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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
Article
  • 15 Downloads

Abstract

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.

Keywords

Rapeseed shell Catalytic pyrolysis HZSM-5 Phosphotungstic acid Aromatics 

Abbreviations

PW

Phosphotungstic acid

TGA

Thermogravimetric analysis

FT/IR

Fourier-transform infrared

GC/MS

Gas chromatography/mass spectroscopy

XRD

X-ray diffraction

BET

Brunner-Emmet-Teller

BJH

Barrett-Joyner-Halenda

NH3-TPD

NH3 temperature programmed desorption

TCD

Thermal conductivity detector

Py-IR

Pyridine infrared

TG

Thermogravimetric

DTG

Differential thermogravimetric

GC

Gas chromatography

NIST

National Institute of Standards and Technology

NMR

Nuclear magnetic resonance

NOE

Nuclear Overhauser effect

HHV

Higher heating value

MAH

Monocyclic aromatic hydrocarbon

PAH

Polycyclic aromatic hydrocarbon

LAH

Light aliphatic hydrocarbon

(H/C)eff

Effective hydrogen to carbon ratio

BTEX

Benzene, toluene, ethylbenzene, xylene

RP

Relative proton

RC

Relative carbon

Symbols

n

Reaction order

E

Activation energy, kJ/mol

A

Frequency factor, s−1

B

Brønsted

L

Lewis

R2

Square of correlation coefficient

Notes

Acknowledgments

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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