Ion-exchange Resin Catalyst Research Articles

Catalytic synthesis of DHHB using solid acids

Abstract DHHB (Diethylamino hydroxybenzoyl hexyl benzoate) is a widely regarded UV absorber with a high degree of safety, excellent efficiency and good solubility characteristics. In the conventional method of DHHB synthesis, H2SO4 is not effective as a catalyst. To address this drawback, we synthesized solid acid (sulfonic acid group-modified ion exchange resin) catalysts to replace H2SO4 by suspension polymerization modification and optimized the process. The experimental results showed that the yield of DHHB could reach 85% at 110 °C for 10 h, and the conversion of DHHB could be maintained above 90% after 10 cycles of the catalyst. SEM, FT-IR characterization and analysis of the solid acid catalysts before and after use revealed that the catalysts did not show any significant changes. The use of solid acid not only improves the yield of DHHB and reduces the energy consumption in the experimental process, but also the solid acid is simple to recover, recycled and has less waste acid. This experiment successfully explored a green and economic synthesis method for synthesizing DHHB.

Epoxidation of neem oil via in situ peracids mechanism with applied ion exchange resin catalyst

Epoxidation of neem oil via in situ peracids mechanism with applied ion exchange resin catalyst

Two-Stage Conversion of Used Cooking Oil to Biodiesel Using Ion Exchange Resins as Catalysts

This study focuses on the development of a novel two-stage (esterification–transesterification) synthesis of biodiesel from used cooking oil (UCO) using ion exchange resins as catalysts. Esterification of the UCO has been conducted using various types of ion exchange resin catalysts. Purolite D5081, a hyper cross-linked resin, showed the best catalytic performance among all the catalysts investigated, with 92% of free fatty acid (FFA) conversion. The transesterification of pre-treated used cooking oil (P-UCO) was carried out sequentially using several acidic and basic ion exchange resin catalysts. In the screening process, the Diaion PA306s catalyst showed the best catalytic performance and was selected for the optimisation study. A triglyceride conversion of ca. 75% was recorded at the optimum reaction conditions (9% (w/w) catalyst loading, 328 K reaction temperature, 18:1 methanol to P-UCO feed mole ratio, and 350 rpm stirring speed). Furthermore, the reusability study of the Diaion PA306s catalyst gave a similar triglyceride conversion after a couple of cycles without losing its catalytic activity. A dry purification technique was found to give the lowest percentage of glycerides and glycerine content and, therefore, was chosen as the best biodiesel purification route.

Investigation of sustainable reactive distillation process to produce malonic acid from dimethyl malonate

The new energy battery is currently a hot research topic, leading to an increase in the demand for malonic acid (MA) as a raw material. The objective of the present work is to find a potential reactive distillation (RD) process to solve the problem of low conversion and high energy consumption in hydrolytic system. In the meantime, the RD technology still faces the problem of how to distribute water in the RD column. Aiming at the problem, four different RD processes are proposed: RD combined water separation process (RDWS), RD combined with MA concentration process (RDMC), RD combined methanol separation process (RDMS), and single RD process (SRD). Beforehand, reaction kinetic of dimethyl malonate (DM) hydrolysis was investigated using the ion exchange resin catalysts, and the developed RD model was verified via pilot-scale RD experiments. Finally, the proposed RD process is analyzed from the aspects of economic and environmental and compared with the traditional reaction + distillation (R + D) process. Consequently, the proposed SRD process is a better economy-saving and environment-friendly technology, and has certain directive significance for the industrial production of MA.

Pervaporation Membrane-Catalytic Reactors for Isoamyl Acetate Production

This study reports the analysis and design of a liquid phase esterification process to convert acetic acid with isoamyl alcohol into isoamyl acetate via reactive pervaporation, in the presence of an Amberlite IR-120 ion exchange resin catalyst. To accomplish this, a catalytic reactor is coupled with a separation membrane unit (Pervaporation Membrane Reactor (PVMR)). In the proposed unit, the chemical reaction equilibrium is favorably shifted towards isoamyl acetate formation by removing water with the help of a separation membrane. The study is developed by using relevant thermodynamics, kinetics, and membrane transport models, and by considering different catalytic reactor-pervaporator membrane configurations such as: (a) a two-step continuous fixed bed-pervaporator process (FBR+PVMU), (b) a two-step continuous slurry reactor-pervaporator process (SR+PVMU), (c) a single-step integrated fixed bed-pervaporator reactor (IFBPVMR), and d) a single step integrated slurry-pervaporator reactor (ISPVMR). The performance of the PVMRs is evaluated by using a R recycle ratio, a Ω membrane area to reactor volume ratio, and Da Damköhler dimensionless parameters. From the various proposed configurations, it is shown that the integrated plug flow reactor-pervaporation reactor (IFBPVMR) provides the best performance. On the basis of various simulations and design charts developed in the present study, operational conditions leading to optimum ester yields as high as 0.94 are predicted. These results provide a valuable prospect for the industrial scale-up and implementation of isoamyl acetate production units.

Evaluation of hybrid amines and alcohol solvent with ion-exchange resin catalysts for energy-efficient CO2 capture

Cation exchange resin catalysts are a novel approach to accomplish improvement in aqueous monoethanolamine (MEA) regeneration.

Controlling reaction selectivity for sugar fatty acid ester synthesis by using resins with different basicities

A strongly basic ion-exchange resin catalyst was reported to exhibit a high catalytic activity in transesterification to produce a bio-based surfactant, sugar ester under mild condition. However, the side-reactions to decompose the reactant and the product were found to occur. This study was aimed to improve the selectivity of sugar ester synthesis by newly focusing on the basicity of the resin. A weakly basic resin (Diaion WA20) with a lower mass transfer resistance suppressed the decompositions while maintaining synthesis rate. Controlling molar ratio of the reactants in the intraparticle reaction field also increased the reaction selectivity, 72.1% and product yield, 57.5%. Both values were drastically increased compared to the reported values with the strongly basic resin (selectivity 50.9%, yield 14.3%). This is the first knowledge to show a high catalytic activity of weakly basic resin. These results suggest that a more efficient continuous production process would be possible.

Hydrolysis of Oligosaccharides and Polysaccharides on Sulfonated Solid Acid Catalysts: Relations between Adsorption Properties and Catalytic Activities.

Sulfonated solid acid materials, such as sulfonated carbon catalysts, are promising materials as heterogeneous catalysts for the hydrolysis of esters and polysaccharides in water solvents. The catalytic active site is a sulfonic acid functional group. Compared to conventional strong acidic ion-exchange resin catalysts, sulfonated carbon materials have less sulfonic acid functional groups but higher catalytic activity for hydrolysis of polysaccharides per catalyst weight. However, the details of catalytic properties and the substrate suitability of both catalysts are unclear. In this study, the hydrolytic activities and the adsorption properties of both catalysts were investigated for various oligosaccharides and polysaccharides with varying degrees of polymerization (DP). The catalytic activities for the hydrolysis with increase of the DP of saccharides were found to increase over the sulfonated carbon catalyst but decrease over strong acidic ion-exchange resin catalyst. The inverse catalytic properties attribute to the dependence of the amounts of adsorption and/or penetration of saccharides on the DP. Moreover, the catalytic activity per acidic sites of strong acidic ion-exchange resin is in good agreement with the value obtained by multiplying the catalytic activity of a dilute sulfuric acid by the penetration degrees.

Synthesis of 5-HMF from an ultrasound-ionic liquid pretreated sugarcane bagasse by using a microwave-solid acid/ionic liquid system

This work aimed at investigating the synthesis of 5-HMF from the ultrasound-ionic liquid pretreated sugarcane bagasse in a microwave-solid acid-ionic liquid system. The XRD analysis indicated that the macrostructure of cellulose remained intact after the ultrasound-ionic pretreatment, [Bmim]OAc showed better performance than [Bmim]Cl. The best conditions for the untreated bagasse conversion to 5-HMF were [Bmim]OAc, ion-exchange resin catalyst, D001-cc, 140 ℃ and 25 min. The ultrasound-ionic liquid pretreatment at different frequencies (20–50 kHz) increased the 5-HMF yield by 39.73–165.43 % compared with that of the untreated bagasse, indicating the role of the acoustic cavitation in enhancing the transformation of bagasse into 5-HMF. The bagasse pretreated with [Bmim]OAc/ultrasound at 40 kHz/30 min showed the highest yield of 5-HMF (65.72 %). The synthesis of 5-HMF from the pretreated sugarcane bagasse in the microwave-solid acid/ionic liquid system could be a promising channel for production of biofuels and related chemicals.

Biomass transformation: Hydration and isomerization reactions of turpentine oil using ion exchange resins as catalyst

The hydration and isomerization of the biomass turpentine have been studied in the presence of Purolite CT175. The ion exchange resin catalyst was active for hydration and selective for producing terpenic alcohols, with a conversion of 97% and showed 57% selectivity for α-terpineol using heating and stirring. The Purolite CT175-catalyzed isomerization of turpentine taken place in a high intensity ultrasound (HIU) condition; and showed conversion of 90% and 30% selectivity for camphene at 30 min. Recyclability of ion exchange resin was evaluated in both reaction and its activity remained good even after four runs.

Production of methyl caffeate as an intermediate product to produce caffeic acid phenethyl ester by esterification using cation-exchange resin

Caffeic acid (CA) could be considered as an important natural anti-oxidant. However, the low solubility and stability of CA in various solvent is limiting the application in industry. It is advantageous to synthesize alkyl ester of caffeic acid based on both their biological function and potential application. One of the caffeic acid derivatives called caffeic acid phenethyl ester (CAPE) is a compound with numerous important biological activities. To synthesize CAPE one of the method used is catalyzed esterification of caffeic acid and phenethyl alcohol using ion exchange resin catalyst. The first step of the process is to perform esterification of caffeic acid and methanol to produce methyl caffeate (MC). MC would then be used to produce CAPE in the presence of phenethyl alcohol. Herein, the reaction condition and kinetic parameters for the synthesis of MC using cation-exchange resin as a catalyst were investigated, and the product was confirmed by high-performance liquid chromatography (HPLC). The highest yield of MC catalyzed by cation-exchange resin attained under the optimum condition as follows: reaction temperature of 60 °C and a reaction time of 4 h. The esterification kinetics of CA and methanol is described by the pseudo-homogeneous​ first order model. The relationship between temperature and the forward rate constant gives activation energy of 51 kJ/mol. These results indicated that cation-exchange resin possesses high catalytic activity in the synthesis of MC, which is an efficient catalyst suitable for MC production.

A combination of low‐temperature reactive and extractive distillation for methoxy‐2‐propyl acetate synthesis and separation process: simulations and experiments

AbstractBACKGROUNDEsterification of methoxy propanol (MP) and acetic acid (HAC) to methoxy‐2‐propyl acetate (MPA) is a typical reversible reaction. The yield of MPA is low owing to the limitation of chemical equilibrium. In the present study, with the goal of increasing the reaction conversion and preventing the NKC‐9 cation exchange resin catalyst from deactivation at high temperature, a process combining low‐temperature reactive and extractive distillation with cyclohexane (C6H12) as entrainer was investigated by process simulations and experiment methods.RESULTSThe intrinsic kinetic parameters were obtained by catalyst activity evaluation in a batch reactor. Binary interaction parameters of thermodynamic models were determined by the measurement and fitting of vapor–liquid equilibrium data. The effects of different operating parameters on the reaction conversion and column performance were examined in detail, and a production process of MPA with an annual output of 56 000 tons was suggested. The results showed that the purity of MPA reached nearly 100% after further purification following reactive distillation, and the reaction temperature was controlled in the range 75–80 °C, which allowed long‐term operation thermal stability of the catalyst.CONCLUSIONThe developed low‐temperature reactive distillation method ensured a long life of the ion exchange resin catalyst, which should provide insights into further advances of MPA industrial production. © 2019 Society of Chemical Industry

Screening of ion exchange resin catalysts for epoxidation of oleic acid under the influence of conventional and microwave heating

AbstractBACKGROUNDFor many chemical systems, it is of great importance to find a durable, active and efficient catalyst that improves the process performance. Epoxidation of oleic acid with peracetic acid (Prilezhaev oxidation) was carried out in an isothermal loop reactor in the presence of heterogeneous catalysts. The kinetic experiments conducted under microwave heating (MW) were compared with identical experiments carried out under conventional (conductive/convective) heating. Extensive screening of heterogeneous catalysts was conducted and the influence of microwave irradiation on the reaction kinetics was studied. Several ion exchange resins were screened to explore their applicability and activity in the epoxidation of oleic acid. The perhydrolysis reaction (peracetic acid formed in situ from acetic acid and H2O2) was promoted with the use of various solid acid catalysts: Amberlite IR‐120, Amberlyst 15, Smopex®, Dowex 50x8‐100, Dowex 50x8‐50, Dowex 50x2‐100 and Nafion™.RESULTSFrom the selected group of catalysts, Dowex 50‐x8100 and Dowex 50x8‐50 produced the highest yield of epoxidized oil. Only minor differences in the reactant conversion and the product yield were found in the experiments carried out under microwave exposure compared to the conventionally heated experiments in the presence of several ion exchange resins.CONCLUSIONSThe catalytic effect was much more prominent than the microwave effect, because the solid acid catalysts enhanced the slow step of the process, the perhydrolysis of acetic acid. The catalytic effect was very dominant and a considerable improvement of the oleic acid conversion and the epoxide yield was observed in the presence of the top‐performing catalysts. © 2019 Society of Chemical Industry

AmberliteTM IRA67: A novel and efficient ion exchange resin catalyst for the synthesis of 1, 8-dioxoxanthene derivatives

The catalytic performance of AmberliteTM IRA67, the heterogeneous weak Base Exchange resin which bears tertiary amine functional group, for the synthesis of 1, 8-dioxoxanthene derivatives were inve...

New method of running the bisphenol A synthesis process using the set of two-zone reactors

The paper presents a new development concept for the bisphenol A synthesis process with use of the innovative two-zone reactors, packed with promoted ion exchange resin catalyst. The operating characteristics of the two-zone reactor have been described using a realistic mathematical model.Empirical studies supporting the modelling calculations were conducted using a pilot reactor similar to the industrial case, utilizing real-life reaction mixtures obtained from industrial BPA synthesis plant.An acceptable model accuracy measured by correlation coefficient (0.926) and the linear regression coefficient (0.99) was obtained. The comparative studies have been performed with the use of the subject innovative two-zone reactor and the reference “conventional” single-stage one.The two of 14-month production cycles of the synthesis unit utilising two-zone reactors and a single stage one have been described in detail.In the case of a BPA synthesis process unit built around a two-zone reactor, it was possible to obtain significantly higher values both for increase of a BPA mass fraction (ΔwBPA=0.171) and for selectivity (SBPA=97.3%) when compared with the synthesis process based on a single-stage reactor. It is also possible to achieve and maintain high stability of the above-mentioned parameters in the course of a production cycle.

Esterification Reaction Kinetics Using Ion Exchange Resin Catalyst by Pseudo-Homogenous and Eley-Ridel Models

This work deals with kinetics and chemical equilibrium studies of esterification reaction of ethanol with acetic acid. The esterification reaction was catalyzed by an acidic ion exchange resin (Amberlyst-15) using a batch stirred tank reactor. The pseudo-homogenous and Eley-Rideal models were successfully fitted with experimental data. At first, Eley-Rideal model was examined for heterogeneous esterification of acetic acid and ethanol. The pseudo-homogenous model was investigated with a power-law model. The apparent reaction order was determined to be (0.88) for Ethanol and (0.92) for acetic acid with a correlation coefficient (R2) of 0.981 and 0.988, respectively. The reaction order was determined to be 4.1087x10-3 L0.8/(mol0.8.min) with R2 of 0.954. The adsorption constants of acetic acid and ethanol were calculated as 0.023 and 0.044 L/mol, respectively and the lumped reaction constant were determined to be 5*10-4 L2/gcat.mol.min. The results of the reaction kinetic study show that the high acetic acid/ethanol molar ratio was favored. The maximum conversion of 70 % was obtained at 70°C for acetic acid/ethanol molar ratio of 4.

A Synthesis, Process Optimization, and Mechanism Investigation for the Formation of Polyoxymethylene Dimethyl Ethers

Polyoxymethylene dimethyl ethers (DMMn) are promising diesel additives. The synthesis of DMMn from methylal (DMM) and paraformaldehyde over the NKC-9 acidic ion-exchange resin catalyst was investigated. Many unrecyclable by-products such as methyl formate, dimethyl ether and formic acid were produced in the reaction. To increase the selectivity of the desired products DMM3‒6 and reduce the amount of unrecyclable by-products, the effects of reaction temperature, time, pressure and the molar ratio of the raw materials were evaluated through a series of single factor experiments. Experiments revealed that trace amount of water could suppress the formation of unrecyclable by-products, and the optimum initial water content (less than 2 wt%) was investigated. In addition, the synthetic process needs to go through the polyoxymethylene hemiformals intermediate stage, and then the DMMn were obtained when polyoxymethylene hemiformals reacted with methanol. Ultimately, a possible mechanism is proposed to describe the formation of DMMn from polyoxymethylene hemiformals in detail, in which it is revealed that the formation of carbocation intermediates is important in the reaction processes.

Electro-Catalytic Biodiesel Production from Canola Oil in Methanolic and Ethanolic Solutions with Low-Cost Stainless Steel and Hybrid Ion-Exchange Resin Grafted Electrodes

Biodiesel is a growing alternative to petroleum fuels and is produced by the catalysed transesterification of fats in presence of an alcohol base. Transesterification processes using homogeneous catalysts are considered to be amongst the most efficient methods but rely on the feedstock quality and low water content in order to avoid undesirable saponification reactions. In this work, the electro-catalytic conversion of canola oil to biodiesel in a 1% aqueous methanolic and ethanolic reaction mixture was performed without the addition of external catalyst or co-solvent. An inexpensive stainless steel electrode and a hybrid stainless steel electrode coated with an ion-exchange resin catalyst were used as cathode materials while the anode was composed of a plain carbon paper. The cell voltages were varied from 10 to 40 V and the reaction temperature maintained at 20 or 40°C. The canola oil conversion rates were found to be superior at 40°C without saponification reactions for cell voltages below 30 V. The conversion rates were as high as 87% for the hybrid electrode and 81% for the plain stainless steel electrode. This work could inspire new process development for the conversion of high water content feedstock for the production of second-generation biodiesel.

Kinetic modeling of carboxylation of propylene oxide to propylene carbonate using ion-exchange resin catalyst in a semi-batch slurry reactor

Kinetic modeling of carboxylation of propylene oxide with CO2 to propylene carbonate has been investigated in a semi-batch slurry reactor. Propylene oxide can be selectively transformed into propylene carbonate (selectivity: 99+%) in the presence of ion exchange resin catalysts with basic functional groups. The effect of reaction temperature (65–95°C), CO2 pressure (0.5–3.0MPa), propylene oxide concentration in propylene carbonate (as a solvent) on the carboxylation rates was studied. Experimental results show that CO2 displays inhibition effect on carboxylation reaction at high pressure conditions. For kinetic modeling, three types of rate models were investigated, including two involving Langmuir-Hinshelwood and one modified Eley-Rideal mechanisms. Details of model discrimination and evaluation of kinetic parameters are discussed. Based on the parameter estimation and rigorous model discrimination, it is found that the proposed modified Eley-Rideal rate model describing surface reaction between free PO and adsorbed CO2 on catalyst surface fits the experimental data very well.

3-11-3 イオン交換樹脂法によるパイロットプラントを用いた高品質バイオディーゼルの連続製造(Session 3-11 BDF等1)

3-11-3 イオン交換樹脂法によるパイロットプラントを用いた高品質バイオディーゼルの連続製造(Session 3-11 BDF等1)