BUHAR FAZINDA ETİL TERSİYER BÜTİL ETER (ETBE) SENTEZİNDE KULLANILAN POLİHEMA BAZLI SİLİKOTUNGSTİK ASİT KATALİZÖRLER
Yıl 2012,
Cilt: 27 Sayı: 3, 0 - , 19.02.2013
Levent Değirmenci
Nuray Oktar
Öz
PoliHEMA-Silikotungstik asit katalizörlerin (PH-STA) aktivitesi buhar fazında, 353-373K sıcaklık aralığında,isobüten/etanol (IB/EtOH) mol oranının 0,17 olduğu reaksiyon koşullarında gerçekleştirilen ETBE üretimi içinincelenmiştir. Çalışmada sentezlenen katalizörler varlığında IB’nin ETBE’ye dönüşümü denge dönüşümdeğerine yakın bulunmuştur. PH-STA’nın (25/75 v/v HEMA/EGDMA) 373K sıcaklık değerinde gerçekleştirilenaktivite deneyleri sonucunda dönüşüm 0,17 olarak elde edilmiştir. Belirtilen dönüşüm değerine katalizördekiaktif madde miktarı (STA) ağırlıkça %8 varlığında ulaşılmıştır. Söz konusu dönüşüm değeri öncekiçalışmalarımızda saf STA katalizörü ile elde edilen dönüşüm değerinden daha yüksektir. Katalizör dayanımıetanol ile işlem görmüş PH-STA katalizörler ile gerçekleştirilen deneyler ile test edilmiştir. TGA analizi ilesentezlenen katalizörlerin moleküler yapısının sıcaklıkla değişimi incelenmiştir. PoliHEMA’nın camsı geçişsıcaklığı (Tg) DSC analizi sonucunda 136 °C olarak belirlenmiştir. PoliHEMA ve PH-STA katalizörlerine aitFTIR ve XPS analizleri polimer yapısının oluşumunu ve yapıdaki STA’nın varlığını göstermektedir.Katalizörlerin asidik karakteri gerçekleştirilen DRIFTS analizi ile belirlenmiştir.
Kaynakça
- Kharoune, M., Pauss, A. and Lebeault, M., J.,
- “Aerobic biodegradation of an oxygenates
- mixture: ETBE, MTBE and TAME in an
- Upflow Fixed-Bed Reactor”, Wat. Res., 35 (7),
- -1674, 2001.
- Manzini, F., “Inserting renewable fuels and
- technologies for transport in Mexico City
- Metropolitan Area”, International Journal of
- Hydrogen Energy, 31, 327-335, 2006.
- Malça, J., Freire, F., “Renewability and lifecycle
- energy efficiency of bioethanol and bioethyl
- tertiary-butyl ether (bioETBE): Assesing
- the implications of allocation”, Energy, 31,
- -3380, 2006.
- Oktar, N., Murtezaoglu, K., Dogu, G.,
- Gonderten, I., Dogu, T., “Etherification Rates of
- -Methyl 2-Butane and 2-Methyl-1- Butene
- with Ethanol for Environmentally Clean
- Gasoline Production”, J. Chem. Tech.
- Biotech., 74, 155-161, 1999.
- Oktar, N., Murtezaoglu, K., Dogu, T., Dogu, G.,
- “Dynamic analysis of adsorption equilibrium
- and rate parameters of reactants and products in
- MTBE, ETBE and TAME production”, Can. J.
- Chem. Eng., 77, 406-412, 1999.
- Boz, N., Dogu, T., Murtezaoglu, K., Dogu, G.,
- “Effect of Hydrogen Ion-Exchange Capacity on
- Activity of Resin Catalysts in Tert-amyl-ethylether
- Synthesis”, Appl. Catal. A: General, 268,
- -182, 2004.
- Dogu, T., Boz, N., Aydin, E., Oktar, N.,
- Murtezaoglu, K., Dogu, G., “DRIFTS Studies
- for the Reaction and Adsorption of Alcohols
- and Isobutylene on Acidic Resin Catalysts and
- the Mechanism of ETBE and MTBE Synthesis”,
- Industrial & Engineering Chemistry
- Research, 40, 23, 5044-5051, 2001.
- Boz, N., Doğu, T., Mürtezaoğlu, K., Doğu, G.,
- “Mechanism of TAME and TAEE synthesis
- from diffuse-reflectance FTIR analysis”,
- Catalysis Today, 100, 419-424, 2005.
- Degirmenci, L., Oktar, N., Dogu, G., “Product
- Distributions in Ethyl- tert-Butyl-Ether
- Synthesis over Different Solid Acid Catalysts”,
- Ind. Eng. Chem. Res., 48, 5, 2566-2576, 2009.
- Degirmenci, L., Oktar, N., Dogu, G., “ETBE
- Synthesis Over Silicotungstic Acid and
- Tungstophosphoric Acid Catalysts Calcined at
- Different Temperatures”, Fuel Processing
- Technology, 91, 737-742, 2010.
- Degirmenci, L., Oktar, N., Dogu, G., “Activated
- Carbon Supported Silicotungstic Acid Catalysts
- for ETBE Synthesis” AIChE Journal.
- DOI: 10,1002/aic.12524, 2011.
- Li, G., Dong, Y., Wang, J., Wang, X., Suo, J.,
- “New progress of Keggin and Wells-Dawson
- type polyoxometalates catalyze acid and
- oxidative reactions”, Journal of Molecular
- Catalysis A: Chemical, 262, 67-76, 2007.
- Cavani, F., “Heteropolycompund-based
- catalysts: A blend of acidic and oxidizing
- properties”, Catalysis Today, 41, 73-86, 1998.
- Kozhevnikov, I.,V., “Heterogeneous Acid
- Catalysis by Heteropoly Acids: Approaches to
- Catalyst Deactivations”, Journal of Molecular
- Catalysis A: Chemical, 305, 104-111, 2009.
- Mestl, G., Ilkenhans, T., Spielbauer, D.,
- Dieterle, M., Timpe, O., Kröhnert, J., Jentoft, F.,
- Knözinger, H., Schlögl, R., “Thermally and
- chemically induced structural transformations of
- Keggin-type heteropoly acid catalysts”, Applied
- Catalysis A: General, 210, 13-34, 2001.
- Shikata, S., Nakata, S., Okuhara, T., Misono,
- M., “Catalysis by Heteropoly Compounds. 32.
- Synthesis of Methyl tert-Butyl Ether Catalyzed
- by Heteropolyacids Supported on Silica”,
- Journal of Catalysis, 166, 263-271, 1997.
- Molnar, A., Keresszegi, C., Török, B.,
- “Heteropoly acids immobilized into a silica
- matrix: characterization and catalytic
- applications”, Applied Catalysis A: General,
- , 217-224, 1999.
- Varisli, D., Dogu, T., Dogu, G., “Silicotungstic
- Acid Impregnated MCM-41-like Mesoporous
- Solid Acid Catalysts for Dehydration of
- Ethanol”, Ind. Eng. Chem. Res., 47, 4071-
- , 2008.
- Lim, S.,S., Park., G.,I., Song, I.,K, Lee, W.,Y.,
- “Heteropolyacid (HPA)-polymer composite
- films as catalytic materials for heterogeneous
- reactions”, Journal of Molecular Catalysis A:
- Chemical, 182-183, 175-183, 2002.
- Monopoli, V.,D., Pizzio, L.,R., Blanco, M.,N.,
- “Polyvinyl alcohol-polyethylenglycol blends
- with tungstophosphoric acid addition: Synthesis
- and characterization”, Materials Chemistry
- and Physics, 108, 331-336, 2008.
- Berry, F.,J., Derrick, G.,R., Marco, J.,F.,
- Mortimer, M., “Silica-Supported Silicotungstic
- Acid: A Study by X-ray Photoelectron
- Spectroscopy”, Materials Chemistry and
- Physics, 114, 1000-1003, 2009.
- Yu, X., Guo, Y., Li, K., Yang, X., Xu, L., Guo,
- Y., Hu, J., “Catalytic Synthesis of Diphenolic
- Acid from Levulinic Acid over Cesium Partly
- Substituted Wells-Dawson Type
- Heteropolyacid”, Journal of Molecular
- Catalysis A: Chemical, 290, 44-53, 2008.
- Thomas, A., Dablemont, C., Basset, J.,M.,
- Lefebvre, F., “Comparison of H3PW12O40 and
- H4SiW12O40 heteropolyacids supported on silica
- by H MAS NMR”, C.R. Chimie, 8, 1969-1974,
- -
- Burguete, M.,I., Fabregat, V., Galindo, F.,
- Izquierdo, M.,A., Luis, S.,V., “Improved
- polyHEMA–DAQ films for the optical analysis
- of nitrite”, European Polymer Journal, 45,
- -1523, 2009.
- Aparacio, M., Castro, Y., Duran, A.,” Synthesis
- and Characterization of Proton Conducting
- Styrene-co-methacrylate-silica Sol-gel
- Membranes Containing Tungstophosphoric
- Acid”, Solid State Ionics, 176, 333-340, 2005.
- Bodas, D.,S., Desai., S.,M., Gangal., S.,A.,
- “Deposition of Plasma-polymerized
- Hydroxyethyl Methacrylate (HEMA) on Silicon
- in Presence of Argon Plasma”, Applied Surface
- Science. 245, 186-190, 2005.
- Gonçalves, I.,C., Martins, M.,C.,L., Barbosa,
- M.,A., Ratner, B.,D., “Protein adsorption and
- clotting time of pHEMA hydrogels modified
- with C18 ligands to adsorb albumin selectively
- and reversibly”, Biomaterials, 30, 5541-5551,
- -
- Terzyk, A., “The influence of activated carbon
- surface chemical composition on the adsorption
- of acetaminophen (paracetamol) in vitro Part II.
- TG, FTIR, and XPS analysis of carbons and the
- temperature dependence of adsorption kinetics
- at the neutral pH” Colloids and Surfaces, 17,
- -45, 2001.
Yıl 2012,
Cilt: 27 Sayı: 3, 0 - , 19.02.2013
Levent Değirmenci
Nuray Oktar
Kaynakça
- Kharoune, M., Pauss, A. and Lebeault, M., J.,
- “Aerobic biodegradation of an oxygenates
- mixture: ETBE, MTBE and TAME in an
- Upflow Fixed-Bed Reactor”, Wat. Res., 35 (7),
- -1674, 2001.
- Manzini, F., “Inserting renewable fuels and
- technologies for transport in Mexico City
- Metropolitan Area”, International Journal of
- Hydrogen Energy, 31, 327-335, 2006.
- Malça, J., Freire, F., “Renewability and lifecycle
- energy efficiency of bioethanol and bioethyl
- tertiary-butyl ether (bioETBE): Assesing
- the implications of allocation”, Energy, 31,
- -3380, 2006.
- Oktar, N., Murtezaoglu, K., Dogu, G.,
- Gonderten, I., Dogu, T., “Etherification Rates of
- -Methyl 2-Butane and 2-Methyl-1- Butene
- with Ethanol for Environmentally Clean
- Gasoline Production”, J. Chem. Tech.
- Biotech., 74, 155-161, 1999.
- Oktar, N., Murtezaoglu, K., Dogu, T., Dogu, G.,
- “Dynamic analysis of adsorption equilibrium
- and rate parameters of reactants and products in
- MTBE, ETBE and TAME production”, Can. J.
- Chem. Eng., 77, 406-412, 1999.
- Boz, N., Dogu, T., Murtezaoglu, K., Dogu, G.,
- “Effect of Hydrogen Ion-Exchange Capacity on
- Activity of Resin Catalysts in Tert-amyl-ethylether
- Synthesis”, Appl. Catal. A: General, 268,
- -182, 2004.
- Dogu, T., Boz, N., Aydin, E., Oktar, N.,
- Murtezaoglu, K., Dogu, G., “DRIFTS Studies
- for the Reaction and Adsorption of Alcohols
- and Isobutylene on Acidic Resin Catalysts and
- the Mechanism of ETBE and MTBE Synthesis”,
- Industrial & Engineering Chemistry
- Research, 40, 23, 5044-5051, 2001.
- Boz, N., Doğu, T., Mürtezaoğlu, K., Doğu, G.,
- “Mechanism of TAME and TAEE synthesis
- from diffuse-reflectance FTIR analysis”,
- Catalysis Today, 100, 419-424, 2005.
- Degirmenci, L., Oktar, N., Dogu, G., “Product
- Distributions in Ethyl- tert-Butyl-Ether
- Synthesis over Different Solid Acid Catalysts”,
- Ind. Eng. Chem. Res., 48, 5, 2566-2576, 2009.
- Degirmenci, L., Oktar, N., Dogu, G., “ETBE
- Synthesis Over Silicotungstic Acid and
- Tungstophosphoric Acid Catalysts Calcined at
- Different Temperatures”, Fuel Processing
- Technology, 91, 737-742, 2010.
- Degirmenci, L., Oktar, N., Dogu, G., “Activated
- Carbon Supported Silicotungstic Acid Catalysts
- for ETBE Synthesis” AIChE Journal.
- DOI: 10,1002/aic.12524, 2011.
- Li, G., Dong, Y., Wang, J., Wang, X., Suo, J.,
- “New progress of Keggin and Wells-Dawson
- type polyoxometalates catalyze acid and
- oxidative reactions”, Journal of Molecular
- Catalysis A: Chemical, 262, 67-76, 2007.
- Cavani, F., “Heteropolycompund-based
- catalysts: A blend of acidic and oxidizing
- properties”, Catalysis Today, 41, 73-86, 1998.
- Kozhevnikov, I.,V., “Heterogeneous Acid
- Catalysis by Heteropoly Acids: Approaches to
- Catalyst Deactivations”, Journal of Molecular
- Catalysis A: Chemical, 305, 104-111, 2009.
- Mestl, G., Ilkenhans, T., Spielbauer, D.,
- Dieterle, M., Timpe, O., Kröhnert, J., Jentoft, F.,
- Knözinger, H., Schlögl, R., “Thermally and
- chemically induced structural transformations of
- Keggin-type heteropoly acid catalysts”, Applied
- Catalysis A: General, 210, 13-34, 2001.
- Shikata, S., Nakata, S., Okuhara, T., Misono,
- M., “Catalysis by Heteropoly Compounds. 32.
- Synthesis of Methyl tert-Butyl Ether Catalyzed
- by Heteropolyacids Supported on Silica”,
- Journal of Catalysis, 166, 263-271, 1997.
- Molnar, A., Keresszegi, C., Török, B.,
- “Heteropoly acids immobilized into a silica
- matrix: characterization and catalytic
- applications”, Applied Catalysis A: General,
- , 217-224, 1999.
- Varisli, D., Dogu, T., Dogu, G., “Silicotungstic
- Acid Impregnated MCM-41-like Mesoporous
- Solid Acid Catalysts for Dehydration of
- Ethanol”, Ind. Eng. Chem. Res., 47, 4071-
- , 2008.
- Lim, S.,S., Park., G.,I., Song, I.,K, Lee, W.,Y.,
- “Heteropolyacid (HPA)-polymer composite
- films as catalytic materials for heterogeneous
- reactions”, Journal of Molecular Catalysis A:
- Chemical, 182-183, 175-183, 2002.
- Monopoli, V.,D., Pizzio, L.,R., Blanco, M.,N.,
- “Polyvinyl alcohol-polyethylenglycol blends
- with tungstophosphoric acid addition: Synthesis
- and characterization”, Materials Chemistry
- and Physics, 108, 331-336, 2008.
- Berry, F.,J., Derrick, G.,R., Marco, J.,F.,
- Mortimer, M., “Silica-Supported Silicotungstic
- Acid: A Study by X-ray Photoelectron
- Spectroscopy”, Materials Chemistry and
- Physics, 114, 1000-1003, 2009.
- Yu, X., Guo, Y., Li, K., Yang, X., Xu, L., Guo,
- Y., Hu, J., “Catalytic Synthesis of Diphenolic
- Acid from Levulinic Acid over Cesium Partly
- Substituted Wells-Dawson Type
- Heteropolyacid”, Journal of Molecular
- Catalysis A: Chemical, 290, 44-53, 2008.
- Thomas, A., Dablemont, C., Basset, J.,M.,
- Lefebvre, F., “Comparison of H3PW12O40 and
- H4SiW12O40 heteropolyacids supported on silica
- by H MAS NMR”, C.R. Chimie, 8, 1969-1974,
- -
- Burguete, M.,I., Fabregat, V., Galindo, F.,
- Izquierdo, M.,A., Luis, S.,V., “Improved
- polyHEMA–DAQ films for the optical analysis
- of nitrite”, European Polymer Journal, 45,
- -1523, 2009.
- Aparacio, M., Castro, Y., Duran, A.,” Synthesis
- and Characterization of Proton Conducting
- Styrene-co-methacrylate-silica Sol-gel
- Membranes Containing Tungstophosphoric
- Acid”, Solid State Ionics, 176, 333-340, 2005.
- Bodas, D.,S., Desai., S.,M., Gangal., S.,A.,
- “Deposition of Plasma-polymerized
- Hydroxyethyl Methacrylate (HEMA) on Silicon
- in Presence of Argon Plasma”, Applied Surface
- Science. 245, 186-190, 2005.
- Gonçalves, I.,C., Martins, M.,C.,L., Barbosa,
- M.,A., Ratner, B.,D., “Protein adsorption and
- clotting time of pHEMA hydrogels modified
- with C18 ligands to adsorb albumin selectively
- and reversibly”, Biomaterials, 30, 5541-5551,
- -
- Terzyk, A., “The influence of activated carbon
- surface chemical composition on the adsorption
- of acetaminophen (paracetamol) in vitro Part II.
- TG, FTIR, and XPS analysis of carbons and the
- temperature dependence of adsorption kinetics
- at the neutral pH” Colloids and Surfaces, 17,
- -45, 2001.