Acid ion-exchange resins catalysts for the liquid-phase dimerization/etherification of isoamylenes in methanol or ethanol presence

Cruz, V.; Izquierdo, J.F.; Cunill, Fidel; Tejero, Javier; Iborra, Montserrat; Fité, Carles

doi:10.1016/j.reactfunctpolym.2005.01.011

Cited by 42 publications

(44 citation statements)

References 36 publications

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“…As observed in Figure 9a, when C4 dimers were forms, the TMP-1/TMP-2 molar ratio was around 4 at the end of runs, consistent with published results [47] and with the thermodynamic equilibrium constant for trimethylpentenes isomerization (R10), which are in the range from 0.26 to 0.29 for the assayed temperatures [31]. From IA dimerization (R12 in Figure 1), a wide variety of diisoamylenes can be formed [49]. Additionally, codimerization between IB and IA (R11 in Figure 1) also occurred.…”

Section: Dimers and Codimers Formationsupporting

confidence: 89%

Equilibrium conversion, selectivity and yield optimization of the simultaneous liquid-phase etherification of isobutene and isoamylenes with ethanol over Amberlyst™ 35

Fité

Ramírez

Cunill

2016

Fuel Processing Technology

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A prospective study on the product distribution at chemical equilibrium for the simultaneous liquid-phase etherification of isobutene and isoamylenes with ethanol over Amberlyst TM 35 is presented. Experiments were performed isothermally in a 200 cm 3 stirred tank batch reactor operating at 2.0 MPa. Initial molar ratios of alcohol/olefins and isobutene/isoamylenes ranged both from 0.5 to 2, and temperature from 323 to 353 K. Reactants equilibrium conversion, selectivities and yields toward products were clearly affected by the experimental conditions. Experimental etherification yields have been modeled using the response surface methodology (RSM), combined with the stepwise regression method to include only the statistically significant variables into the model. The multiobjective optimization (MOO) of etherification yields has been carried out numerically, by means of the desirability functions approach, and graphically, by using the overlaid contour plots (OCP).Optimal conditions for the simultaneous production of ethyl tert-butyl ether (ETBE) and tertamyl ethyl ether (TAEE) have been found to be at low temperatures (323 to 337 K) and initial molar ratio alcohol/olefins close to 0.9 and isobutene/isoamylenes close to 0.5. 2

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Section: Dimers and Codimers Formationsupporting

confidence: 89%

Equilibrium conversion, selectivity and yield optimization of the simultaneous liquid-phase etherification of isobutene and isoamylenes with ethanol over Amberlyst™ 35

Fité

Ramírez

Cunill

2016

Fuel Processing Technology

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“…The reactor pressure was kept with nitrogen at 2.0 MPa to maintain the liquid phase over the reaction. More detailed information about the experimental setup is described elsewhere (Cruz et al, 2005). …”

Section: Methodsmentioning

confidence: 99%

Equilibrium of the simultaneous etherification of isobutene and isoamylenes with ethanol in liquid-phase

Fité

Ramírez

Cunill

2014

Chemical Engineering Research and Design

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ARTICLE IN PRESS CHERD-1418; No. of Pages 13 chemical engineering research and design x x x ( 2 0 1 3 ) xxx-xxx ethyl tert-butyl ether formation, tert-amyl ethyl ether formation from isoamylenes (2-methyl-1-butene and 2-methyl-2-butene) and isomerization reaction between both isoamylenes. Equilibrium data were obtained in a batchwise IntroductionIn order to reduce hazardous and evaporative gasoline exhausts and from refueling emissions, as well as their environmental impact at the time that engines energetic efficiency is enhanced, new legislation and major efforts have been devoted to fuel reformulation. The European Directive 2009/28/EC promotes the usage of combustibles from renewable resources, such as bioethanol, and the directive 2009/30/EC establishes the main guidelines related to fuel reformulation.As it is well known, olefins of the C 5 fraction from oil, mainly the reactive isoamylenes (IA) 2-methyl-1-butene (2M1B) and 2-methyl-2-butene (2M2B), present some disadvantages as components of a gasoline, particularly in tropical zones. This is because these are the olefins with the highest * Corresponding author. Tel.: +34 934034769; fax: +34 934021291. E-mail addresses: rsotolop7@alumnes.ub.edu (R. Soto), fite@ub.edu (C. Fité), eliana.ramirez-rangel@ub.edu (E. Ramírez), rogerbringue@ub.edu (R. Bringué), fcunill@ub.edu (F. Cunill).Received 25 Reid vapor pressure (RVP), the highest atmospheric reactivity, the highest potential of tropospheric ozone formation (around 90%) and these are the largest amount of the olefins present in a gasoline (above 25 wt.% of the C 5 fraction from fluid catalytic cracking, FCC) (Rock et al., 1992). Thus, to diminish the impact of their use as fuel components on the environment, the reduction of the content of these compounds by means of either its etherification with primary alcohols or via oligomerization would result in a more suitable alternative than the reduction of the total olefin content of a gasoline. Oxygenated compounds have been gradually gaining importance in the gasoline market since lead compounds were banned as octane enhancers. The two main types of oxygenates used as high octane additives are alcohols and ethers. Among alcohols, the most widely used is ethanol (EtOH), whereas the main tertiary ethers are methyl tert-buty ether

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“…The higher conversion of C6 olefins with ethanol over that with methanol also has been previously observed by Rihko and Krause [57]. These contrasting results might be explained by the study of Cruz et al [69]. They declared that ethanol can react with alkenes easier than methanol due to the higher acidity of ethanol.…”

Section: Gasoline Composition and Reaction Activitiesmentioning

confidence: 71%

Self-Etherification Process for Cleaner Fuel Production

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The process of fluidized catalytic cracking (FCC) gasoline self-etherification with ethanol has several benefits. Firstly, the gasoline volume is effectively increased by adding ethers produced from ethanol which is renewable. Secondly, the etherified gasoline product has higher octane number with lower blending Reid vapor pressure (bRvp) and amount of olefins content. Two catalysts; i.e., Amberlyst 16 and Beta-zeolite are used for etherification in this study. The bRvp of etherified FCC gasoline is lower than that of ethanol direct blend gasoline (called gasohol) and also could be lower than that of original FCC gasoline with moderate ethanol conversion. However, the octane number of etherified FCC gasoline catalyzed by Amberlyst 16 is slightly lower than that of gasohol. Beta-zeolite is a more suitable catalyst than Amberlyst 16 for the etherification of FCC gasoline with ethanol because not only a better catalytic activity for etherification, but some isomerization also occurs without aromatization. Therefore it offers improved gasoline products with higher research octane number and gasoline renewability with lower bRvp than that of gasohol. Olefins and ethanol conversions increase with increasing ethanol ratio in feed. Nevertheless, ethanol feed ratio is limited specification of distillation temperatures which are dependent on the evaporation of ethanol and its amount. The cold start problem might not be occurred even in low bRvp as proven by satisfied drivability index.

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Acid ion-exchange resins catalysts for the liquid-phase dimerization/etherification of isoamylenes in methanol or ethanol presence

Cited by 42 publications

References 36 publications

Equilibrium conversion, selectivity and yield optimization of the simultaneous liquid-phase etherification of isobutene and isoamylenes with ethanol over Amberlyst™ 35

Equilibrium conversion, selectivity and yield optimization of the simultaneous liquid-phase etherification of isobutene and isoamylenes with ethanol over Amberlyst™ 35

Equilibrium of the simultaneous etherification of isobutene and isoamylenes with ethanol in liquid-phase

Self-Etherification Process for Cleaner Fuel Production

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