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Reliability of the synthesis of C10–C16 linear ethers from 1-alkanols over acidic ion-exchange resins

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Abstract

More-than-nine-carbon-atom-containing linear ethers such as ethyl octyl ether (EOE), di-n-pentyl ether (DNPE), di-n-hexyl ether (DNHE) or di-n-octyl ether (DNOE) increase the quality of the diesel blends making them environmentally friendly. In this work, dehydration of 1-pentanol, 1-hexanol and 1-octanol to DNPE, DNHE and DNOE, respectively, as well as the reaction between 1-octanol and ethanol to give EOE are shown to be a good path for obtaining these linear ethers. Acidic macroreticular and gel-type polystyrene-divinylbenzene (PS-DVB) ion-exchange resins have been tested as catalysts for these reactions in liquid phase at 423 K. In the dehydration reactions of 1-pentanol, 1-hexanol and 1-octanol, as a rule, selectivity to linear ether decreased with the length of the ether over macroreticular resins of high and medium DVB%. On the contrary, no differences in selectivity to DNPE, DNHE and DNOE were observed over gel-type and macroreticular resins of low DVB%. In the reaction for obtaining EOE from ethanol and 1-octanol, EOE synthesis competes with those of DNOE and diethyl ether. The best selectivity to EOE and DNOE were found in gel-type and macroreticular resins of low DVB% too. Swelling of the resin in the polar reaction medium was found to be a decisive factor to enhance the selectivity to long linear ethers. Therefore, Amberlyst 121 and CT 224 are proposed to catalyze the synthesis of these ethers; Amberlyst 70 is suggested as the best one for working above 423 K.

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Abbreviations

DEE:

Diethyl ether

DNBE:

Di-n-butyl ether

DNHE:

Di-n-hexyl ether

DNOE:

Di-n-octyl ether

DNPE:

Di-n-pentyl ether

DVB:

Divinylbenzene

EOE:

Ethyl octyl ether

EtOH:

Ethanol

HeOH:

Hexanol

[H+]:

Acid capacity (meq H+/g)

ISEC:

Inverse steric exclusion chromatography

n :

Moles

\( n_{\text{HeOH}}^0 \) :

Initial moles of 1-hexanol

\( n_{\text{OcOH}}^0 \) :

Initial moles of 1-octanol

\( n_{\text{PeOH}}^0 \) :

Initial moles of 1-pentanol

\( n_{\text{ROH}}^0 \) :

Initial moles of 1-alkanol

OcOH:

Octanol

PeOH:

Pentanol

PS-DVB:

Polystyrene-divinylbenzene

S :

Selectivity (% mol/mol)

t :

Time (h)

T :

Temperature (K)

T max :

Maximum operation temperature (K)

X :

Conversion (% mol/mol)

Y :

Yield (% mol/mol)

Y′:

Yield (% g/g)

V :

Volume (cm3)

W :

Dry catalyst mass (g)

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Acknowledgements

Financial support was provided by the Science and Education Ministry of Spain (project CTQ2007-60691/PPQ and CTQ2010-16047). The authors thank Rohm and Haas France and Purolite for providing Amberlyst and CT ion-exchange resins, respectively. We thank also Dr. Karel Jerabek of Institute of Chemical Process Fundamentals (Prague, Czech Republic) for the structural and textural analysis made by the ISEC method.

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Authors and Affiliations

  1. Department of Chemical Engineering, University of Barcelona, C/Martí i Franquès 1, 08028, Barcelona, Spain

    C. Casas, J. Guilera, E. Ramírez, R. Bringué, M. Iborra & J. Tejero

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  1. C. Casas
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Correspondence to J. Tejero.

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Casas, C., Guilera, J., Ramírez, E. et al. Reliability of the synthesis of C10–C16 linear ethers from 1-alkanols over acidic ion-exchange resins. Biomass Conv. Bioref. 3, 27–37 (2013). https://doi.org/10.1007/s13399-012-0051-5

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