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PRODUCTION OF VALUABLE CHEMICALS VIA ESTERIFICATION AND ACETYLATION OF GLYCEROL, BY-PRODUCT OF BIODIESEL

Yıl 2015, Cilt: 30 Sayı: 3, 443 - 450, 30.09.2015
https://doi.org/10.17341/gummfd.97245

Öz

Biodiesel is an alternative fuel to gasoline due to its environmental and economical benefits. Glycerol is the main
by-product of the biodiesel production by transesterification of vegetable oil with methanol or ethanol. The
esterification of glycerol with acetic acid can be a good choice for utilization of by-product glycerol. In this work
esterification of glycerol with acetic acid was performed in liquid phase autoclave batch reactor in the presence
of Smopex-101. Complete glycerol conversion was achieved in the reaction studies even at room temperatures.
Effects of reaction temperatures and initial reactant molar ratios on the glycerol conversions and product
selectivity were also investigated. The maximum diacetin (77 %) and triacetin (23 %) selectivities were achieved
at 363 K and glycerol/acetic acid; 1/12 molar ratio. Acetylation reactions were performed with acetyl chloride in
the presence of Smopex-101 in order to increase triacetin selectivity. 66 % triacetin selectivity was achieved in
acetylation reaction studies in a period of 1200 minutes at room temperature.

Kaynakça

  • Gonçalves, L.C., Pinto, B.P., Silva, J.C., Mota C.J.A., “Acetylation of glycerol catalyzed by different solid acids” Catalysis Today, Cilt 133, 673–677, 2008.
  • Liao X., Zhu, Y., Wang, S.-G., Li, Y., “Producing triacetylglycerol with glycerol by two steps: Esterification and acetylation” Fuel Processing Technology,, Cilt 90, 988–993, 2009.
  • Garcia, E., Laca, M., Perez, E., Garrido, A., Peinado, J., “New Class of Acetal Derived from Glycerin as a Biodiesel Fuel Component” Energy Fuels, Cilt 22, 4274–4280, 2008.
  • Casas, A., Ruiz, J., R., Ramos, M.,J., Perez, A., “Effects of Triacetin on Biodiesel Quality” Energy Fuels, Cilt 24, 4481–4489, 2010.
  • Sawant, D. P., Vinu, A., Justus, J., Srinivasu, P., Halligudi S.B., “Catalytic performances of silicotungstic acid/zirconia supported SBA-15 in an esterification of benzyl alcohol with acetic acid”, Journal of Molecular Catalysis A: Chemical, Cilt 276, 150-157, 2007.
  • Rönnback, R., Salmi, T., Vuori, A., Haario, H., Lehtonen, J., Sundqvist, A., Tirronen, E., “Development of a kinetic model for the esterification of acetic acid with methanol in the presence of a homogeneous acid catalyst”, Chemical Engineering Science, Cilt 52, 3369-3381, 1997.
  • Jermy, B.R., Pandurangan, A., “A highly efficient catalyst for the esterification of acetic acid using n-butyl alcohol”, Journal of Molecular Catalysis A: Chemical, Cilt 237, 146-154, 2005.
  • Yadav, G., D., Mehta, P., H., “Heterogeneous catalysis in esterification reactions - preparation of phenethyl acetate and cyclohexyl acetate by using a variety of solid acidic catalysts”, Ind. Eng. Chem. Res., Cilt 33, 2198-2208, 1994.
  • Corma, A., Garcia, H., Iborra, S., Primo J., “Modified faujasite zeolites as catalysts in organic reactions: Esterification of carboxylic acids in the presence of HY zeolites”, Journal of Catalysis, Cilt 120, 78-87, 1989.
  • Pereira,C., S., M., Pinho, S., P., Silva, V., M., T., M., Rodrigues, A., E., “Thermodynamic equilibrium and reaction kinetics for the esterification of lactic acid with ethanol catalyzed by ion-exchange resin”, Ind. Eng. Chem. Res., Cilt 47, 1453-1463, 2008.
  • Yu, G., X., Zhou, X., L., Li, C., L., Chen, L., F., Wang, J., A., “Esterification over rare earth oxide and alumina promoted SO42−/ZrO2”, Catalysis Today, Cilt 148, 169-173, 2009.
  • Peters, T., A., Benes, N., E., Holmen, A., Keurentjes, J., T., F., “Comparison of commercial solid acid catalysts for the esterification of acetic acid with butanol” , Applied Catalysis A: General, Cilt 297:182, 2006.
  • Ferreira, P., Fonseca, I.M., Ramos, A.M., Vital J., Castanheiro, J.E., “Esterification of glycerol with acetic acid over dodecamolybdophosphoric acid encaged in USY zeolite”, Catalysis Communications, Cilt 10, 481–484, 2009.
  • Zhou, L., Nguyen, T.-H., Adesina, A., A., “The acetylation of glycerol over Amberlyst-15: Kinetic and product distribution”, Fuel Processing Technology, Cilt 104, 310-318, 2012.
  • Balaraju, M., Nikhitha, P., Jagadeeswaraiah, K., Srilatha, K., Sai Prasad,P.S., Lingaiah N., “Acetylation of glycerol to synthesize bioadditives over niobic acid supported tungstophosphoric acid catalysts”, Fuel Processing Technology, Cilt 91, 249–253, 2010.
  • Maki- Arvela, P., Salmi, T., Sundell, M., Ekman, K., Peltonen, R., Lehtonen, J., “Comparison of polyvinylbenzene and polyolefin supported sulphonic acid catalysts in the esterification of acetic acid”, Applied Catalysis A: General, Cilt 184, 25-32, 1999.
  • Lilja, J., Aumo, J., Salmi, T., Murzin, D., Maki- Arvela, P., Sundell, M., Ekman, K., Peltonen, R., Vainio, H., “ Kinetics of esterification of propanoic acid with methanol over a fibrous polymer- supported sulphonic acid catalyst”, Applied Catalysis A: General, Cilt 228, 253-267, 2002.
  • Peters, A.N., Benes, N.E., “Comparison of commercial solid acid catalysts for the esterification of acetic acid with butanol”, Applied Catalysis A: General, Cilt 297, 182-188, 2006.
  • Khayoon, M., S., Hameed B., H., “Synthesis of Hibrid SBA-15 functionalized with molybdophosphoric acid as efficient catalyst for glycerol esterification to fuel additives”, Applied Catalysis A: General, Cilt 433-434, 152-161, 2012.
  • Melero, J., A., Grieken, R., Morales, G., Nuno, V., “Friedel Crafts acylation of aromatic compounds over arenesulfonic containing mesostructured SBA-15 materials”, Catalysis Communications, Cilt 5, 131-136, 2004.

BİYODİZEL YAN ÜRÜNÜ GLİSERİNİN ESTERLEŞME VE ASETİLASYONU İLE DEĞERLİ KİMYASALLARIN ÜRETİMİ

Yıl 2015, Cilt: 30 Sayı: 3, 443 - 450, 30.09.2015
https://doi.org/10.17341/gummfd.97245

Öz

Çevreci bir yakıt olan biyodizel çeşitli avantajlarından ötürü dizel yakıta alternatif bir yakıttır. Bitkisel yağın metanol veya etanol ile transesterleşmesiyle biyodizel üretilmekte ve yan ürün olarak önemli miktarda gliserin oluşmaktadır. Gliserinin asetik asitle esterleşmesi biyodizel üretiminden kaynaklanan artan gliserinin değerlendirilmesi açısından alternatif bir çözüm teşkil eder. Yapılan çalışmada gliserinin asetik asitle esterleşme reaksiyonu Smopex-101 varlığında sıvı faz kesikli otoklav reaktörde incelenmiştir. Yapılan reaksiyon çalışmalarında oda sıcaklığında oldukça kısa sürede (25 dakika) %100 gliserin dönüşümüne ulaşılmıştır. Reaksiyon sıcaklığı ve başlangıç reaktan molar oranlarının gliserin dönüşümü ve ürün seçiciliği açısından etkisi incelenmiştir. En yüksek diasetin (%77) ve triasetin (%23) seçiciliğine 363K’de ve gliserin/asetik asit;1/12 molar oranında ulaşılmıştır. Triasetin seçiciliğini artırmaya yönelik asetil klorür ile Smopex-101 varlığında asetilasyon reaksiyonu gerçekleştirimiştir. Oda sıcaklığında gerçekleştirilen çalışmalarda 1200 dakika sonunda %60 triasetin seçiciliğine ulaşılmıştır.

Kaynakça

  • Gonçalves, L.C., Pinto, B.P., Silva, J.C., Mota C.J.A., “Acetylation of glycerol catalyzed by different solid acids” Catalysis Today, Cilt 133, 673–677, 2008.
  • Liao X., Zhu, Y., Wang, S.-G., Li, Y., “Producing triacetylglycerol with glycerol by two steps: Esterification and acetylation” Fuel Processing Technology,, Cilt 90, 988–993, 2009.
  • Garcia, E., Laca, M., Perez, E., Garrido, A., Peinado, J., “New Class of Acetal Derived from Glycerin as a Biodiesel Fuel Component” Energy Fuels, Cilt 22, 4274–4280, 2008.
  • Casas, A., Ruiz, J., R., Ramos, M.,J., Perez, A., “Effects of Triacetin on Biodiesel Quality” Energy Fuels, Cilt 24, 4481–4489, 2010.
  • Sawant, D. P., Vinu, A., Justus, J., Srinivasu, P., Halligudi S.B., “Catalytic performances of silicotungstic acid/zirconia supported SBA-15 in an esterification of benzyl alcohol with acetic acid”, Journal of Molecular Catalysis A: Chemical, Cilt 276, 150-157, 2007.
  • Rönnback, R., Salmi, T., Vuori, A., Haario, H., Lehtonen, J., Sundqvist, A., Tirronen, E., “Development of a kinetic model for the esterification of acetic acid with methanol in the presence of a homogeneous acid catalyst”, Chemical Engineering Science, Cilt 52, 3369-3381, 1997.
  • Jermy, B.R., Pandurangan, A., “A highly efficient catalyst for the esterification of acetic acid using n-butyl alcohol”, Journal of Molecular Catalysis A: Chemical, Cilt 237, 146-154, 2005.
  • Yadav, G., D., Mehta, P., H., “Heterogeneous catalysis in esterification reactions - preparation of phenethyl acetate and cyclohexyl acetate by using a variety of solid acidic catalysts”, Ind. Eng. Chem. Res., Cilt 33, 2198-2208, 1994.
  • Corma, A., Garcia, H., Iborra, S., Primo J., “Modified faujasite zeolites as catalysts in organic reactions: Esterification of carboxylic acids in the presence of HY zeolites”, Journal of Catalysis, Cilt 120, 78-87, 1989.
  • Pereira,C., S., M., Pinho, S., P., Silva, V., M., T., M., Rodrigues, A., E., “Thermodynamic equilibrium and reaction kinetics for the esterification of lactic acid with ethanol catalyzed by ion-exchange resin”, Ind. Eng. Chem. Res., Cilt 47, 1453-1463, 2008.
  • Yu, G., X., Zhou, X., L., Li, C., L., Chen, L., F., Wang, J., A., “Esterification over rare earth oxide and alumina promoted SO42−/ZrO2”, Catalysis Today, Cilt 148, 169-173, 2009.
  • Peters, T., A., Benes, N., E., Holmen, A., Keurentjes, J., T., F., “Comparison of commercial solid acid catalysts for the esterification of acetic acid with butanol” , Applied Catalysis A: General, Cilt 297:182, 2006.
  • Ferreira, P., Fonseca, I.M., Ramos, A.M., Vital J., Castanheiro, J.E., “Esterification of glycerol with acetic acid over dodecamolybdophosphoric acid encaged in USY zeolite”, Catalysis Communications, Cilt 10, 481–484, 2009.
  • Zhou, L., Nguyen, T.-H., Adesina, A., A., “The acetylation of glycerol over Amberlyst-15: Kinetic and product distribution”, Fuel Processing Technology, Cilt 104, 310-318, 2012.
  • Balaraju, M., Nikhitha, P., Jagadeeswaraiah, K., Srilatha, K., Sai Prasad,P.S., Lingaiah N., “Acetylation of glycerol to synthesize bioadditives over niobic acid supported tungstophosphoric acid catalysts”, Fuel Processing Technology, Cilt 91, 249–253, 2010.
  • Maki- Arvela, P., Salmi, T., Sundell, M., Ekman, K., Peltonen, R., Lehtonen, J., “Comparison of polyvinylbenzene and polyolefin supported sulphonic acid catalysts in the esterification of acetic acid”, Applied Catalysis A: General, Cilt 184, 25-32, 1999.
  • Lilja, J., Aumo, J., Salmi, T., Murzin, D., Maki- Arvela, P., Sundell, M., Ekman, K., Peltonen, R., Vainio, H., “ Kinetics of esterification of propanoic acid with methanol over a fibrous polymer- supported sulphonic acid catalyst”, Applied Catalysis A: General, Cilt 228, 253-267, 2002.
  • Peters, A.N., Benes, N.E., “Comparison of commercial solid acid catalysts for the esterification of acetic acid with butanol”, Applied Catalysis A: General, Cilt 297, 182-188, 2006.
  • Khayoon, M., S., Hameed B., H., “Synthesis of Hibrid SBA-15 functionalized with molybdophosphoric acid as efficient catalyst for glycerol esterification to fuel additives”, Applied Catalysis A: General, Cilt 433-434, 152-161, 2012.
  • Melero, J., A., Grieken, R., Morales, G., Nuno, V., “Friedel Crafts acylation of aromatic compounds over arenesulfonic containing mesostructured SBA-15 materials”, Catalysis Communications, Cilt 5, 131-136, 2004.
Toplam 20 adet kaynakça vardır.

Ayrıntılar

Birincil Dil Türkçe
Konular Mühendislik
Bölüm Makaleler
Yazarlar

Emine Kaya Ekinci

Gamze Gündüz

Nuray Oktar

Yayımlanma Tarihi 30 Eylül 2015
Gönderilme Tarihi 30 Eylül 2015
Yayımlandığı Sayı Yıl 2015 Cilt: 30 Sayı: 3

Kaynak Göster

APA Kaya Ekinci, E., Gündüz, G., & Oktar, N. (2015). BİYODİZEL YAN ÜRÜNÜ GLİSERİNİN ESTERLEŞME VE ASETİLASYONU İLE DEĞERLİ KİMYASALLARIN ÜRETİMİ. Gazi Üniversitesi Mühendislik Mimarlık Fakültesi Dergisi, 30(3), 443-450. https://doi.org/10.17341/gummfd.97245
AMA Kaya Ekinci E, Gündüz G, Oktar N. BİYODİZEL YAN ÜRÜNÜ GLİSERİNİN ESTERLEŞME VE ASETİLASYONU İLE DEĞERLİ KİMYASALLARIN ÜRETİMİ. GUMMFD. Ekim 2015;30(3):443-450. doi:10.17341/gummfd.97245
Chicago Kaya Ekinci, Emine, Gamze Gündüz, ve Nuray Oktar. “BİYODİZEL YAN ÜRÜNÜ GLİSERİNİN ESTERLEŞME VE ASETİLASYONU İLE DEĞERLİ KİMYASALLARIN ÜRETİMİ”. Gazi Üniversitesi Mühendislik Mimarlık Fakültesi Dergisi 30, sy. 3 (Ekim 2015): 443-50. https://doi.org/10.17341/gummfd.97245.
EndNote Kaya Ekinci E, Gündüz G, Oktar N (01 Ekim 2015) BİYODİZEL YAN ÜRÜNÜ GLİSERİNİN ESTERLEŞME VE ASETİLASYONU İLE DEĞERLİ KİMYASALLARIN ÜRETİMİ. Gazi Üniversitesi Mühendislik Mimarlık Fakültesi Dergisi 30 3 443–450.
IEEE E. Kaya Ekinci, G. Gündüz, ve N. Oktar, “BİYODİZEL YAN ÜRÜNÜ GLİSERİNİN ESTERLEŞME VE ASETİLASYONU İLE DEĞERLİ KİMYASALLARIN ÜRETİMİ”, GUMMFD, c. 30, sy. 3, ss. 443–450, 2015, doi: 10.17341/gummfd.97245.
ISNAD Kaya Ekinci, Emine vd. “BİYODİZEL YAN ÜRÜNÜ GLİSERİNİN ESTERLEŞME VE ASETİLASYONU İLE DEĞERLİ KİMYASALLARIN ÜRETİMİ”. Gazi Üniversitesi Mühendislik Mimarlık Fakültesi Dergisi 30/3 (Ekim 2015), 443-450. https://doi.org/10.17341/gummfd.97245.
JAMA Kaya Ekinci E, Gündüz G, Oktar N. BİYODİZEL YAN ÜRÜNÜ GLİSERİNİN ESTERLEŞME VE ASETİLASYONU İLE DEĞERLİ KİMYASALLARIN ÜRETİMİ. GUMMFD. 2015;30:443–450.
MLA Kaya Ekinci, Emine vd. “BİYODİZEL YAN ÜRÜNÜ GLİSERİNİN ESTERLEŞME VE ASETİLASYONU İLE DEĞERLİ KİMYASALLARIN ÜRETİMİ”. Gazi Üniversitesi Mühendislik Mimarlık Fakültesi Dergisi, c. 30, sy. 3, 2015, ss. 443-50, doi:10.17341/gummfd.97245.
Vancouver Kaya Ekinci E, Gündüz G, Oktar N. BİYODİZEL YAN ÜRÜNÜ GLİSERİNİN ESTERLEŞME VE ASETİLASYONU İLE DEĞERLİ KİMYASALLARIN ÜRETİMİ. GUMMFD. 2015;30(3):443-50.