Enhancement of Bio-based para-Xylene Selectivity in Catalytic Fast Pyrolysis of Cellulose Using a Surface-modified Mg/P/HZSM-5 Catalyst

Abstract

With the growing consumption of oil, the production of p-xylene(PX) from renewable biomass has gained significant attention recently. This work demonstrated that cellulose, a main component in lignocellulosic biomass, was directly converted into PX over the Mg/P surface-modified zeolites. The catalysts modified by the incorporation of P₂O₅ and MgO into HZSM-5(HZ) promoted the isomerization of m-/o-xylenes to p-xylene. The PX selectivity was greatly enhanced using the modified zeolites due to the deactivation of external surface and the adjustment of pore entrance. In addition, the addition of methanol to cellulose was beneficial to increase the selectivity of xylenes due to the alkylation reactions and the Diels-Alder reactions between cellulose-derived furans and methanol-derived olefins. The highest PX yield of 10.7%(molar fraction) with a high PX selectivity in xylenes(97.1%) was obtained over the 10%Mg/5%P/HZ catalyst. The reaction pathway for the formation of p-xylene was addressed according to the study of the key reactions and the characterization of catalysts.

Keywords

Cellulose / p-Xylene / Diels-Alder reaction / Isomerization / Alkylation

References

[1] Stocker M. Angew. Chem. Int. Ed., 2008, 47(48): 9200.

[2] Jiang P W, Wu X P, Zhu L J, Jin F, Liu J X, Xia T Y, Wang T J, Li Q X. Energy Conversion and Management, 2016, 120: 338.

[3] Binder J B, Raines R T. J. Am. Chem. Soc., 2009, 131(5): 1979.

[4] Liu J X, Jin F, Fan M H, Zhu L J, Tang C, Chang R, Jia Q F, Li Q X. Fuel, 2018, 226: 322.

[5] Wang K G, Kim K H, Brown R C. Green Chem., 2014, 16(2): 727.

[6] Mihalcik D J, Mullen C A, Boateng A A. J. Anal. Appl. Pyrolysis, 2011, 92(1): 224.

[7] Wang S R, Ru B, Lin H Z, Sun W X, Yu C J, Luo Z Y. Chem. Res. Chinese Universities., 2014, 30(5): 848.

[8] Carlson T R, Tompsett G A, Conner W C, Huber G W. Top. Catal., 2009, 52(3): 241.

[9] Chang R, Zhu L J, Jin F, Fan M H, Liu J X, Jia Q F, Tang C, Li Q X. J. Chem. Technol. Biotechnol., 2018, 93(11): 3292.

[10] Xu L J, Yao Q, Deng J, Han Z, Zhang Y, Fu Y, Huber G W, Guo Q X. ACS Sustain. Chem. Eng., 2015, 3(11): 2890.

[11] Li X Y, Zhang H F, Li J, Su L, Zuo J E, Komarneni S, Wang Y J. Appl. Catal. A: Gen., 2013, 455: 114.

[12] Cheng Y T, Wang Z P, Gilbert C J, Fan W, Huber G W. Angew. Chem. Int. Ed., 2012, 51(44): 11097.

[13] Cheng Y T, Jae J, Shi J, Fan W, Huber G W. Angew. Chem. Int. Ed., 2012, 51(6): 1387.

[14] Ashraf M T, Chebbi R, Darwish N A. Ind. Eng. Chem. Res., 2013, 52(38): 13730.

[15] Pang J F, Zheng M Y, Sun R Y, Wang A Q, Wang X D, Zhang T. Green Chem., 2016, 18(2): 342.

[16] Maneffa A, Priecel P, Lopez-Sanchez J A. ChemSusChem, 2016, 9(19): 2736.

[17] Chang C C, Cho H J, Yu J Y, Gorte R J, Gulbinski J, Dauenhauer P, Fan W. Green Chem., 2016, 18(5): 1368.

[18] Williams C L, Chang C C, Do P, Nikbin N, Caratzoulas S, Vlachos D G, Lobo R F, Fan W, Dauenhauer P J. ACS Catal., 2012, 2(6): 935.

[19] Do P T M, McAtee J R, Watson D A, Lobo R F. ACS Catal., 2013, 3(1): 41.

[20] Chang C C, Green S K, Williams C L, Dauenhauer P J, Fan W. Green Chem., 2014, 16(2): 585.

[21] Tang C, Zhu L J, Fan M H, Li Q X. Chin. J. Chem. Phys., 2018, 31(6): 843.

[22] Jin F, Fan M H, Jia Q F, Li Q X. Chin. J. Chem. Phys., 2017, 30(3): 348.

[23] Zhang J G, Qian W Z, Kong C Y, Wei F. ACS Catal., 2015, 5(5): 2982.

[24] Wu X P, Jiang P W, Jin F, Liu J X, Zhang Y H, Zhu L J, Xia T Y, Shao K L, Wang T J, Li Q X. Fuel, 2017, 188: 205.

[25] Wu X P, Fan M H, Li Q X. Chin. J. Chem. Phys., 2017, 30(4): 479.

[26] Zhu L J, Jin F, Fan M H, Liu J X, Chang R, Jia Q F, Tang C, Li Q X. Chem. Eng. Technol., 2018, 41(5): 1027.

[27] Zhang Y H, Fan M H, Chang R, Li Q X. Chin. J. Chem. Phys., 2017, 30(5): 588.

[28] Fan M H, Ge S L, Zhang Z, Xie Y S, Li Q X. Chin. J. Chem. Phys., 2018, 31(5): 725.

[29] Lu J H, Zhou S, Ma K, Meng M, Tian Y. Chin. J. Catal., 2015, 36(8): 1295.

[30] Yu X, Zhang Y W, Liu B, Ma H Y, Wang Y, Bao Q, Wang Z L. Chem. Res. Chinese Universities, 2018, 34(3): 485.

[31] Mao D S, Yang W M, Xia J C, Zhang B, Song Q Y, Chen Q L. J. Catal., 2005, 230(1): 140.

[32] Jia Q F, Zhu L J, Fan M H, Li Q X. Chin. J. Org. Chem., 2018, 38(8): 2101.

[33] Zhou G Q, Li J, Yu Y Q, Li X Y, Wang Y J, Wang W, Komarneni S. Appl. Catal. A: Gen., 2014, 487: 45.

[34] Dorado C, Mullen C A, Boateng A A. Appl. Catal. B: Environ., 2015, 162: 338.

[35] Cheng Y T, Huber G W. Green Chem., 2012, 14(11): 3114.

[36] Mettler M S, Vlachos D G, Dauenhauer P J. Energy Environ. Sci., 2012, 5(7): 7797.