through reactive distillation (RD); this technique allows simultaneously the recovery of carboxylic acids and the elimination of most part of the water. The reactive distillation, experimental and simulation, of glycolic acid was performed, based on kinetic and thermodynamic models developed. For the thermodynamic model, binary parameters of the missing couples were determined experimentally, and the non-random two-liquid (NRTL) model was selected as the most suitable to represent the binary behavior. The kinetic study of the esterification in the presence of homogeneous and heterogeneous catalysis concluded that the heterogeneous reaction can be accurately described either by a pseudo-homogeneous model or the Langmuir–Hinshelwood (L-H) adsorption model. Reactive distillation was conducted in a distillation column filled with random packing sulfonated ion-exchange resin, Nafion NR50®, or with extruded TiO2-Wox. The conversion rate of glycolic acid in reactive distillation increases from 14% without catalyst to 30% and 36% using Nafion NR50® and TiO2-Wox, respectively. As opposed to the batch reactor study, the conversion rate of glycolic acid was better with TiO2-Wox than with sulfonated ion-exchange resin. The better performance was related to an increase in the hydrodynamics inside the column. Tests using water in the feed confirm the hypothesis by increasing the conversion rate because of the decrease in the mass transfer resistance by reducing the average diffusion coefficient. The simulation of the reactive distillation column with ProSim® Plus showed that the yield of the ester increased operating at a low feed rate with reactive stripping. In the presence of water in the feed, nonreactive stages are required, including an enrichment region to separate water vapor.