화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of Industrial and Engineering Chemistry, Vol.79, 452-464, November, 2019
DOI10.1016/j.jiec.2019.07.021  Export Citation
Hierarchical faujasite zeolite-supported heteropoly acid catalyst for acetalization of crude-glycerol to fuel additives
Amin Talebian-Kiakalaieh, and Sara Tarighi†
  • Faculty of Petrochemicals, Iran Polymer and Petrochemical Institute (IPPI), P.O. Box 14975-112, Tehran, Iran
E-mail:
Glycerol acetalization in the presence of aldehydes/ketals and acid catalysts leads to production of fueladditives, which could improve clean fuel ignition, promote combustion process, and reduce fuel gelling in the engine. In this study, hierarchical faujasite zeolite-supported heteropoly acid catalysts (HR/Y) were prepared followed by impregnation of 10, 20 and 30 wt% phosphotungstic acid (HPW). The synthesized catalysts (HR/Y-Wx) were characterized using XRD, FTIR, FESEM, EDX, TEM, NH3-TPD and N2 physisorption analyses. The impregnated hierarchical zeolites along with NaY zeolite were used as catalysts in crude-glycerol acetalization to produce a fuel additive, 4-hydroxymethyl-2,2-dimethyl-1,3- dioxolane (solketal). The catalysts possessed high thermal stability, large specific surface area, large pore diameter (mesoporous structure) and strong acidic sites. The highest solketal yield of 97.85% at 100% crude-glycerol conversion was obtained over the HR/Y-W20 catalyst. Optimization studies revealed that the best solketal yield of 97.87% at complete reaction conversion could be achieved at 40 °C with 10 wt% catalyst weight and 10/1 MR of AC/Gl in 2 h. The synthesized catalyst even maintained its activity after 30 h reaction time due to its mesoporous structure and strong acidity. The impact of real impurities (e.g. water, methanol, and NaCl) on catalyst activity was evaluated and the results revealed that crude-glycerol acetalization over HR/Y-W20 acid catalyst was promising for solketal production with >86% solketal yield at >97% glycerol conversion in the presence of high concentrations of impurities (15 wt% water, 10 wt% methanol, and 15 wt% NaCl). Results confirmed that the prepared HR/Y-W20 catalyst can be a potential candidate for future large scale research and development.
Keywords:Hierarchical faujasite zeolite;Heteropoly acid;Mesoporous structure;Crude-glycerol acetalization;Fuel additives
  1. Liu Z, Wang J, Kang M, Yin N, Wang X, Tan Y, Zhu Y, J. Ind. Eng. Chem., 21, 394 (2015)
  2. Hu K, Wang H, Liu Y, Yang C, J. Ind. Eng. Chem., 28, 334 (2015)
  3. Yang HJ, Lee T, Kim JR, Choi YE, Park CH, J. Ind. Eng. Chem., 75, 158 (2019)
  4. Yin H, Yin H, Wang A, Shen L, J. Ind. Eng. Chem., 57, 226 (2018)
  5. Chieregato A, Soriano MD, Basile F, Liosi G, Zamora S, Concepcion P, Cavani F, Nieto JML, Appl. Catal. B: Environ., 150-151, 37 (2014)
  6. Liu R, Lyu S, Wang T, J. Ind. Eng. Chem., 37, 354 (2016)
  7. Aghbashlo M, Tabatabaei M, Rastegari H, Ghaziaskar HS, Shojaei TR, Renew. Energy, 126, 242 (2018)
  8. Aghbashlo M, Hosseinpour S, Tabatabaei M, Rastegari H, Ghaziaskar HS, Renew. Energ (2018).
  9. Mota CJ, da Silva CX, Rosenbach N, Costa J, da Silva F, Energy Fuel., 24, 2733 (2010)
  10. Bivona LA, Vivian A, Fusaro L, Fiorilli S, Aprile C, Appl. Catal. B Environ. (2019).
  11. Fischer E, Pfahler E, Eur. J. Inorg. Chem., 53, 1606 (1920)
  12. Newman MS, Renoll M, J. Am. Chem. Soc., 67, 1621 (1945)
  13. Chen L, Nohair B, Zhao D, Kaliaguine S, ChemCatChem, 10, 1918 (2018)
  14. Ferreira C, Araujo A, Calvino-Casilda V, Cutrufello MG, Rombi E, Fonseca AM, Microporous Mesoporous Mater., 271, 243 (2018)
  15. Vicente G, Melero JA, Morales G, Paniagua M, Martin E, Green Chem., 12, 899 (2010)
  16. Abreu AV, Meyer CI, Padro C, Martins L, Microporous Mesoporous Mater., 273, 219 (2018)
  17. Vieira LH, Possato LG, Chaves TF, Pulcinelli SH, Santilli CV, Martins L, Mol. Catal., 458, 161 (2018)
  18. Gomes IS, de Carvalho DC, Oliveira AC, Rodriguez-Castellon E, Tehuacanero-Cuapa S, Freire PTC, Filho JM, Saraiva GD, de Sousa FF, Lang R, Chem. Eng. J., 334, 1927 (2018)
  19. Renzo FD, Fajula F, Studies in Surface Science and Catalysis, vol. 157, Elsevier, pp.1 2005.
  20. Primo A, Garcia H, Chem. Soc. Rev., 43, 7548 (2014)
  21. Kuzniarska-Biernacka I, Biernacki K, Magalhaes AL, Fonseca AM, Neves IC, J. Catal., 278(1), 102 (2011)
  22. Stawicka K, Diaz-Alvarez AE, Calvino-Casilda V, Trejda M, Banares MA, Ziolek M, J. Phys. Chem. C, 120, 16699 (2016)
  23. Gonzalez MD, Cesteros Y, Salagre P, Microporous Mesoporous Mater., 144, 162 (2011)
  24. Kowalska-Kus J, Held A, Nowinska K, React. Kinet. Mech. Catal., 117, 341 (2016)
  25. Groen JC, Zhu W, Brouwer S, Huynink SF, Kapteijn F, Moulijn JA, J. Am. Ceram. Soc., 129, 355 (2007)
  26. Li L, Koranyi TI, Sels BF, Pescarmona PP, Green. Chem., 14, 1611 (2012)
  27. Jamil F, Saxena SK, Al-Muhtaseb AH, Baawain M, Al-Abri M, Viswanandham N, J. Clean Prod., 165, 1090 (2017)
  28. Kowalska-Kus J, Held A, Frankowski M, Nowinska K, J. Mol. Catal. A-Chem., 426, 205 (2017)
  29. Verboekend D, Perez-Ramirez J, Catal. Sci. Technol., 1, 879 (2011)
  30. Vogt ETC, Weckhuysen BM, Chem. Soc. rev. (2015).
  31. Zhu SH, Qiu YN, Zhu YL, Hao SL, Zheng HY, Li YW, Catal. Today, 212, 120 (2013)
  32. Alsalme AM, Wiper PV, Khimyak YZ, Kozhevnikova EF, Kozhevnikov IV, J. Catal., 276(1), 181 (2010)
  33. Katryniok B, Paul S, Capron M, Lancelot C, Bellere-Beca V, Rey P, Dumeignil F, Green Chem., 12, 1922 (2010)
  34. Massa M, Andersson A, Finocchio E, Busca G, Lenrick F, Wallenberg LR, J. Catal., 297, 93 (2013)
  35. Massa M, Andersson A, Finocchio E, Busca G, J. Catal., 307, 170 (2013)
  36. Gu YL, Liu SZ, Li CY, Cui QK, J. Catal., 301, 93 (2013)
  37. Castanheiro JE, Fonseca IM, Ramos AM, Oliveira R, Vital J, Catal. Today, 104(2-4), 296 (2005)
  38. Choi JS, Song IK, Lee WY, Catal. Today, 67(1-3), 237 (2001)
  39. Narkhede N, Patel A, R. Soc. Chem. Adv., 4, 19294 (2014)
  40. Garcia-Martinez J, Johnson M, Valla J, Li K, Ying JY, Catal. Sci. technol, 2, 987 (2012)
  41. Etim UJ, Xu BJ, Zhang Z, Zhong ZY, Bai P, Qiao K, Yan ZF, Fuel, 178, 243 (2016)
  42. Mohamed RM, Mkhalid IA, Barakat MA, Arab. J. Chem., 8, 48 (2015)
  43. Gutierrez-Acebo E, Guerrero-Ruiz F, Centenero M, Martinez JS, Salagre P, Cesteros Y, Open Chem., 16, 386 (2018)
  44. Barton DG, Shtein M, Wilson RD, Soled SL, Iglesia E, J. Phys. Chem. B, 103(4), 630 (1999)
  45. Ferreira P, Fonseca IM, Ramos AM, Vital J, Castanheiro JE, Appl. Catal. B: Environ., 98(1-2), 94 (2010)
  46. Maksimovskaya RI, Maksimov GM, Litvak GS, J. Chem. Bull. Int. Ed., 25, 103 (2003)
  47. Talebian-Kiakalaieh A, Amin NAS, Catal. Today, 256, 315 (2015)
  48. Talebian-Kiakalaieh A, Amin NAS, Chin. J. Catal., 38, 1697 (2017)
  49. Kozhevnikov IV, Chem. Rev., 98(1), 171 (1998)
  50. Sulikowski B, Rachwalik R, Appl. Catal. A: Gen., 256(1-2), 173 (2003)
  51. Corma A, Solid State Mater. Sci., 2, 63 (1997)
  52. Pizzio LA, Blanco MN, Microporous Mesoporous Mater., 103, 40 (2007)
  53. Kuang WX, Rives A, Fournier M, Hubaut R, Appl. Catal. A: Gen., 250(2), 221 (2003)
  54. Hussain AI, Aitani AM, Kubu M, Cejka J, Al-Khattaf S, Fuel, 167, 226 (2016)
  55. Ding J, Liu H, Yuan P, Shi G, Bao X, ChemCatChem, 5, 2258 (2013)
  56. Izumi Y, Ono M, Kitagawa M, Yoshida M, Urabe K, Micropor. Mater., 5, 255 (1995)
  57. Chai SH, Wang HP, Liang Y, Xu BQ, Green Chem., 10, 1087 (2008)
  58. Atia H, Armbruster U, Martin A, J. Catal., 258(1), 71 (2008)
  59. Tanabe K, Determination of acidic properties on solid surfaces, Solid Acids and Bases, Academic Press, pp.5 1970.
  60. Talebian-Kiakalaieh A, Amin NAS, Zakaria ZY, J. Ind. Eng. Chem., 34, 300 (2016)
  61. Koyano G, Ueno K, Misono M, Appl. Catal. A: Gen., 181(2), 267 (1999)
  62. Katryniok B, Paul S, Capron M, Belliere-Beca V, Rey P, Dumeignil F, ChemSusChem, 5, 1298 (2012)
  63. Said AA, Abd El-Wahab MMM, Alian AM, J. Chem. Technol. Biotechnol., 82(6), 513 (2007)
  64. Babad-Zakhryapin AA, Gorunov BS, Otd. Khim. N. 14 (1963).
  65. Hodnett BK, Moffat JB, J. Catal., 88, 253 (1984)
  66. Leng Y, Wang J, Jiang P, Catal. Commun., 27, 101 (2012)
  67. Kar P, Mishra BG, Chem. Eng. J., 223, 647 (2013)
  68. Badday AS, Abdullah AZ, Lee KT, Appl. Energy, 105, 380 (2013)
  69. Kapkowski M, Ambrozkiewicz W, Siudyga T, Sitko R, Szade J, Klimontko J, Balin K, Leltko J, Polanski J, Appl. Catal. B: Environ., 202, 335 (2017)
  70. da Silva MJ, Julio AA, Dorigetto FCS, RSC Adv., 5, 44499 (2015)
  71. da Silva CXA, Goncalves VLC, Mota CJA, Green Chem., 11, 38 (2009)
  72. Chandrasekhar S, Chem. Soc. Rev., 16, 313 (1987)
  73. da Silva CXA, Mota CJA, Biomass Bioenergy, 35, 3547e3 (2011)
  74. Shirani M, Ghaziaskar HS, Xu CC, Fuel. Proc. Technol., 124, 206 (2014)
  75. Manjunathan P, Maradur SP, Halgeri AB, Shanbhag GV, J. Mol. Catal. A-Chem., 396, 47 (2015)
  76. Sonar SK, Shinde AS, Asok A, Niphadkar PS, Mayadevi S, Joshi PN, Environ. Prog. Sustain. Energy, 37, 797 (2018)
  77. Trifoi AR, Agachi PS, Pap T, Renew. Sust. Energ. Rev., 62, 804 (2016)
  78. Ruiz VR, Velty A, Santos LL, Leyva-Perez A, Sabater MJ, Iborra S, Corma A, J. Catal., 271(2), 351 (2010)
  79. Li ZB, Miao ZC, Wang X, Zhao JP, Zhou J, Si WJ, Zhuo SP, Fuel, 233, 377 (2018)
  80. Hasabnis A, Mahajani S, Ind. Eng. Chem. Res., 53(31), 12279 (2014)