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.