Catalytic Conversion of Biomass for Aromatics Over HZSM-5 Modified by Dawson-Type Phosphotungstic Acid

  • Yongsheng FanEmail author
  • Lele Fan
  • Lei Zhu
  • Jiawei Wang
  • Wei Ji
  • Yixi Cai
  • Weidong Zhao


The multi-functional zeolites modified with different phosphotungstic acid (PW) ratios were prepared and characterized. Thermogravimetric tests coupled with kinetics analysis were performed to evaluate catalytic pyrolysis behavior of biomass; The presence of HZSM-5 inhibited the product diffusion, causing a slight delay of pyrolysis; The PW modification made the reaction more complex; reaction order increased from 1.96 to 2.12. The activation energy decreased from 53.32 to 31.15 kJ/mol with the increase of PW. Then, fixed-bed catalytic experiments were further conducted to investigate aromatics production; 10%PW modification gave the appropriate acidic distribution and pore structure, resulting in oxygen being more likely to be removed in the form of COx. Although the organic yield was only 10.73%, HHV reached 38.01 MJ/kg. The organic phase catalyzed by 10%PW/HZSM-5 exhibited higher aromatization degree, and the structures of benzene ring were mainly single-rings. The oxygenates (especially for phenols from 16.88% to undetected) reduced obviously with increasing PW loading, and the 10%PW modification gave the highest content (peak area, %) of desirable mono-aromatic hydrocarbons (52.29%). The GC/MS analysis results were basically consistent with the 1H/13C NMRs. Besides, the 10%PW/HZSM-5 had the highest catalytic stability and the spent catalyst could recover high activity after regeneration. Therefore, catalytic pyrolysis of biomass using Dawson-structured PW-modified HZSM-5 is a promising approach for production of light aromatic hydrocarbons.


Rapeseed shell Catalytic pyrolysis HZSM-5 Phosphotungstic acid Aromatics 



Phosphotungstic acid


Thermogravimetric analysis


Fourier-transform infrared


Gas chromatography/mass spectroscopy


X-ray diffraction






NH3 temperature programmed desorption


Thermal conductivity detector


Pyridine infrared




Differential thermogravimetric


Gas chromatography


National Institute of Standards and Technology


Nuclear magnetic resonance


Nuclear Overhauser effect


Higher heating value


Monocyclic aromatic hydrocarbon


Polycyclic aromatic hydrocarbon


Light aliphatic hydrocarbon


Effective hydrogen to carbon ratio


Benzene, toluene, ethylbenzene, xylene


Relative proton


Relative carbon



Reaction order


Activation energy, kJ/mol


Frequency factor, s−1






Square of correlation coefficient



The authors thank the Analysis and Testing Center of Yancheng Institute of Technology for the technical support.

Funding information

This work is currently supported by the National Natural Science Foundation of China (51806186) and the Scientific Research Project for the Introduction Talent of Yancheng Institute of Technology (XJ201708).

Supplementary material

12155_2019_10075_MOESM1_ESM.doc (1.7 mb)
ESM 1 (DOC 1775 kb)


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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Automotive EngineeringYancheng Institute of TechnologyYanchengPeople’s Republic of China
  2. 2.Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu ProvinceYancheng Institute of TechnologyYanchengPeople’s Republic of China
  3. 3.School of Automotive and Traffic EngineeringJiangsu UniversityZhenjiangPeople’s Republic of China

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