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.
Similar content being viewed by others
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)
References
Nylund NO, Aakko P, Niemi S, Paanu T, Berg R (2005) Alcohols and ethers as oxygenates in diesel fuel. IEA Advanced Motor Fuels Annex XXVI
Pecci GC, Clerici MG, Giavazzi F, Ancillotti F, Marchiona M, Patrini (1991) Oxygenated diesel fuels-structure and properties correlation. Proc IX Int Symp Alcohols Fuels (ISAF, Firenze) 1:321–335
Olah GA (1996) Cleaner burning and cetane enhancing diesel fuel supplements. US Patent US5520710A
Ndou AS, Plint N, Coville NJ (2003) Dimerisation of ethanol to butanol over solid-base catalysts. App Catal A Gen 251:337–345
Tsuchida T, Sakuma S, Takeguchi T, Ueda W (2006) Direct synthesis of n-butanol from ethanol over nostoichiometric hydroxyapatite. Ind Eng Chem Res 45:8634–8642
Dekishima Y, Lan EI, Shen CR, Cho KM, Liao JCJ (2011) Extending carbon chain length of 1-butanol pathway for 1-hexanol synthesis from glucose by engineered Escherichia coli. J Am Chem Soc 133:11399–11401
Shen CR, Lan EI, Dekishima Y, Baez A, Cho KM, Liao JC (2011) Driving forces enable high-titer anaerobic 1-butanol synthesis in Escherichia coli. Appl Environ Microbiol 77:2905–2915
Hansen AC, Zhanga Q, Lyne PWL (2005) Ethanol–diesel fuel blends—a review. Bioresour Technol 96:277–285
Kwanchareon P, Luengnaruemitchai A, Jai-Inb S (2007) Solubility of a diesel–biodiesel–ethanol blend, its fuel properties, and its emission characteristics from diesel engine. Fuel 86:1053–1061
Norris JF, Rigby GW (1932) The reactivity of atoms and groups in organic compounds. J Am Chem Soc 54:2088–2100
Corma A, García H (2008) Crossing the borders between homogeneous and heterogeneous catalysis: develo** recoverable and reusable catalytic systems. Top Catal 48:8–31
Siril PF, Gross HE, Brown DR (2008) New polystyrene sulfonic acid resin catalysts with enhanced acidic and catalytic properties. J Mol Catal A Chem 279:63–68
Dow website: www.dow.com. Accessed 20 January 2012
Purolite website: www.purolite.com. Accessed 20 January 2012
Tejero J, Cunill F, Iborra M, Izquierdo JF, Fité C (2002) Dehydration of 1-pentanol to di-n-pentyl ether over ion-exchange resin catalysts. J Mol Catal A Chem 182–183:541–554
Bringué R, Tejero J, Iborra M, Izquierdo JF, Fité C, Cunill F (2007) Water effect on the kinetics of 1-pentanol dehydration to di-n-pentyl ether (DNPE) on Amberlyst 70. Top Catal 45:181–186
Medina E, Bringué R, Tejero J, Iborra M, Fité C (2010) Conversion of 1-hexanol to di-n-hexyl ether on acidic catalysts. Appl Catal A Gen 374:41–47
Casas C, Bringué R, Ramírez E, Iborra M, Tejero J (2011) Liquid-phase dehydration of 1-octanol, 1-hexanol and 1-pentanol to linear symmetrical ethers over ion exchange resins. Appl Catal A Gen 396:129–139
Pros S (2009) Ethyl octyl ether synthesis over acidic ion-exchange resins. Ms. Ch. Eng. Thesis, University of Barcelona
Kiviranta-Pääkkönen PK, Struckmann LK, Linnekoski JA, Krause AOI (1998) Dehydration of the alcohol in the etherification of isoamylenes with methanol and ethanol. Ind Eng Chem Res 37:18–24
dos Reis SCM, Lachter ER, Nascimento RSV, Rodrigues JA, Reid MG (2005) Transesterification of Brazilian vegetable oils with methanol over ion-exchange resins. J Am Oil Chem Soc 82:661–665
Honkela ML, Root A, Lindbland M, Outi A, Krause I (2005) Comparison of ion-exchange resin catalysts in the dimerisation of isobutene. Appl Catal A Gen 295:216–223
Kapila D et al (2005) Methods for preparing cycloalkylidene bisphenols.US Patent US2005/0137428A1
Jerabek K (1996) Cross evaluation of strategies in size-exclusion chromatography. ACS Symp Ser 635:211
Ogston AG (1958) The spaces in a uniform random suspension of fibers. Trans Faraday Soc 54:1754
Jerabek K, Holub L (2009) Working state morphology of ion exchange catalysts and its influence on reaction kinetics. 13th Int IUPAC Conf on Polym Organic Chem
Medina E, Bringué R, Tejero J, Iborra M, Fité C, Izquierdo JF, Cunill F (2007) Dehydrocon-densation of 1-hexanol to di-n-hexyl ether (DNHE) on Amberlyst 70. Proc. 6th European Conf. Chem. Eng. Copenhagen. www.nt.ntnu.no/users/skoge/prost/proceedings/ecce6_sep07/upload/1686.pdf
Bringué R, Iborra M, Tejero J, Izquierdo JF, Cunill F, Fité C, Cruz VJ (2006) Thermally stable ion-exchange resins as catalysts for the liquid phase dehydration of 1-pentanol to di-n-pentyl ether (DNPE). J Catal 244:33–42
Harvey BG, Meylemans HA (2011) The role of butanol in the development of sustainable fuel technologies. J Chem Technol Biotechnol 86:2–9
Dogu T, Varisli D (2007) Alcohols as alternatives to petroleum for environmentally clean fuels and petrochemicals. Turk J Chem 31:551–567
Llorente X, Tejero J, Iborra M, Bringué B, Cunill F, Izquierdo JF, Fité C (2009) Conversión de 1-octanol a di-n-octil éter sobre resinas ácidas con eliminación simultánea de agua. 9th SECAT Congress. Ciudad Real
Petrus L, Stamhuis EH, Joosten EH (1981) Thermal deactivation of strong-acid ion-exchange resin in water. Ind Eng Chem Prod Res Dev 20:366–71
Bothe N, Döscher F, Klein J, Widdecke H (1979) Thermal stability of sulfonated styrene-divinylbenzene resins. Polymer 20:850–54
Alonso DM, Bond JQ, Serrano-Ruiz JC, Dumesic JA (2010) Production of liquid hydrocarbon transportation fuels by oligomerization of biomass-derived C9 alkenes. Green Chem 12:992–999
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.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
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
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13399-012-0051-5