Enhancing MTBE rate equation by considering reaction medium influence

Fité, Carles; Tejero, Javier; Iborra, Montserrat; Izquierdo, J.F.

doi:10.1002/aic.690441016

Cited by 23 publications

(25 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For models were kDT was significant, its value was lower than 0.1 MPa 1/2 K -1 , which is comparable with that determined in previous kinetic studies using a similar catalyst [14].…”

Section: Modeling Resultssupporting

confidence: 74%

“…It has been reported that it follows a linear dependence with temperature in the assayed temperature range [14], and similarly to the solubility parameter dependency of pure species.…”

Section: 11 Expmentioning

confidence: 99%

“…The inclusion of ψ in the kinetic equation has been proved to enhance the prediction of the reaction rate equation for similar systems [14,28]. In Eq.…”

Section: 1 Kinetic Equationsmentioning

confidence: 99%

“…Further progress was made by Oktar et al [10] and Zhang et al [1] concerning TAEE formation reactions. The influence of the reaction medium on etherification reactions was also studied [7,[11][12][13][14], and adsorption equilibrium and also kinetic parameters were estimated [15]. More recently, reviews on ETBE [16] and TAEE [17] isolated syntheses gathered the main progresses and the future prospects for the synthesis of these ethers.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Kinetic modeling of the simultaneous etherification of ethanol with C4 and C5 olefins over Amberlyst™ 35 using model averaging

Fité

Ramírez

Bringué

et al. 2017

Chemical Engineering Journal

Self Cite

View full text Add to dashboard Cite

Graphical abstract Highlights Model averaging provides the kinetic model taking into account model uncertainty  ETBE is formed faster than TAEE in the simultaneous etherification  Reactions mechanism is deduced from the proposed kinetic model  Active sites are mainly occupied by adsorbed ethanol, ETBE and TAEE  Two active sites participate in etherification reactions, and one in isomerization AbstractA kinetic study on the simultaneous liquid-phase etherification of ethanol with isobutene (IB), 2-methyl-1-butene (2M1B) and 2-methyl-2-butene (2M2B) catalyzed by Amberlyst™ 35 to form ethyl tert-butyl ether (ETBE) and tert-amyl ethyl ether (TAEE) is presented. Isothermal experimental runs were carried out in a stirred tank batch reactor in the temperature range 323-353 K at 2.0 MPa, starting from different initial concentrations. Obtained reaction rates were free of catalyst load, internal, and external mass transfer effects. Mathematical fitting of a series 2 of systematically originated models, model selection, and model averaging procedures were applied to find the best model and to draw conclusions about the reaction mechanism. The selected model involves a saturated catalytic surface with the participation of two active sites in etherification reactions and one active site in isoamylenes isomerization. Apparent activation energies for ETBE formation from IB and EtOH, TAEE formation from 2M1B and EtOH, TAEE formation from 2M2B and EtOH, and double bond isomerization between 2M1B and 2M2B were 72.8±1.4, 74.9±2.8, 81.2±2.2 and, 76.5±7.2 kJ/mol, respectively. The alkenes with the double bond in terminal position were more reactive towards EtOH than 2M2B, with the double bond in internal position.

show abstract

“…For models were kDT was significant, its value was lower than 0.1 MPa 1/2 K -1 , which is comparable with that determined in previous kinetic studies using a similar catalyst [14].…”

Section: Modeling Resultssupporting

confidence: 74%

“…It has been reported that it follows a linear dependence with temperature in the assayed temperature range [14], and similarly to the solubility parameter dependency of pure species.…”

Section: 11 Expmentioning

confidence: 99%

“…The inclusion of ψ in the kinetic equation has been proved to enhance the prediction of the reaction rate equation for similar systems [14,28]. In Eq.…”

Section: 1 Kinetic Equationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Kinetic modeling of the simultaneous etherification of ethanol with C4 and C5 olefins over Amberlyst™ 35 using model averaging

Fité

Ramírez

Bringué

et al. 2017

Chemical Engineering Journal

Self Cite

View full text Add to dashboard Cite

show abstract

“…An attempt to take this phenomenum into account has been the use of the Hildebrand solubility parameter to characterize the influence of the reaction medium on the catalytic activity. The parameter is directly related to the swelling and to the accessibility of the active sites [7]. Another approach has been to describe the equilibrium between the polymer phase and the liquid phase through the extended Flory-Huggins theory [8].…”

Section: Introductionmentioning

confidence: 99%

Simultaneous Isomerization and Etherification of Isoamylenes with Methanol

Kiviranta-Pääkkönen¹,

Krause²

2003

Chem Eng & Technol

View full text Add to dashboard Cite

The effect of feed MeOH/2M1B molar ratio on the initial isomerization and etherification rates of 2-methyl-1-butene (2M1B) was studied in a batch reactor. The initial reaction rates for etherification and isomerization increased when the MeOH/2M1B molar ratio decreased. The ratio of etherification and isomerization rate was 2±3 until at lowest initial MeOH/2M1B molar ratio 0.2, where the isomerization rate increased significantly. At MeOH/2M1B molar ratio 0.2 the isomerization reaction rate was twice as high as the etherification reaction rate. Several kinetic formulations were tested to explain this new data and the data obtained in earlier studies. According to the statistics, a kinetic model based on three active sites gave the best fit, but it was discussed that the basic Langmuir-Hinshelwood mechanism might be more adequate. An improved fit of the LangmuirHinshelwood model was obtained, when a correction factor describing the acceleration of isomerization rate with the molar fraction of 2M1B was added into the kinetic equations.

show abstract

Kinetics of the liquid phase dehydration of 1‐octanol to di‐n‐octyl ether on Amberlyst 70

et al. 2017

Self Cite

View full text Add to dashboard Cite

The kinetics of the liquid phase dehydration of 1-octanol to di-n-octyl ether (DNOE) over Amberlyst 70 was studied at 413-453K. Mechanistic rate models assuming water and 1-octanol adsorbed on the resin, and the free sites fraction negligible, were selected from 1-octanol dehydration experiments.Next, the influence of DNOE, water and 1,4-dioxane (solvent) concentration was evaluated. DNOE and 1,4-dioxane do not affect significantly the reaction rate, while water inhibits it strongly. Water effect was quantified by splitting the rate constant into a "true one" and a correction factor related to the fraction of active sites blocked by water. The best kinetic model stemmed from an Eley-Rideal mechanism with water adsorbed onto the resin and DNOE released directly to the liquid phase, with a correction factor for water inhibitory effect based on a Freundlich isotherm-like function; activation energy being 110±5 kJ·mol -1 based in line with literature data on homologous reactions.

show abstract

Enhancing MTBE rate equation by considering reaction medium influence

Cited by 23 publications

References 17 publications

Kinetic modeling of the simultaneous etherification of ethanol with C4 and C5 olefins over Amberlyst™ 35 using model averaging

Kinetic modeling of the simultaneous etherification of ethanol with C4 and C5 olefins over Amberlyst™ 35 using model averaging

Simultaneous Isomerization and Etherification of Isoamylenes with Methanol

Kinetics of the liquid phase dehydration of 1‐octanol to di‐n‐octyl ether on Amberlyst 70

Contact Info

Product

Resources

About