TY  - JOUR
T1  - TUNGSTOFOSFORİK ASİTLE MODİFİYE H-BETA ZEOLİT KATALİZÖRLER VARLIĞINDA DİFENİLMETAN SENTEZİ
TT  - SYNTHESIS OF DIPHENYLMETHANE OVER TUNGSTOPHOSPHORIC ACID MODIFIED H-BETA ZEOLITE CATALYSTS
AU  - Akyalçın, Sema
AU  - Akyalçın, Levent
AU  - Keskin, Fatma Hande
AU  - Satır, Çağan
PY  - 2024
DA  - December
Y2  - 2024
DO  - 10.31796/ogummf.1464296
JF  - Eskişehir Osmangazi Üniversitesi Mühendislik ve Mimarlık Fakültesi Dergisi
JO  - ESOGÜ Müh Mim Fak Derg
PB  - Eskişehir Osmangazi University
WT  - DergiPark
SN  - 2630-5712
SP  - 1556
EP  - 1564
VL  - 32
IS  - 3
LA  - tr
AB  - Bu çalışmada, H-Beta (HB) zeolit destekli tungstofosforik asit (TPA) üzerinde benzenin benzil alkol ile reaksiyonundan difenilmetan (DPM) sentezi araştırılmıştır. Destek zeoliti üzerinde ağırlıkça %5 ila %20 arasında değişen TPA yüklemeleri ıslak emdirme yöntemi kullanılarak elde edilmiş ve desteklenen katalizörler kalsinasyon işlemine tabi tutulmuştur. Hazırlanan katalizörler ICP-OES, XRD, azot adsorpsiyon-desorpsiyon izotermleri, amonyağın sıcaklık programlı desorpsiyonu (NH3-TPD) ve FT-IR ile karakterize edilmiştir. Sonuçlar, %98,9 benzil alkol dönüşümü ve %87,3 difenilmetan seçiciliği ile %5TPA-HB'nin hazırlanan diğer katalizörlerden daha yüksek bir katalitik performansa sahip olduğunu göstermiştir. Çalışma, %5TPA-HB'nin uygun gözenek büyüklüğü ve yüksek erişilebilir güçlü asit bölgelerinin iyi bir kombinasyonu sayesinde DPM sentezinde potansiyel uygulamalara sahip olduğunu göstermiştir.
KW  - Benzilasyon
KW  - Benzil alkol
KW  - Difenilmetan
KW  - Heteropoli Asit
KW  - H-Beta
N2  - In this study, the synthesis of diphenylmethane (DPM) from the reaction of benzene with benzyl alcohol over tungstophosphoric acid (TPA) supported on H-Beta (HB) zeolite was investigated. TPA loadings on the support zeolite ranging from 5 to 20% w/w were achieved using the wet impregnation method, and the supported catalysts were subjected to calcination treatment. The prepared catalysts were characterized by ICP-OES, XRD, nitrogen adsorption-desorption isotherms, temperature-programmed desorption of ammonia (NH3-TPD), and FT-IR. The results showed that 5%TPA-HB had a higher catalytic performance than the other prepared catalysts, with 98.9 % benzyl alcohol conversion and 87.3 % diphenylmethane selectivity. The study suggested that 5%TPA-HB has potential applications in the synthesis of DPM owing to a good combination of suitable pore size and large accessible strong acid sites.
CR  - Akyalcin, S., Akyalcin, L. & Bjørgen, M. (2019). Optimization of desilication parameters of low-silica ZSM-12 by Taguchi method. Microporous and Mesoporous Materials, 273, 256–264. doi: https://doi.org/10.1016/j.micromeso.2018.07.014
CR  - Almulla, F. M., Ali, S. A., Aldossary, M. R., Alnaimi, E. I., Jumah, A. bin & Garforth, A. A. (2020). Transalkylation of 1,2,4-trimethylbenzene with toluene over large pore zeolites: Role of pore structure and acidity. Applied Catalysis A: General, 608, 117886. doi: https://doi.org/10.1016/j.apcata.2020.117886
CR  - Atalay, B. & Gündüz, G. (2011). Isomerizaton of α-pinene over H3PW12O40 catalysts supported on natural zeolite. Chemical Engineering Journal, 168(3), 1311–1318. doi: https://doi.org/10.1016/j.cej.2011.02.037
CR  - Bai, G., Li, T., Yang, Y., Zhang, H., Lan, X., Li, F., Han, J., Ma, Z., Chen, Q. & Chen, G. (2012). Microwave-assisted Friedel-Crafts acylation of indole with acetic anhydride over tungstophosphoric acid modified Hβ zeolite. Catalysis Communications, 29, 114–117. doi: https://doi.org/10.1016/j.catcom.2012.09.028
CR  - Baroi, C. & Dalai, A. K. (2014). Esterification of free fatty acids (FFA) of Green Seed Canola (GSC) oil using H-Y zeolite supported 12-Tungstophosphoric acid (TPA). Applied Catalysis A: General, 485, 99–107. doi: https://doi.org/10.1016/j.apcata.2014.07.033
CR  - Bhatt, N. & Patel, A. (2011). Supported 12-tungstophosphoricacid: A recoverable solid acid catalyst for liquid phase Friedel-Crafts alkylation of phenol. Journal of the Taiwan Institute of Chemical Engineers, 42(2), 356–362. doi: https://doi.org/10.1016/j.jtice.2010.07.017
CR  - Candu, N., Florea, M., Coman, S. M. & Parvulescu, V. I. (2011). Benzylation of benzene with benzyl alcohol on zeolite catalysts. Applied Catalysis A: General, 393(1–2), 206–214. doi: https://doi.org/10.1016/j.apcata.2010.11.044
CR  - Candu, N., Wuttke, S., Kemnitz, E., Coman, S. M. & Parvulescu, V. I. (2012). Replacing benzyl chloride with benzyl alcohol in heterogeneous catalytic benzylation of aromatic compounds. Pure and Applied Chemistry, 84(3), 427–437. doi: https://doi.org/10.1351/PAC-CON-11-09-34
CR  - Chaube, V. D. (2004). Benzylation of benzene to diphenylmethane using zeolite catalysts. Catalysis Communications, 5(6), 321–326. doi: https://doi.org/10.1016/j.catcom.2004.02.013
CR  - Devassy, B. M. & Halligudi, S. B. (2005). Zirconia-supported heteropoly acids: Characterization and catalytic behavior in liquid-phase veratrole benzoylation. Journal of Catalysis, 236(2), 313–323. doi: https://doi.org/10.1016/j.jcat.2005.09.016
CR  - Freitas, E. F., Araújo, Á. A. L., Paiva, M. F., Dias, S. C. L. & Dias, J. A. (2018). Comparative acidity of BEA and Y zeolite composites with 12-tungstophosphoric and 12-tungstosilicic acids. Molecular Catalysis, 458, 152–160. doi: https://doi.org/10.1016/j.mcat.2018.03.005
CR  - Freitas, E. F., Paiva, M. F., Dias, S. C. L. & Dias, J. A. (2017). Generation and characterization of catalytically active sites of hetoropolyacids on zeolite Y for liquid-phase esterification. Catalysis Today, 289, 70–77. doi: http://dx.doi.org/10.1016/j.cattod.2016.08.010
CR  - Jansen, J. C., Creyghton, E. J., Njo, S. L., van Koningsveld, H. & van Bekkum, H. (1997). On the remarkable behaviour of zeolite Beta in acid catalysis. Catalysis Today, 38(2), 205–212. doi: https://doi.org/10.1016/S0920-5861(97)00070-9
CR  - Jin, H., Ansari, M. B., Jeong, E. Y. & Park, S. E. (2012). Effect of mesoporosity on selective benzylation of aromatics with benzyl alcohol over mesoporous ZSM-5. Journal of Catalysis, 291, 55–62. doi: https://doi.org/10.1016/j.jcat.2012.04.006
CR  - Jovic, A., Bajuk-Bogdanovic, D., Nedic Vasiljevic, B., Milojevic-Rakic, M., Krajisnik, D., Dondur, V., Popa, A., Uskokovic-Markovic, S. & Holclajtner-Antunovic, M. (2017). Synthesis and characterization of 12-phosphotungstic acid supported on BEA zeolite. Materials Chemistry and Physics, 186, 430-437. doi: http://dx.doi.org/10.1016/j.matchemphys.2016.11.015
CR  - Kamalakar, G., Komura, K., Kubota, Y. & Sugi, Y. (2006). Friedel-Crafts benzylation of aromatics with benzyl alcohols catalyzed by heteropoly acids supported on mesoporous silica. Journal of Chemical Technology and Biotechnology, 81(6), 981–988. doi: https://doi.org/10.1002/jctb.1488
CR  - Karabulut, D. & Akyalcin, S. (2021). Friedel-Crafts alkylation of benzene with benzyl alcohol over H-MCM-22. International Journal of Chemical Reactor Engineering, 19(5), 541–551. doi: https://doi.org/10.1515/ijcre-2020-0175
CR  - Katryniok, B., Paul, S., Capron, M., Bellière-Baca, V., Rey, P. & Dumeignil, F. (2012). Regeneration of silica-supported silicotungstic acid as a catalyst for the dehydration of glycerol. ChemSusChem, 5(7), 1298–1306.  doi: https://doi.org/10.1002/cssc.201100635
CR  - Kozhevnikov, I. V. (2007). Sustainable heterogeneous acid catalysis by heteropoly acids. Journal of Molecular Catalysis A: Chemical, 262(1–2), 86–92. doi: https://doi.org/10.1016/j.molcata.2006.08.072
CR  - Kuai, L., Wang, M., Meng, X., Shi, L. & Liu, N. (2022). W Modified HY Zeolite as Catalyst for Alkylation of Aromatic. Catalysis Letters, 152(8), 2480–2490. doi: https://doi.org/10.1007/s10562-021-03820-4
CR  - Kurnia, I., Karnjanakom, S., Bayu, A., Yoshida, A., Rizkiana, J., Prakoso, T., Abudula, A. & Guan, G. (2017). In-situ catalytic upgrading of bio-oil derived from fast pyrolysis of lignin over high aluminum zeolites. Fuel Processing Technology, 167, 730–737. doi: https://doi.org/10.1016/j.fuproc.2017.08.026
CR  - Leng, K., Sun, S., Wang, B., Sun, L., Xu, W. & Sun, Y. (2012). Benzylation of benzene with benzyl chloride on iron-containing mesoporous mordenite. Catalysis Communications, 28, 64–68. doi: https://doi.org/10.1016/j.catcom.2012.08.016
CR  - Li, J., Zhou, Y., Mao, D., Chen, G., Wang, X., Yang, X., Wang, M., Peng, L. & Wang, J. (2014). Heteropolyanion-based ionic liquid-functionalized mesoporous copolymer catalyst for Friedel-Crafts benzylation of arenes with benzyl alcohol. Chemical Engineering Journal, 254, 54–62. doi: https://doi.org/10.1016/j.cej.2014.05.124
CR  - Narkhede, N. & Patel, A. (2013). Biodiesel production by esterification of oleic acid and transesterification of soybean oil using a new solid acid catalyst comprising 12-tungstosilicic acid and zeolite hβ. Industrial and Engineering Chemistry Research, 52(38), 13637–13644. doi: https://doi.org/10.1021/ie402230v
CR  - Pithadia, D., Patel, A. & Hatiya, V. (2022). 12-Tungstophosphoric acid anchored to MCM-22, as a novel sustainable catalyst for the synthesis of potential biodiesel blend, levulinate ester. Renewable Energy, 187, 933–943. doi: https://doi.org/10.1016/j.renene.2022.01.106
CR  - Sakthivel, A., Komura, K. & Sugi, Y. (2008). MCM-48 supported tungstophosphoric acid: An efficient catalyst for the esterification of long-chain fatty acids and alcohols in supercritical carbon dioxide. Industrial and Engineering Chemistry Research, 47(8), 2538–2544. doi: https://doi.org/10.1021/ie071314z
CR  - Satam, J. R. & Jayaram, R. V. (2008). Liquid phase Friedel-Crafts benzylation of aromatics on a polymer-supported 12-tungstophosphoric acid catalyst. Catalysis Communications, 9(9), 1937–1940. doi: https://doi.org/10.1016/j.catcom.2008.03.018
CR  - Sing, K. S. W., Everett, D. H., Haul, R. A. W., Moscou, L., Pierotti, R. A., Rouquerol, J. & Siemieniewska, T. (1985). Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure and Applied Chemistry, 57(4), 603–619. doi: https://doi.org/10.1351/pac198557040603
CR  - Singh, A. P., Bhattacharya, D. & Sharma, S. (1995). Benzoylation of toluene with benzoyl chloride over zeolite catalysts. Journal of Molecular Catalysis A: Chemical, 102(3), 139–145. doi: https://doi.org/10.1016/1381-1169(95)00104-2
CR  - Sun, Y. & Prins, R. (2008). Friedel-Crafts alkylations over hierarchical zeolite catalysts. Applied Catalysis A: General, 336(1–2), 11–16. doi: https://doi.org/10.1016/j.apcata.2007.08.015
CR  - Viswanadham, B., Nagaraju, N., Rohitha, C. N., Vishwanathan, V. & Chary, K. V. R. (2018). Synthesis, Characterization and Catalytic Dehydration of Glycerol to Acrolein Over Phosphotungstic Acid Supported Y-Zeolite Catalysts. Catalysis Letters, 148(1), 397–406. doi: https://doi.org/10.1007/s10562-017-2236-9
CR  - Viswanadham, B., Pavankumar, V. & Chary, K. V. R. (2014). Vapor phase dehydration of glycerol to acrolein over phosphotungstic acid catalyst supported on niobia. Catalysis Letters, 144(4), 744–755. doi: https://doi.org/10.1007/s10562-014-1204-x
CR  - Wang, Y., Sun, Y., Lancelot, C., Lamonier, C., Morin, J. C., Revel, B., Delevoye, L. & Rives, A. (2015). Effect of post treatment on the local structure of hierarchical Beta prepared by desilication and the catalytic performance in Friedel-Crafts alkylation. Microporous and Mesoporous Materials, 206, 42–51. doi: https://doi.org/10.1016/j.micromeso.2014.12.017
CR  - Wang, Y., Song, H. & Sun, X. (2016). Alkylation of toluene with tert-butyl alcohol over HPW-modified Hβ zeolite. Cuihua Xuebao/Chinese Journal of Catalysis, 37(12), 2134–2141. doi: https://doi.org/10.1016/S1872-2067(16)62587-1
CR  - Wang, Z. & Liu, L. (2021). Mesoporous silica supported phosphotungstic acid catalyst for glycerol dehydration to acrolein. Catalysis Today, 376, 55–64. doi: https://doi.org/10.1016/j.cattod.2020.08.007
CR  - Wu, Y., Ye, X., Yang, X., Wang, X., Chu, W. & Hu, Y. (1996). Heterogenization of Heteropolyacids: A General Discussion on the Preparation of Supported Acid Catalysts. Industrial and Engineering Chemistry Research, 35(8), 2546–2560. doi: https://doi.org/10.1021/ie950473s
CR  - Yin, D., Li, C., Tao, L., Yu, N., Hu, S. & Yin, D. (2006). Synthesis of diphenylmethane derivatives in Lewis acidic ionic liquids. Journal of Molecular Catalysis A: Chemical, 245(1–2), 260–265. doi: https://doi.org/10.1016/j.molcata.2005.10.010
CR  - Zeng, X., Wang, Z., Ding, J., Wang, L., Jiang, Y., Stampfl, C., Hunger, M. & Huang, J. (2019). Catalytic arene alkylation over H-Beta zeolite: Influence of zeolite shape selectivity and reactant nucleophilicity. Journal of Catalysis, 380, 9–20. doi: https://doi.org/10.1016/j.jcat.2019.09.035
UR  - https://doi.org/10.31796/ogummf.1464296
L1  - https://dergipark.org.tr/en/download/article-file/3844349
ER  -