Article pubs.acs.org/IECR
Selective Production of 4‑Vinylphenol by Fast Pyrolysis of Herbaceous Biomass Yan-Chao Qu,† Zhi Wang,† Qiang Lu,*,‡ and Ying Zhang*,† †
Anhui Province Key Laboratory of Biomass Clean Energy, University of Science and Technology of China, Hefei 230026, P. R. China ‡ National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, Beijing, P. R. China S Supporting Information *
ABSTRACT: 4-Vinylphenol is an important chemical that can be used as the monomer for the production of poly(4vinylphenol) (PVPh). Currently, 4-vinylphenol was prepared by the dehydrogenation of 4-ethylphenol over chromia/alumina catalyst at 600 °C. In this study, a low-cost process involving low-temperature fast pyrolysis of biomass without any catalyst was developed to selectively produce 4-vinylphenol. Pyrolysis gas chromatography/mass spectrometry (Py−GC/MS) was used for the fast pyrolysis of bagasse, cornstalk, bamboo, rice husk, rice straw, cotton straw, and poplar wood to investigate the effects of different materials on the selectivity of 4-vinylphenol. It was found that some of the herbaceous materials, such as bagasse, cornstalk, and bamboo, were suitable for the production of 4-vinylphenol, whereas woody materials were not applicable. The effects of temperature on 4-vinylphenol production were also investigated. 4-Vinylphenol contents of up to 7 and 20 wt % were achieved at 300 °C from bagasse and bagasse EMAL, respectively. For the first time, 4-vinylphenol was separated from the pyrolysis oil obtained by the fast pyrolysis of bagasse using a benchtop unit, and its structure was confirmed by various methods. Additionally, it was verified that 4-vinylphenol could be produced from compounds with a β-5 linkage, and a possible mechanism for the generation of 4-vinylphenol from a lignin model compound with a β-5 linkage is proposed.
1. INTRODUCTION With continuing concerns over fossil-fuel shortages and severe environmental problems, it is imperative to develop economical and energy-efficient processes for obtaining sustainable fuels and chemicals.1,2 In this respect, the utilization of lignocellulosic biomass resources will play an increasingly important role.3 Biomass can be converted into a variety of fuels or chemicals by many technologies. Among the available technologies, fast pyrolysis, the thermal decomposition of biomass in the absence of oxygen to solid, liquid, and gaseous products, has been extensively studied.4−6 Fast pyrolysis has many advantages over other conversion processes, including that it (1) converts solid biomass into liquid products in a single step with one reactor, (2) operates with short residence times (
