Deactivating species in the transformation of crude bio-oil with methanol into hydrocarbons on a HZSM-5 catalyst

Abstract

A study has been carried out by using different techniques (TPO, FTIR, Raman, 13C NMR, GC/MS of the coke dissolved in CH 2Cl 2) on the nature of the coke deposited on a HZSM-5 catalyst modified with Ni in the transformation of the crude bio-oil obtained by flash pyrolysis of lignocellulosic biomass (pine sawdust) into hydrocarbons. The reaction system has two steps in-line. In the first one, the components of crude bio-oil derived from the pyrolysis of biomass lignin are polymerized at 400 °C. In the second one, the remaining volatile oxygenates are transformed into hydrocarbons in a fluidized bed catalytic reactor at 450 °C. The reaction has been carried out with different bio-oil/methanol mass ratios in the feed (from 100/0 to 0/100). Co-feeding methanol significantly attenuates coke deposition, and the nature of the coke components varies according to the bio-oil/methanol ratio in the feed. When bio-oil is co-fed, the coke deposited on the catalyst has a significant content of oxygenates and oxo-aromatics and consists of two fractions, identified by temperature programmed oxidation, corresponding to external and internal coke in the zeolite crystals. The fraction of external coke is soluble in CH 2Cl 2, with a high content of oxygenates and oxo-aromatics, and is generated by polymerization of products derived from biomass lignin pyrolysis activated by the zeolite acid sites. The fraction of coke retained within the zeolite crystals is partially insoluble and is formed by several routes: from the intermediates in the transformation of both methanol and bio-oil oxygenates into hydrocarbons; by evolution of the other coke fraction; from the hydrocarbons (with high aromatics content) in the reaction medium. © 2011 Elsevier Inc. All rights reserved.