Biyodizel Yan Ürünü Olan Gliserolden Üretilen Katalizör ile Yakıt Katkı Maddesi Bütil Levulinat Sentezi

Yıl 2019, Cilt: 8 Sayı: 1, 214 - 226, 12.03.2019

Derya Ünlü

https://doi.org/10.17798/bitlisfen.453633

Öz

Biyodizelin yan ürünü olarak gliserol üretiminin
fazlalığı gliserolün değerlendirilmesi için araştırmacıları yeni ürün
arayışlarına itmiştir. Bu çalışmada biyo-türevli gliserol, tek bir adımda karbonizasyon
ve sülfonasyon yoluyla heterojen katı asit katalizör sentezi için bir karbon başlatıcısı
olarak kullanılmıştır. Üretilen katalizör, 
yakıt biyokatkı maddesi bütil levulinat sentezlemek üzere levulinik asit
ile bütanolün esterleşme reaksiyonunu katalizlemek için kullanılmıştır. Katalizör
karakterizasyonu; FTIR, TGA ve XRD cihazları kullanılarak yapılmıştır.
Katalizörün katalitik aktivitesini belirlemek için  deneyler farklı reaksiyon sıcaklıklarında,
farklı molar besleme oranlarında ve farklı katalizör yükleme oranlarında
kesikli reaktörde gerçekleştirilmiştir. En yüksek dönüşüm değeri 70^oC’de,
molar besleme oranı (alkol/asit) 9:1 kullanılarak ve %7 katalizör yükleme
oranında altı saatin sonunda %96.25 olarak elde edilmiştir. Katalizör esterleşme
reaksiyonunun polar ortamından zarar görmemektedir.  Bu nedenle, katalitik aktivitesini
kaybetmeden sekiz kez tekrar kullanılmıştır.

Anahtar Kelimeler

Biyodizel, Bütil Levulinat, Gliserol, Karbon Katalizör, Levulinik Asit

Kaynakça

• [1] Gonçalves V.L.C., Pinto B.P., Silva J.C., Mota C.J.A. 2008. Acetylation of glycerol catalyzed by different solid acids, Catalysis Today, 2008, 133–135:73–677.
• [2] Rodrígue I.D., Adriany C., Gaigneaux E.M. 2011. Glycerol acetylation on sulphated zirconia in mild conditions, Catalysis Today, 167 (1): 56–63.
• [3] Zhu S., Zhu Y., Gao X., Mo T., Zhu Y., Lia Y. 2013. Production of bioadditives from glycerol esterification over zirconia supported heteropolyacids, Bioresource Technology, 130: 45-51.
• [4] Khayoon M.S., Hameed B.H. 2012. Synthesis of hybrid SBA-15 functionalized with molybdophosphoric acid as efficient catalyst for glycerol esterification to fuel additives, Applied Catalysis A: General, 433–434: 152–161.
• [5] Kuwahara Y., Fujitani T., Yamashita H. 2014. Esterification of levulinic acid with ethanol over sulfated mesoporous zirconosilicates: Influences of the preparation conditions on the structural properties and catalytic performances, Catalysis Today, 237: 18–28.
• [6] Fernandes D.R., Rocha A.S., Mai E.F., Mota J.A., Silva V. 2012. Levulinic acid esterification with ethanol to ethyl levulinate production over solid acid catalysts, Applied Catalysis A: General, 425–426: 199–204.
• [7] Yang J., Li G., Zhang L., Zhang S. 2018. Efficient Production of N-Butyl Levulinate Fuel Additive from Levulinic Acid Using Amorphous Carbon Enriched with Oxygenated Groups, Catalysts, 8 (1): 14.
• [8] Ramli, N.A.S., Zaharudin N.H., Amin N.A.S. 2017. Esterification of Renewable Levulinic Acid To Levulinate Esters Using Amberlyst-15 As A Solid Acid Catalyst, 79 (1): 137–142.
• [9] Dharne S., Bokade V.V. 2011. Esterification of levulinic acid to n-butyl levulinate over heteropolyacid supported on acid-treated clay, Journal of Natural Gas Chemistry, 20: 18–24.
• [10] Maheria K.C., Kozinski J., Dalai A. 2013. Esterification of Levulinic Acid to n-Butyl Levulinate Over Various Acidic Zeolites, Catalysis Letters, 143: 1220–1225.
• [11] Devi B.LA.P, Gangadhar K.N., Prasad P.S.S, Jagannadh B., Prasad R.B.N. 2009. A Glycerol-based Carbon Catalyst for the Preparation of Biodiesel, 2: 617-620.
• [12] Okoye P.U., Abdullah A.Z., Hameed B.H. 2017. Synthesis of oxygenated fuel additives via glycerol esterification with acetic acid over bio-derived carbon catalyst, Fuel, 209: 538–544.
• [13] Varkolu M., Moodley V., Potwana F.S.W., Jonnalagadda S.B., Zyl W.E. 2017. Esterification of levulinic acid with ethanol over bio-glycerol derived carbon–sulfonic-acid, Reaction Kinetics Mechanisms and Catalysis, 120 (1): 69–80.
• [14] Ummadisetti C., Rachapudi B.N.P., Bethala L.A.P.D. 2014. Glycerol‐based SO3H‐Carbon Catalyst: A green recyclable catalyst for the chemoselective synthesis of pentaerythritol diacetals, European Journal of Chemistry 5 (3): 536‐540.
• [15] Ribeiro R.S., Silva A.M.T., Pinho M.T., Figueiredo J.L., Faria J.L., Gomes H.T. 2014. Development of glycerol-based metal-free carbon materials for environmental catalytic applications, Catalysis Today, 240: 61-66.
• [16] Gangadhar K.N., Vijay M., Prasad R.B.N., Devi B.L.A.P. 2013. Glycerol-Based Carbon-SO3H Catalyzed Benign Synthetic Protocol for the Acetylation of Alcohols, Phenols and Amines under Solvent-Free Conditions, Green and Sustainable Chemistry, 3: 122-128.
• [17] Ilgen O. 2014. Investigation of reaction parameters, kinetics and mechanism of oleic acid esterification with methanol by using Amberlyst 46 as a catalyst, Fuel Processing Technology, 124: 134-139.
• [18] Jamil F., Al-Muhtaseb A.H., Naushad M., Baawain M., Al-Mamun A., Saxena S.K., Viswanadham N. 2017. Evaluation of synthesized green carbon catalyst from waste date pits for tertiary butylation of phenol, inpress, DOI: 10.1016/j.arabjc.2017.04.009.
• [19] Khayoon M.S., Hameed B.H. 2011. Acetylation of glycerol to biofuel additives over sulfated activated carbon catalyst, Bioresource Technology, 102 (19): 9229–9235.
• [20] Zhou L., Al-Zaini E., Adesina A.A. 2013. Catalytic characteristics and parameters optimization of the glycerol acetylation over solid acid catalysts, Fuel, 103: 617–625.
• [21] Zhang W., Qing W., Ren Z., Li W., Chen J. 2014. Lipase immobilized catalytically active membrane for synthesis of lauryl stearate in a pervaporation membrane reactor, Bioresource Technology, 172: 16-21.
• [22] Karakus S., Pervaporasyon Esterleşme Hi̇bri̇t Prosesi̇ i̇le İzobuti̇l Akri̇lat Sentezi̇, Yüksek Lisans Tezi, Ege Üniversitesi, Fen Bilimleri Enstitüsü, İzmir, 2014, 371480.
• [23] Sert E., Atalay F.S. 2014. n-Butyl acrylate production by esterification of acrylic acid with n-butanol combined with pervaporation, Chemical Engineering and Processing: Process Intensification, 81: 41-47.
• [24] Chen Y., Zhang X., Dong M., Wu Y., Zheng G., Huang J., Zheng, X. 2016. MCM-41 immobilized 12-silicotungstic acid mesoporous materials: Structural and catalytic properties for esterification of levulinic acid and oleic acid, Journal of the Taiwan Institute of Chemical Engineers, 61: 147-155.
• [25] Jyoti G., Keshav A., Anandkumar J. 2017. Esterification of acrylic acid with ethanol using pervaporation membrane reactor, Korean Journal of Chemical Engineering, 34 (6): 1661–1668.
• [26] Parida K.M., Mallick S. 2007. Silicotungstic acid supported zirconia : An effective catalyst for esterification reaction, Journal of Molecular Catalysis A: Chemical, 275: 77–83.
• [27] Balaraju M., Nikhitha P., Jagadeeswaraiah K., Srilatha K., Prasad P.S.S., Lingaiah N. 2010. Acetylation of glycerol to synthesize bioadditives over niobic acid supported tungstophosphoric acid catalysts, Fuel Processing Technology, 91(2): 249–253.
• [28] Jyoti G., Keshav A., Anandkumar J. 2015. Review on Pervaporation :Theory, Membrane Performance, and Application to Intensification of Esterification Reaction, Journal of Engineering, 2015: 1-24.
• [29] Ramli N.A.S., Sivasubramaniam D., Amin N.A.S. 2017. Esterification of Levulinic Acid Using ZrO2-Supported Phosphotungstic Acid Catalyst for Ethyl Levulinate Production, BioEnergy Research, 10 (4): 1105–1116.
• [30] Delgado P., Sanz M.T., Beltrán S., Alberto L. 2010. Ethyl lactate production via esterification of lactic acid with ethanol combined with pervaporation, Chemical Engineering Journal, 165: 693–700.
• [31] Qing W., Chen J., Shi X., Wu J., Hu J., Zhang W. 2016. Conversion enhancement for acetalization using a catalytically active membrane in a pervaporation membrane reactor, Chemical Engineering Journal, 313: 1396–1405.
• [32] Peters T.A., Tuin J.V.D., Houssin C., Vorstman M.A.G., Benes N.E., Vroon Z.A.E.P., Holmen A., Keurentjes J.T.F. 2005. Preparation of zeolite-coated pervaporation membranes for the integration of reaction and separation, Catalysis Today, 104 (2–4): 288–295.
• [33] Castanheiro J.E., Ramos A.M., Fonseca I.M., Vital J. 2006. Esterification of acetic acid by isoamylic alcohol over catalytic membranes of poly(vinyl alcohol) containing sulfonic acid groups, Applied Catalysis A: General, 311 (1–2): 17–23.