Abstract

Biomass and waste polystyrene plastic (ratio 1:1) were co-pyrolysed followed by catalysis in a two-stage fixed bed reactor system to produce upgraded bio-oils for production of liquid fuel and aromatic chemicals. The catalysts investigated were ZSM-5 impregnated with different metals, Ga, Co, Cu, Fe and Ni to determine their influence on bio-oil upgrading. The results showed that the different added metals had a different impact on the yield and composition of the product oils and gases. Deoxygenation of the bio-oils was mainly via formation of CO2 and CO via decarboxylation and decarbonylation with the Ni–ZSM-5 and Co–ZSM-5 catalysts whereas higher water yield and lower CO2 and CO was obtained with the ZSM-5, Ga–ZSM-5, Cu–ZSM-5 and Fe–ZSM-5 catalysts suggesting hydrodeoxygenation was dominant. Compared to the unmodified ZSM-5, the yield of single-ring aromatic compounds in the product oil was increased for the Co–ZSM-5, Cu–ZSM-5, Fe–ZSM-5 and Ni–ZSM-5 catalysts. However, for the Ga–ZSM-5 catalyst, single-ring aromatic compounds were reduced, but the highest yield of polycyclic aromatic hydrocarbons was produced. A higher biomass to polystyrene ratio (4:1) resulted in a markedly lower oil yield with a consequent increased yield of gas.

Highlights

  • Lignocellulosic biomass waste includes agricultural residues, forestry waste and municipal solid waste and represents a huge potential global biomass resource

  • We report on the two-stage co-pyrolysis of waste biomass and waste polystyrene directly coupled with a catalyst reactor containing metal-modified (Ga, Co, Cu, Fe, Ni) ZSM-5 zeolite catalysts

  • The results showed that, compared with unmodified ZSM-5 catalyst, the introduction of metal to the ZSM-5 variously influenced the yield of oil, with little effect for the Cu–ZSM-5 and Fe–ZSM-5 catalysts, increased oil yield for the Co–ZSM-5 and Ga–ZSM-5 and lowered oil yield for the Ni–ZSM-5 catalysts

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Summary

Introduction

Lignocellulosic biomass waste includes agricultural residues, forestry waste and municipal solid waste and represents a huge potential global biomass resource. The characteristics of the product bio-oil are not suitable for use directly as a transport fuel or even as a petroleum refinery feedstock since it is chemically very complex containing many different functional groups, it has a high oxygen and moisture content and a tendency to polymerise over a period of time [2]. To overcome these issues there has been extensive research into upgrading the bio-oil by removing the oxygen to produce a hydrocarbon-rich oil suitable for petrochemical feedstock or direct use as a liquid fuel. Routes to removing oxygen from the bio-oil centre on hydrotreatment involving added hydrogen with processing at high pressure (10–20 MPa) [3] or catalytic deoxygenation using zeolite catalysts at atmospheric pressure and moderate temperature (~ 500 °C) [4, 5]

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