Biogasoline production by co-cracking of model compound mixture of bio-oil and ethanol over HSZM-5

doi:10.1016/S1872-2067(14)60046-2

Chinese Journal of Catalysis ›› 2014, Vol. 35 ›› Issue (5): 709-722.DOI: 10.1016/S1872-2067(14)60046-2

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Biogasoline production by co-cracking of model compound mixture of bio-oil and ethanol over HSZM-5

Shurong Wang, Qinjie Cai, Xiangyu Wang, Li Zhang, Yurong Wang, Zhongyang Luo

State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2013-12-05 Revised:2014-01-22 Online:2014-04-18 Published:2014-04-24
Supported by:
This work was supported by the National Natural Science Foundation of China (51276166), the National Basic Research Program of China (973 Program, 2013CB228101), the National Science and Technology Supporting Plan Through Contract (2011BAD22B06), Zhejiang Provincial Natural Science Foundation of China (R1110089), and the Program for New Century Excellent Talents in University (NCET-10-0741).

Abstract

Abstract:

Acids and ketones in biomass pyrolysis oil (bio-oil) can be readily cracked to produce hydrocarbons. They can also be enriched in the distilled fraction using molecular distillation techniques. To simulate the actual composition of the distilled fraction, the co-cracking performance of mixtures of hydroxypropanone, cyclopentanone, and acetic acid with ethanol in a fixed-bed reactor over an HZSM-5 catalyst was studied. The influences of reaction temperature and pressure on the reactant conversion, selectivity, and composition of the oil phase were investigated. At a low reaction temperature of 340 ℃, the conversions of acetic acid and ethanol were as low as 67.9% and 74.4%, respectively, and the oil phase had a low hydrocarbon content of 59.8%, with large amounts of oxygenated byproducts. Cracking under atmospheric pressure also generated a low-quality oil phase with a very low selectivity of only 10.8%. Increasing the reaction temperature promoted reactant conversion and improved the deoxygenation efficiency, whereas increasing the reaction pressure significantly promoted hydrocarbon production. The optimum conditions for biogasoline production were 400 ℃ and 2 MPa. Under these conditions, the reactant conversion reached 100% and the oil phase selectivity was 31.5 wt%. This oil phase consisted entirely of hydrocarbons, 91.5 wt% of which were aromatic hydrocarbons, indicating that the HZSM-5 catalyst had high activity for deoxygenation and aromatization reactions during cracking. In addition, characterization of the spent catalysts and stability tests showed that the catalyst was deactivated after a long reaction time. However, the catalytic activity was recovered by catalyst regeneration.

Key words: Bio-oil, Molecular distillation, Mixed-model compound mixtures, Co-cracking, Bio-gasoline

Shurong Wang, Qinjie Cai, Xiangyu Wang, Li Zhang, Yurong Wang, Zhongyang Luo. Biogasoline production by co-cracking of model compound mixture of bio-oil and ethanol over HSZM-5[J]. Chinese Journal of Catalysis, 2014, 35(5): 709-722.

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Biogasoline production by co-cracking of model compound mixture of bio-oil and ethanol over HSZM-5

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