Reactor sizing for butane steam reforming over Ni and Ru catalysts

We obtained kinetics data on steam reforming of butane and calculated the appropriate reactor size based on the kinetics data. Using commercial Ni and Ru catalysts, steam reforming reactions of butane were performed while changing the reaction temperature and partial pressure of reactants. After comparing the power law model and the Langmuir-Hinshelwood model by using the kinetics data obtained from the experiment, it is revealed that the reaction rate could be determined by both models in the reforming reaction of butane over commercial Ni and Ru catalysts. Also, calculation of the steam reforming reactor size using a PRO/II simulation with a kinetic model equation showed that the reactor size using the Ni catalyst is smaller than that with the Ru catalyst to obtain the same conversion.     

Kinetic study of the competitive hydrogenation of glycolaldehyde and glucose on Ru/C with or without AMT

The competitive hydrogenation of glycolaldehyde and glucose over 1% Ru/C catalyst was studied in a batch reactor at 373–403 K and 6 MPa hydrogen pressure, with or without the presence of ammonium metatungstate (AMT). It was found that the presence of AMT retarded significantly the hydrogenation of both aldoses, and this suppressing effect was more pronounced on the glucose hydrogenation. The hydrogenation of glycolaldehyde occurred always preferentially to the glucose hydrogenation, with or without the presence of AMT. The kinetic data in the absence of AMT were well modeled based on Langmuir–Hinshelwood–Hougen–Watson kinetics assuming the surface reaction being rate‐determining and noncompetitive adsorption of dissociatively chemisorbed hydrogen and aldose. However, in the presence of AMT, the complexing between AMT and aldose and the strong adsorption of AMT on Ru surface must be considered in the development of new kinetic model. The as‐modified model described the data satisfactorily. © 2014 American Institute of Chemical Engineers AIChE J, 61: 224–238, 2015     

A study on the curing kinetics of epoxy molding compounds with various latent catalysts using differential scanning calorimetry

We performed kinetic analysis in an epoxy curing system with differential scanning calorimetry (DSC) using a dynamic approach to investigate the reaction behavior of epoxy molding compounds (EMCs) according to three types of catalysts with varying latencies: triphenyl phosphine (TPP), triphenylphosphine‐1,4‐benzoquinone (TPP‐BQ), and tetraphenylphosphonium tetraphenylborate (TPP‐TPB). In dynamic approach, the well‐known model free kinetic (MFK) method was applied first to find out the variation of activation energy by the extent of conversion. By applying the MFK method, it was found that activation energy as a function of reaction conversion was nearly constant for TPP‐BQ and TPP‐TPB, but significantly reduced for TPP. By the dependence of activation energy, the model fitting method with single step reaction could be applied for TPP‐BQ and TPP‐TPB, and the nth order model was in good agreement with the MFK results. By contrast, in TPP, the reaction curve derived from MFK did not match with plot from nth order model. Isothermal curing experiments were also carried out to determine whether the assumption on kinetic predictions for the three catalysts was correct or not. As a result, TPP‐TPB and TPP‐BQ followed both MFK and nth order model. Nevertheless, TPP was more likely to follow MFK rather than nth order model. In addition, TPP‐TPB showed definitely lower conversion rate and degree of conversion compared with TPP, TPP‐BQ as expected from the catalyst structure and basicity. This study indicates the curing kinetic reaction of EMC depends on the latency of catalysts, and the MFK method can be used to describe the kinetics of curing reaction more accurately. These results help engineers in relevant fields to improve the reliability of EMCs by understanding the curing kinetic reaction of EMC with various latent catalysts. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45252.     

Kinetic modeling of hemicellulose hydrolysis in the presence of homogeneous and heterogeneous catalysts

Kinetic models were developed for the hydrolysis of O‐acetyl‐galactoglucomannan (GGM), a hemicellulose appearing in coniferous trees. Homogeneous and heterogeneous acid catalysts hydrolyze GGM at about 90°C to the monomeric sugars galactose, glucose, and mannose. In the presence of homogeneous catalysts, such as HCl, H₂SO₄, oxalic acid, and trifluoroacetic acid, the hydrolysis process shows a regular kinetic behavior, while a prominent autocatalytic effect was observed in the presence of heterogeneous cation‐exchange catalysts, Amberlyst 15 and Smopex 101. The kinetic models proposed were based on the reactivities of the nonhydrolyzed sugar units and the increase of the rate constant (for heterogeneous catalysts) as the reaction progresses and the degree of polymerization decreases. General kinetic models were derived and special cases of them were considered in detail, by deriving analytical solutions for product distributions. The kinetic parameters, describing the autocatalytic effect were determined by nonlinear regression analysis. The kinetic model described very well the overall kinetics, as well as the product distribution in the hydrolysis of water soluble GGM by homogeneous and heterogeneous catalysts. The modelling principles developed in the work can be in principle applied to hydrolysis of similar hemicelluloses as well as starch and cellulose. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1066–1077, 2014     

Kinetics of glycerol conversion to hydrocarbon fuels over Pd/H‐ZSM‐5 catalyst

The utilization of glycerol, primary byproduct of biodiesel production, is important to enhance process economics. In our recent prior work, it was shown that glycerol can be converted to hydrocarbon fuels over bifunctional catalysts, containing a noble metal supported on H‐ZSM‐5. Over Pd/H‐ZSM‐5 catalyst, an optimal ～60% yield of hydrocarbon fuels was obtained. In the present work, based on experimental data over Pd/H‐ZSM‐5 catalyst, a lumped reaction network and kinetic model are developed. Using differential kinetic experiments over the temperature range 300–450°C, the rate constants, reaction orders, and activation energies are obtained for each reaction step. The predicted values match well with experimental data for glycerol conversion up to ～90%. © 2017 American Institute of Chemical Engineers AIChE J, 63: 5445–5451, 2017     

Kinetics of esterification of palmitic acid with isopropanol using p‐toluene sulfonic acid and zinc ethanoate supported over silica gel as catalysts

Kinetic data on the esterification of palmitic acid with isopropanol were obtained using homogeneous (para‐toluene sulfonic acid, p‐TSA) and heterogeneous (zinc ethanoate coated on silica gel, ZnA/SG) catalysts in a batch reactor. The ZnA/SG catalyst was prepared using a sol–gel technique. The esterification reaction was studied at different reaction temperatures (373–443 K), initial reactants molar ratio (1–5), catalyst loading (1–5 gcat dm^?3) and water concentration in feed (0–15 vol%). A power law rate equation was used for homogeneous kinetics analysis. The Langmuir Hinshelwood Hougen Watson (LHHW) model was used for heterogeneous kinetics. The kinetic parameters of both models were obtained using Polymath software. The reaction parameters were used to obtain simulated values of conversion for both catalytic systems. The simulated values were compared with the experimental values and were in good agreement. Copyright © 2004 Society of Chemical Industry     

Matlab用于葡萄糖加氢催化反应动态模拟

对用于葡萄糖催化加氢反应的钌碳催化剂的催化反应数据进行分析和曲线拟合。用Matlab进行计算机模拟实验,找出比表面积和孔容对催化反应的转化率和选择性影响的最优条件,预测最佳催化反应选择性和反应转化率区间,优化筛选催化剂载体的条件,以改进催化剂的活性。     

A kinetic study on the autocatalytic cure reaction of a cyanate ester resin

The cure of a novolac‐type cyanate ester monomer, which reacts to form a polycyanurate network, was investigated by using differential scanning calorimeter. The conversions and the rates of cure were determined from the exothermic curves at several isothermal temperatures (513–553 K). The experimental data, showing an autocatalytic behavior, conforms to the kinetic model proposed by Kamal, which includes two reaction orders, m and n, and two rate constants, k₁ and k₂. These kinetic parameters for each curing temperature were obtained by using Kenny's graphic‐analytical technique. The overall reaction order was about 1.99 (m = 0.99, n = 1.0) and the activation energies for the rate constants, k₁ and k₂, were 80.9 and 82.3 kJ/mol, respectively. The results show that the autocatalytic model predicted the curing kinetics very well at high curing temperatures. However, at low curing temperatures, deviation from experimental data was observed after gelation occurred. The kinetic model was, therefore, modified to predict the cure kinetics over the whole range of conversion. After modification, the overall reaction order slightly decreased to be 1.94 (m = 0.95, n = 0.99), and the activation energies for the rate constants, k₁ and k₂, were found to be 86.4 and 80.2 kJ/mol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3067–3079, 2004     

Homopolymerization of 4‐propionoxybenzoic acid: A kinetic study

A kinetic study of the synthesis of poly(4‐oxybenzoate) by melt‐step growth polymerization using para‐propionoxybenzoic acid is reported. The polycondensations obey second‐order kinetics, irrespective of whether the reaction was catalyzed or uncatalyzed. Breaks are observed in the kinetic plots, suggesting the presence of different kinetic regimes during the course of the reaction. An elaborate kinetic model that presupposes precipitation of oligomers predicts two‐stage kinetics as well as breaks in the rate plots and fits experimental data well throughout the course of the reaction and the performance of two transesterification catalysts are estimated. No isokinetic temperature is displayed for the transesterification reaction. Activation energy values for catalyzed reactions are found to be higher than the uncatalyzed reaction, indicating that entropy factors drive the reaction to completion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 467–476, 1999     

Refinement of the kinetic model for guaiacol hydrodeoxygenation over platinum catalysts

In our prior work (Ind Eng Chem Res, 2015, 54, 10638-10644), hydrodeoxygenation (HDO) kinetics of guaiacol, a well-known model compound of bio-oil, over Pt/AC (activated carbon) catalysts were investigated under integral operating conditions. It was found that the pseudo-homogeneous plug-flow model utilizing these kinetics describes the experimental observations well (with normalized RMS error = 7.6%). In the present work, under differential operating conditions instead, we refine the kinetic model for the same reaction network over the same catalyst. We show that among the five reaction steps in the network, the reaction order of one step differs from our prior work, while the orders remain unchanged for the other four steps. The activation energies of two steps differ from our prior values by 10–15 kJ/mol, and for the other three steps remain essentially consistent with our prior work. The kinetic parameters from the present work are used to predict fixed-bed reactor performance under integral operating conditions as well. The comparison between experimental and predicted values for both the prior and new sets of data is excellent and even better than our prior model (with reduced normalized RMS error = 4.2%). The kinetic analysis additionally proposed that the direct and indirect pathways of phenol formation from guaiacol HDO depend on guaiacol conversion values. The present work demonstrates that kinetic expressions and parameters obtained from a gradientless differential reactor are more reliable and can be used to successfully predict integral reactor performance data.     

Kinetic Modeling of Sunflower Oil Methanolysis Catalyzed by Calcium‐Based Catalysts

The kinetic model originally developed for quicklime‐catalyzed methanolysis of sunflower oil was tested for another three calcium‐based catalysts, namely, neat CaO, Ca(OH)₂, and CaO·ZnO. This model includes the changing reaction mechanism and the triacylglycerol (TAG) mass transfer. The applicability and generalization capability of this model for heterogeneous methanolysis reaction catalyzed by calcium‐based catalysts was evaluated. As indicated by the high coefficient of determination and the relatively small mean relative percentage deviation, the model was a reliable predictor of the time variation of TAG conversion degree in the sunflower oil methanolysis over all four calcium‐based catalysts within the ranges of the reaction conditions applied. This model is recommended in general for describing the kinetics of sunflower oil methanolysis over calcium‐based catalysts.     

Kinetic study of retro‐aldol condensation of glucose to glycolaldehyde with ammonium metatungstate as the catalyst

The kinetics of the retro‐aldol condensation of glucose to glycolaldehyde was studied in a batch reactor at 423–453 K using ammonium metatungstate (AMT) as the catalyst. Three consecutive reactions were considered: retro‐aldol condensation of glucose to erythrose and glycolaldehyde (R1), retro‐aldol condensation of erythrose to two moles of glycolaldehyde (R2), and further conversion of glycolaldehyde to side products (R3). Fitting of the experimental data showed that R1 was first‐order reaction while R2 and R3 were 1.7th‐ and 2.5th‐order reaction, respectively. Conversely, the reaction rate of R1 was 0.257th‐order dependence on the concentration of AMT catalyst. The apparent activation energies for R1, R2, and R3 were 141.3, 79.9, and 52.7 kJ/mol, respectively. The high activation energy of R1 suggests that a high temperature is favorable to the formation of glycolaldehyde. The experimental C–t curves at different temperatures and initial glucose concentrations were well predicted by the kinetic model. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3804–3813, 2014     

Reaction modeling on the phosphorous-treated Ru/Co/Zr/SiO2 Fischer-Tropsch catalyst with the estimation of kinetic parameters and hydrocarbon distribution

The catalytic performances and the kinetics model of the cobalt-based Fischer-Tropsch (FT) catalyst were investigated on Ru/Co/Zr/SiO₂ with different amounts of phosphorous. The preliminary analysis of the CO conversion, the hydrocarbon selectivity and the activation energy revealed that the 0.5 wt.% phosphorous-treated Ru/Co/Zr/SiO₂ catalyst was found to have the highest catalytic activity because of the good dispersion of the cobalt species and the suppressed aggregation during the FT reaction. Kinetics model was concomitantly developed on the selected catalyst. The model that was reported in the literature was modified in order to explain the characteristics that were observed in the experimental studies, and the kinetic parameters were estimated to fit the experimental data under various reaction conditions. The simulation results along with the estimated kinetic parameters satisfactorily predicted the effects of the operating conditions on both the CO conversion and the entire hydrocarbon distribution.     

Kinetics for phenolysis of ethyl 2‐bromoisobutyrate via phase‐transfer catalysis in a solid–liquid system

The kinetics of phase‐transfer catalyzed etherification of sodium phenoxide with ethyl 2‐bromoisobutyrate to produce ethyl 2‐phenoxyisobutyrate in a solid–liquid system has been investigated. Being catalyzed by the quaternary ‘onium salts, the reaction was carried out in a stirred batch reactor to explore the effects of various operating variables. At a temperature of 80 °C and a molar ratio of tetra‐n‐butylammonium bromide to sodium phenoxide equal to 0.372, 94% conversion was obtained after 4 h, and no other side products were observed. A kinetic model of pseudo‐first‐order reaction accompanied by catalyst deactivation was proposed to describe the overall reaction. A deactivation function was employed to evaluate the kinetic parameters. The decay of catalytic activity was mainly caused by the deposition of the salts produced on the surface of solid particles. The results show that the initial reaction rate was not influenced by the agitation rate when exceeding 350 rpm, but the deactivation rate increased with increasing stirring speed and the amount of catalyst used. The intrinsic organic reaction was conducted by the phase‐transfer catalytic intermediate. The order of reactivity for different phase‐transfer catalysts was determined as tetra‐n‐butylphosphonium bromide > tetra‐n‐butylammonium bromide > tetra‐n‐butylammonium iodide ≈ tetra‐n‐butylammonium hydrogen sulfate ≈ Aliquat 336. The apparent activation energy for tetra‐n‐butylammonium bromide was estimated as 51.4 kJ mol⁻¹. This work provides an improved method for synthesizing phenolic substances in solid–liquid phases and preventing unfavorable side reactions. © 2000 Society of Chemical Industry     

Investigation into Photocatalytic Degradation of Gaseous Benzene in a Circulated Photocatalytic Reactor (CPCR)

Due to the fact that suspended TiO₂ powder enjoys free contact with gaseous pollutant molecules in photocatalytic reactors, it can generally achieve better efficiency than immobilized TiO₂ catalysts. However, difficulties with the separation of this catalyst powder from treated pollutants and its re‐use often limit its application. Therefore, a circulated photocatalytic reactor (CPCR) was designed to enhance the performance of the photocatalytic degradation of gaseous benzene. TiO₂ film photocatalysts were prepared by the sol‐gel method at low temperatures and coated onto the inner wall of this reactor by a bonding agent composed of poly‐(2, 2‐dimethyl)‐acrylic ethylene ester emulsion in which TiO₂ powder was characterized by FTIR, TEM and SEM. In particular, the influences of initial concentration and gas flow rate of benzene on the degradation conversion, D_p, apparent reaction rate constants, k_r, initial degradation rate, r, and the deactivation and regeneration of catalyst in the CPCR, were investigated. The results indicated that the degradation conversion, apparent reaction rate constants and initial degradation rate were closely correlated to the initial concentration of benzene. To elucidate the factors governing the observations, the adsorption characteristics and kinetics of the photocatalytic degradation of benzene were analyzed using the Langmuir adsorption isotherm and Langmuir‐Hinshelwood kinetic model. It was found that the reaction kinetics were best described by a fixed pseudo‐first‐order kinetic equation of photocatalytic degradation of gaseous benzene in the CPCR.     

Electro-oxidation of ethanol and ethylene glycol on carbon-supported nano-Pt and -PtRu catalyst in acid solution

Present paper reports kinetics of electro-oxidation of ethanol (EtOH) and ethylene glycol (EG) onto Pt and PtRu nanocatalysts of different compositions in the temperature range of 298–318 K. These catalysts have been characterized by SEM, EDX, XRD, CV and amperometry. It has been observed that apparent activation energies for oxidation of EtOH and EG pass through a minimum at about 15–20 at.% of Ru in the PtRu alloy catalysts. Anodic peak current vs. composition curve also shows a maximum around this composition.The results have been explained by a geometric model, which proposes requirement of an ensemble of three Pt atoms with an adjacent Ru atom onto PtRu surface for an efficient electro-oxidation of EtOH or EG. This is further supported from statistical data analysis of probability of occurrence of such ensembles onto PtRu alloy surface.Present results also suggest that electro-oxidation of EG onto nano-PtRu catalyst surfaces follows a different path from that of EtOH at alloy composition less than 15 at.% of Ru.     

DSC curing study of catalytically synthesized maleic‐acid‐based unsaturated polyesters

Unsaturated polyesters were synthesized based on ethylene glycol and maleic acid as unsaturated dicarboxylic acid, using a variety of saturated acids in the initial acid mixture, without or with different catalysts. The curing of the polyesters produced with styrene was studied using differential scanning calorimetry (DSC) under dynamic‐ and isothermal‐heating conditions. The FTIR spectra of the initial polyesters and cured polyesters were also determined. Curing is not complete at the end of DSC scan and the unreacted bonds were quantitatively determined from the FTIR spectra and by estimation based on literature data. The value of the mean degree of conversion (α) of all double bonds (styrene unit and maleate unit) was approximately α = 0.40. Using an appropriate kinetic model for the curing exotherm of polyesters, the activation energy (E_a), the reaction order (x) and the frequency factor (k_o) were determined. Because the kinetic parameters (ie E_a, k, x) affect the kinetics in various different ways, the curves of degree of conversion versus time at various isothermal conditions are more useful to compare and characterize the curing of polyesters. The kinetic parameters are mainly influenced by the proportion of maleic acid in the polyesterification reaction mixture and secondarily by the residual polyesterification catalyst. The degree of conversion of already crosslinked polyesters is greatly increased by post‐curing them at elevated temperature and for a prolonged time. © 2002 Society of Chemical Industry     

Catalytic combustion kinetics of isopropanol over novel porous microfibrous‐structured ZSM‐5 coating/PSSF catalyst

Porous thin‐sheet cobalt–copper–manganese mixed oxides modified microfibrous‐structured ZSM‐5 coating/PSSF catalysts were developed by the papermaking/sintering process, secondary growth process, and incipient wetness impregnating method. Paper‐like sintered stainless steel fibers (PSSF) support with sinter‐locked three‐dimensional networks was built by the papermaking/sintering process, and ZSM‐5 coatings were fabricated on the surface of stainless steel fibers by the secondary growth process. Catalytic combustion performances of isopropanol at different concentrations over the microfibrous‐structured Co–Cu–Mn (1:1:1)/ZSM‐5 coating/PSSF catalysts were measured to obtain kinetics data. The catalytic combustion kinetics was investigated using power–rate law model and Mars–Van Krevelen model. It was found that the Mars–Van Krevelen model provided fairly good fits to the kinetic data. The catalytic combustion reaction occurred by interaction between isopropanol molecule and oxygen‐rich centers of modified microfibrous‐structured ZSM‐5 coating/PSSF catalyst. The reaction activation energies for the reduction and oxidation steps are 60.3 and 57.19 kJ/mol, respectively. © 2014 American Institute of Chemical Engineers AIChE J, 61: 620–630, 2015     

Synthesis of carvacrol by Friedel–Crafts alkylation of o‐cresol with isopropanol using superacidic catalyst UDCaT‐5

BACKGROUND: Alkylation of o‐cresol with propylene or isopropyl alcohol (IPA) over solid acid catalysts results in the formation of carvacrol, which finds potential applications in the synthesis of fine chemicals, intermediates, specialty chemicals, flavours and fragrances. RESULTS: The present work covers evaluation of novel mesoporous superacidic catalysts namely UDCaT‐4, UDCaT‐5 and UDCaT‐6 in the greener synthesis of carvacrol. The catalysts are modified versions of zirconia showing high catalytic activity, stability and reusability. The catalytic activity increases in the following order: UDCaT‐5 > UDCaT‐4 > UDCaT‐6 > sulfated zirconia. The process was optimized and a mathematical model developed to describe the reaction pathway in liquid phase. Carvacrol could be efficiently obtained with a selectivity up to 82% at an isopropanol conversion of 98% after 2 h over UDCaT‐5 at 180 °C. CONCLUSION: The reaction is free from any external mass transfer as well as intraparticle diffusion limitations and is intrinsically kinetically controlled. An overall second‐order kinetic equation was used to fit the experimental data. The activation energy was found to be 19.2 kcal/mol. The reaction was carried out without any solvent in order to make the process cleaner and greener. Copyright © 2009 Society of Chemical Industry