Abstract
This communication reports the kinetics analysis of ethylation of ethylbenzene (EB) with ethanol over large pore size mordenite catalysts. In this regard, two different catalyst samples are selected with SiO2/Al2O3 = 180 and 21, respectively. The higher acidic sample (SiO2/Al2O3 = 21) is desilicated to study the effects of desilication on the EB ethylation. The EB ethylation experiments are conducted in a fluidized CREC Riser Simulator using equimolar amount of EB and ethanol as feed. Under the studied reaction conditions, diethylbenzene (DEB) is the main product while a small amount of benzene and lighter gases are also produced. In addition to DEB, the higher acidic mordenite sample also produces benzene via dealkylation of EB. On the other hand, the large pore size mordenite sample gives triethylbenzene (TEB) as a secondary alkylation product. The desilicated sample shows slightly higher DEB selectivity but the EB conversion with this sample is low. Power law–based kinetics evaluation also confirms the above observations by showing low activation energy for DEB formation while high activation energies for benzene and TEB formations.
Acknowledgment
The authors would like to acknowledge the financial support by the Ministry of Higher Education, Saudi Arabia through the Center of Research Excellence in Petroleum Refining and Petrochemicals (CoRE-PRP) at King Fahd University of Petroleum and Minerals. The authors also are thankful to Mr. Mariano Gica for his support on the CREC Riser Simulator experimental runs.
List of the symbols
- Ci
concentration of specie i in the riser simulator (mol/m3)
- CL
confidence limit
- Ei
apparent activation energy of the ith reaction (kJ/mol)
- ki
apparent rate constant for the ith reaction (m3/kg of catalyst .s)
- koi
pre-exponential factor for the ith reaction after re-parameterization (m3/kg of catalyst .s)
- MWi
molecular weight of specie i
- ri
rate of reaction for species i
- R
universal gas constant (kJ/kmol K)
- t
reaction time (s)
- T
reaction temperature (K)
- To
average temperature of the experiment
- V
volume of the riser (45 cm3)
- Wc
mass of the catalyst (0.81 g)
- Whc
total mass of the hydrocarbon injected the riser (0.162 g)
- yi
mass fraction of ith component
- Greek letters
- α
apparent deactivation function
Abbreviations
- BZ
benzene
- EB
ethylbenzene
- DEB
diethylbenzene
- TEB
triethylbenzene
- EtOH
ethanol
References
1. WaziriSM, Al-KhattafS. Kinetics of ethylbenzene ethylation with ethanol over a ZSM-5 based catalyst in a riser simulator. Ind Eng Chem Res2009;48:8341–8.10.1021/ie900497dSuche in Google Scholar
2. OsmanM, HossainMM, Al-KhattafS. Kinetics study of ethylbenzene alkylation with ethanol over medium and large pore zeolites. Ind Eng Chem Res2013;52:13613–21.10.1021/ie4016717Suche in Google Scholar
3. TsaiT, LiuS, WangI. Disproportionation and transalkylation of alkylbenzenes over zeolite catalysts. Appl Catalysis A Gen1999;181:355–98.10.1016/S0926-860X(98)00396-2Suche in Google Scholar
4. ZhuZ, ChenQ, XieZ, YangW, KongD, LiC. Shape-selective disproportionation of ethylbenzene to para-diethylbenzene over ZSM-5 modified by chemical liquid deposition and MgO. J Mol Catalysis A Chem2006;248:152–8.10.1016/j.molcata.2005.10.023Suche in Google Scholar
5. VijayaraghavanVR, RajKJ. Ethylation of benzene with ethanol over substituted large pore aluminophosphate-based molecular sieves. J Mol Catalysis Chem2004;207:41–50.10.1016/S1381-1169(03)00468-0Suche in Google Scholar
6. OsmanM, AtandaL, HossainMM, Al-KhattafS. Kinetics modeling of disproportionation and ethylation of ethylbenzene over HZSM-5: effects of SiO2/Al2O3 ratio. Chem Eng J2013;222:498–511.10.1016/j.cej.2013.02.040Suche in Google Scholar
7. YadavGD, GoelPK. A new efficient catalyst UDCaT-1 for the alkylation of ethylbenzene with ethanol to diethylbenzene. Clean Technol Environ Policy2002;4:165–70.10.1007/s10098-002-0149-8Suche in Google Scholar
8. ZhirongZ, QinglingC, ZaikuX, WeiminY, DejinK, CanLi. Shape-selective disproportionation of ethylbenzene to para-diethylbenzene over ZSM-5 modified by chemical liquid deposition and MgO. J Mol Catalysis A Chem2006;248:152–8.10.1016/j.molcata.2005.10.023Suche in Google Scholar
9. WichterlovfiB, CejkaJ. A comparison of the ethylation of ethylbenzene and toluene on acid, cationic and silylated ZSM-5 zeolites. Catalysis Lett1992;16:421–9.10.1007/BF00764900Suche in Google Scholar
10. WangI, AyC, LeeB, ChenM. Para-selectivity of dialkylbenzenes over modified HZSM-5 by vapour phase deposition of silica. Appl Catalysis1989;54:257–66.10.1016/S0166-9834(00)82368-4Suche in Google Scholar
11. ChenNY. Industrial application of shape selective catalysis. Stud Surface Sci Catalysis1988;38:153–63.10.1016/S0167-2991(09)60652-2Suche in Google Scholar
12. WeberRW, MöllerKP, O’ConnorCT. The chemical vapour and liquid deposition of tetraethoxysilane on ZSM-5, mordenite and beta. Microporous Mesoporous Mater2000;35–36:533–43.10.1016/S1387-1811(99)00248-6Suche in Google Scholar
13. OdedairoT, Al-KhattafS. Comparative study of zeolite catalyzed alkylation of benzene with alcohols of different chain length: H-ZSM-5 versus mordenite. Catalysis Today2013;204:73–84.10.1016/j.cattod.2012.05.052Suche in Google Scholar
14. BhandarkarV, BhatiaS. Selective formation of ethyltoluene by alkylation of toluene with ethanol over modified HZSM-5 zeolites. Zeolites1994;14:439–49.10.1016/0144-2449(94)90170-8Suche in Google Scholar
15. SrideviU, RaoBK, PradhanNC. Kinetics of alkylation of benzene with ethanol on AlCl3-impregnated 13x zeolites. Chem Eng J2001;83:185–9.10.1016/S1385-8947(00)00253-9Suche in Google Scholar
16. de LasaHI. Riser simulator for catalytic cracking studies. U.S. Patent 5,102,628, 1992.Suche in Google Scholar
17. HossainMM, AtandaL, NabilY, Al-KhattafS. Kinetics modeling of ethylbenzene dehydrogenation to styrene over a mesoporous alumina supported iron catalyst. Chem Eng J2012;207–8:308–21.10.1016/j.cej.2012.06.108Suche in Google Scholar
18. HossainMM, de LasaHI. Chemical-looping combustion (CLC)for inherent CO2 separation-a review. Chem Eng Sci2008;63:4433–51.10.1016/j.ces.2008.05.028Suche in Google Scholar
19. HalgeriAB, JagannathD. Recent advances in selectivation of zeolites for para-disubstituted aromatics. Catalysis Today2002;73:65–73.10.1016/S0920-5861(01)00519-3Suche in Google Scholar
20. SongY-Q, FengY-L, LiuF, KangC-L, ZhouX-L, XuL-Y, et al. Effect of variations in pore structure and acidity of alkali treated ZSM-5 on the isomerization performance. J Mol Catalysis A Chem2009;310:130–7.10.1016/j.molcata.2009.06.006Suche in Google Scholar
21. GilB, MokrzyckiŁ, SulikowskiB, OlejniczakZ, WalasS. Desilication of ZSM-5 and ZSM-12 zeolites: impact on textural, acidic and catalytic properties. Catalysis Today2010;152:24–32.10.1016/j.cattod.2010.01.059Suche in Google Scholar
22. SharnappaN, PaiS, BokadeVV. Selective alkylation and disproportionation of ethylbenzene in the presence of other aromatics. J Mol Catalysis A Chem2004;217:185–91.10.1016/j.molcata.2004.03.031Suche in Google Scholar
23. Al-KhattafSS, de LasaHI. Catalytic cracking of cumene in a riser simulator: a catalyst activity decay model. Ind Eng Chem Res2001;40:5398–404.10.1021/ie001141cSuche in Google Scholar
24. MentzelUV, HøjholtKT, HolmaMS, FehrmannR, BeatoP. Conversion of methanol to hydrocarbons over conventional and mesoporous H-ZSM-5 and H-ga-MFI: major differences in deactivation behavior. App Catalysis A2012;417–418:290–7.10.1016/j.apcata.2012.01.003Suche in Google Scholar
25. TochaK, ThybautaJW, VandegehuchteaBD, NarasimhanbCS, DomokosbL, MarinGB. A single-event MICroKINETIC model for “ethylbenzene dealkylation/xylene isomerization” on pt/H-ZSM-5 zeolite catalyst. App Catalysis A2012;425–6:130–44.10.1016/j.apcata.2012.03.011Suche in Google Scholar
26. WaziriSM, AitaniAM, Al-KhattafS. Transformation of toluene and 1,2,4-trimethylbenzene over ZSM-5 and mordenite catalysts: A comprehensive kinetic model with reversibility. Ind Eng Chem Res2010;49:6376–87.10.1021/ie100527xSuche in Google Scholar
©2014 by De Gruyter
Artikel in diesem Heft
- Frontmatter
- Research Articles
- Simulation of CO Preferential Oxidation (COPrOx) Monolithic Reactors
- Simulation of a New Chemical-Looping Combustion Process without Sulfur Evolution Based on Ca-Based Oxygen Carrier
- Syngas Production from Reforming of Methane with CO2 and O2 over LaNi1–xCoxO3 Perovskites
- Investigation of the Effect of Outlet Structures on the Jet Flow Characteristics in the Circulating Jet Tank
- Transesterification of Sunflower Oil in Microreactors
- Influence of the Photoreactor Configuration and of Different Light Sources in the Photocatalytic Treatment of Highly Polluted Wastewater
- Stability and Emissions of a Lean Pre-Mixed Combustor with Rich Catalytic/Lean-burn Pilot
- Carica Papaya Seed as a Biosorbent for Removal of Cr (VI) and Ni (II) Ions from Aqueous Solution: Thermodynamics and Kinetic Analysis of Experimental Data
- Chemical Equilibrium Model and Prediction for Coal Hydrogasification
- Use of Experimental Designs to Establish a Kinetic Law for a Gas Phase Photocatalytic Process
- Application of Support Vector Machine Modeling on Phase Distribution in the Riser of an LSCFB Reactor
- Characteristics of the Bending Moment Acting on an Overhung Shaft in a Stirred Vessel
- Conversion of Glycerol into Value-Added Products Over Cu–Ni Catalyst Supported on γ-Al2O3 and Activated Carbon
- Analysis of Equilibrium Shifting by Inter-Stage Reactant Feeding in a Series of Isothermal Reactors
- Single and Multi-Channel Reactor for Oxidative Coupling of Methane
- Effect of Peak Temperature Limitations on the Design of Processes with Cooled Tubular Reactors
- Genetic Optimization of Energy Consumption of Pellet Shaft Furnace Combustor Based on Support Vector Machine (SVM)
- Effect of CuO on the Thermal Stability of Polyaniline Nanofibers
- Kinetics and Mechanism of Formaldehyde-Free Phenol-Glucose Novolac Resin Cured with an Epoxy
- Micromixing Characteristics in an Aerated Stirred Tank with Half Elliptical Blade Disk Turbine
- Application of Response Surface Methodology and Central Composite Rotatable Design for Modeling and Optimization of Catalyst Compositions in Ethanol Synthesis via CO Hydrogenation
- Accurate Measurement of the Photon Flux Received Inside Two Continuous Flow Microphotoreactors by Actinometry
- A Non-linear Inverse Problem in Estimating the Reaction Rate Function for an Annular-Bed Reactor
- Passive Microextractor with Internal Fluid Recirculation for Two Immiscible Liquids
- Oxidative Desulfurization of Dibenzothiophene by Zirconia-Based Catalysts
- Studies on Performance Analysis and Computer Aided Design of Inverse Fluidized Bed Bioreactors with Nanosupport Particles
- Modeling the Industrial Propylene–Ethylene Copolymerization FBR at Emergency Accidents
- Modelling of the Membrane Permeability Effect on the H2 Production Using CFD Method
- SBA-15 Supported Bimetallic Catalysts for Enhancement Isomers Production During n-Heptane Decomposition
- Effects of Microwave and Ultrasonic-Assisted Aging on the Synthesis of H-ZSM-5 Nanozeolite and Its Catalytic Performance in Methanol Dehydration
- Oxydehydrogenation of Ethylbenzene to Styrene: Membrane Reactor Analysis and Design
- Methanol Electrooxidation Study on Mesoporous Silica Supported Pt–Co Direct Methanol Fuel Cell Anode
- An Experimental Study of the Synthesis of Ultrafine Titania Powder in Plasmachemical Flow-Type Reactor
- Tesla Valves in Micromixers
- Kinetic Modelling of Photoconversion of Phenol by a Photo-Fenton Reagent and UV
- Overall Effectiveness Factor for Slab Geometry in a Three-Phase Reaction System
- Effect of Surface Chemistry and Structure of Sludge Particles on Their Co-slurrying Ability with Petroleum Coke
- CFD-DEM Modeling of CO2 Capture using Alkali Metal-Based Sorbents in a Bubbling Fluidized Bed
- Reaction Kinetics of Catalytic Esterification of Nonanoic Acid with Ethanol over Amberlyst 15
- Numerical and Experimental Investigation of the Effect of Geometrical Parameters on the Performance of a Contraction-Expansion Helical Mixer
- Comparative Study of Removal of Cadmium (II) and Chromium (III) Ions from Aqueous Solution Using Low-Cost Biosorbent
- Ethylation of Ethylbenzene with Ethanol over Mordenite-Based Catalysts: Effects of Acidity, Desilication and Kinetics Analysis
- A Two-Phase CFD Modeling Approach to Investigate the Flow Characteristics in Radial Flow Moving-Bed Reactors
- Esterification of Free Fatty Acids in Crude Palm Oil Using Sulfated Cobalt–Tin Mixed Oxide Catalysts
- Numerical Simulation of Chemical Stripping Process in Resid Fluid Catalytic Cracking Stripper
- Experiment on Simultaneous Absorption of NO and SO2 from Sintering Flue Gas by Oxidizing Agents of KMnO4/NaClO
- Analysis of the Simultaneous Gas–Liquid CO2 Absorption and Liquid–Gas NH3 Desorption in a Hydrometallurgical Waelz Oxides Purification Process
- Investigation on Fluidized Bed Bioreactor Treating Ice Cream Wastewater Using Response Surface Methodology and Artificial Neural Network
- Rapid Determination of the Residence Time Distribution (RTD) Function in an Oscillatory Baffled Reactor (OBR) Using a Design of Experiments (DoE) Approach
- α-Amylase Aspergillus oryzae Immobilized on Modified Expanded Perlite
- Diffusion and Equilibrium Adsorption Coefficients of Aromatic Hydrocarbon Species in Capillary Columns
- Design and Optimization of the Preparation of Calcium Carbonate from Calcium Sulfate and Ammonium Bicarbonate
- Short Communications
- Effect of Different Silicate Supports on the Catalytic Performance of MoVTeO Mixed Oxides in Partial Oxidation of Isobutane
- Liquid Flow and Mixing in Bottom Regions of Baffled and Unbaffled Vessels Agitated by Turbine-Type Impeller
- Review
- Progress in Reactors for High-Temperature Fischer–Tropsch Process: Determination Place of Intensifier Reactor Perspective
- Errata
- Erratum to Two-Dimensional Modeling of an Externally Irradiated Slurry Photoreactor
- Erratum to Photocatalytic Purification of Wastewater Polluted by Odorant Sulfur Compounds Using Titanium Oxide in a Continuous Photoreactor
Artikel in diesem Heft
- Frontmatter
- Research Articles
- Simulation of CO Preferential Oxidation (COPrOx) Monolithic Reactors
- Simulation of a New Chemical-Looping Combustion Process without Sulfur Evolution Based on Ca-Based Oxygen Carrier
- Syngas Production from Reforming of Methane with CO2 and O2 over LaNi1–xCoxO3 Perovskites
- Investigation of the Effect of Outlet Structures on the Jet Flow Characteristics in the Circulating Jet Tank
- Transesterification of Sunflower Oil in Microreactors
- Influence of the Photoreactor Configuration and of Different Light Sources in the Photocatalytic Treatment of Highly Polluted Wastewater
- Stability and Emissions of a Lean Pre-Mixed Combustor with Rich Catalytic/Lean-burn Pilot
- Carica Papaya Seed as a Biosorbent for Removal of Cr (VI) and Ni (II) Ions from Aqueous Solution: Thermodynamics and Kinetic Analysis of Experimental Data
- Chemical Equilibrium Model and Prediction for Coal Hydrogasification
- Use of Experimental Designs to Establish a Kinetic Law for a Gas Phase Photocatalytic Process
- Application of Support Vector Machine Modeling on Phase Distribution in the Riser of an LSCFB Reactor
- Characteristics of the Bending Moment Acting on an Overhung Shaft in a Stirred Vessel
- Conversion of Glycerol into Value-Added Products Over Cu–Ni Catalyst Supported on γ-Al2O3 and Activated Carbon
- Analysis of Equilibrium Shifting by Inter-Stage Reactant Feeding in a Series of Isothermal Reactors
- Single and Multi-Channel Reactor for Oxidative Coupling of Methane
- Effect of Peak Temperature Limitations on the Design of Processes with Cooled Tubular Reactors
- Genetic Optimization of Energy Consumption of Pellet Shaft Furnace Combustor Based on Support Vector Machine (SVM)
- Effect of CuO on the Thermal Stability of Polyaniline Nanofibers
- Kinetics and Mechanism of Formaldehyde-Free Phenol-Glucose Novolac Resin Cured with an Epoxy
- Micromixing Characteristics in an Aerated Stirred Tank with Half Elliptical Blade Disk Turbine
- Application of Response Surface Methodology and Central Composite Rotatable Design for Modeling and Optimization of Catalyst Compositions in Ethanol Synthesis via CO Hydrogenation
- Accurate Measurement of the Photon Flux Received Inside Two Continuous Flow Microphotoreactors by Actinometry
- A Non-linear Inverse Problem in Estimating the Reaction Rate Function for an Annular-Bed Reactor
- Passive Microextractor with Internal Fluid Recirculation for Two Immiscible Liquids
- Oxidative Desulfurization of Dibenzothiophene by Zirconia-Based Catalysts
- Studies on Performance Analysis and Computer Aided Design of Inverse Fluidized Bed Bioreactors with Nanosupport Particles
- Modeling the Industrial Propylene–Ethylene Copolymerization FBR at Emergency Accidents
- Modelling of the Membrane Permeability Effect on the H2 Production Using CFD Method
- SBA-15 Supported Bimetallic Catalysts for Enhancement Isomers Production During n-Heptane Decomposition
- Effects of Microwave and Ultrasonic-Assisted Aging on the Synthesis of H-ZSM-5 Nanozeolite and Its Catalytic Performance in Methanol Dehydration
- Oxydehydrogenation of Ethylbenzene to Styrene: Membrane Reactor Analysis and Design
- Methanol Electrooxidation Study on Mesoporous Silica Supported Pt–Co Direct Methanol Fuel Cell Anode
- An Experimental Study of the Synthesis of Ultrafine Titania Powder in Plasmachemical Flow-Type Reactor
- Tesla Valves in Micromixers
- Kinetic Modelling of Photoconversion of Phenol by a Photo-Fenton Reagent and UV
- Overall Effectiveness Factor for Slab Geometry in a Three-Phase Reaction System
- Effect of Surface Chemistry and Structure of Sludge Particles on Their Co-slurrying Ability with Petroleum Coke
- CFD-DEM Modeling of CO2 Capture using Alkali Metal-Based Sorbents in a Bubbling Fluidized Bed
- Reaction Kinetics of Catalytic Esterification of Nonanoic Acid with Ethanol over Amberlyst 15
- Numerical and Experimental Investigation of the Effect of Geometrical Parameters on the Performance of a Contraction-Expansion Helical Mixer
- Comparative Study of Removal of Cadmium (II) and Chromium (III) Ions from Aqueous Solution Using Low-Cost Biosorbent
- Ethylation of Ethylbenzene with Ethanol over Mordenite-Based Catalysts: Effects of Acidity, Desilication and Kinetics Analysis
- A Two-Phase CFD Modeling Approach to Investigate the Flow Characteristics in Radial Flow Moving-Bed Reactors
- Esterification of Free Fatty Acids in Crude Palm Oil Using Sulfated Cobalt–Tin Mixed Oxide Catalysts
- Numerical Simulation of Chemical Stripping Process in Resid Fluid Catalytic Cracking Stripper
- Experiment on Simultaneous Absorption of NO and SO2 from Sintering Flue Gas by Oxidizing Agents of KMnO4/NaClO
- Analysis of the Simultaneous Gas–Liquid CO2 Absorption and Liquid–Gas NH3 Desorption in a Hydrometallurgical Waelz Oxides Purification Process
- Investigation on Fluidized Bed Bioreactor Treating Ice Cream Wastewater Using Response Surface Methodology and Artificial Neural Network
- Rapid Determination of the Residence Time Distribution (RTD) Function in an Oscillatory Baffled Reactor (OBR) Using a Design of Experiments (DoE) Approach
- α-Amylase Aspergillus oryzae Immobilized on Modified Expanded Perlite
- Diffusion and Equilibrium Adsorption Coefficients of Aromatic Hydrocarbon Species in Capillary Columns
- Design and Optimization of the Preparation of Calcium Carbonate from Calcium Sulfate and Ammonium Bicarbonate
- Short Communications
- Effect of Different Silicate Supports on the Catalytic Performance of MoVTeO Mixed Oxides in Partial Oxidation of Isobutane
- Liquid Flow and Mixing in Bottom Regions of Baffled and Unbaffled Vessels Agitated by Turbine-Type Impeller
- Review
- Progress in Reactors for High-Temperature Fischer–Tropsch Process: Determination Place of Intensifier Reactor Perspective
- Errata
- Erratum to Two-Dimensional Modeling of an Externally Irradiated Slurry Photoreactor
- Erratum to Photocatalytic Purification of Wastewater Polluted by Odorant Sulfur Compounds Using Titanium Oxide in a Continuous Photoreactor