BACKGROUND: The catalytic processes for valorizing the bio-oil obtained from lignocellulosic biomass pyrolysis face the problem that a great amount of carbonaceous material is deposited on the catalyst due to the polymerization of phenol-derived compounds in the crude bio-oil. This carbonaceous material blocks the catalytic bed and contributes to rapid catalyst deactivation. This paper studies an on-line two-step process, in which the first one separates the polymerizable material and produces a reproducible material whose valorization is of commercial interest. RESULTS: The establishment of a step for pyrolytic lignin deposition at 400 degrees C avoids the blockage of the on-line catalytic bed and attenuates the deactivation of a HZSM-5 zeolite based catalyst used for hydrocarbon production. The origin of catalyst deactivation is coke deposition, which has two fractions (thermal and catalytic), whose content is attenuated by prior pyrolytic lignin separation and by co-feeding methanol. The morphology and properties of the material deposited in the first step (pyrolytic lignin) are similar to lignins obtained as a by-product in wood pulp manufacturing. CONCLUSIONS: The proposed reaction strategy, with two steps (thermal and catalytic) in series, valorizes the crude bio-oil by solving the problems caused by the polymerization of phenolic compounds, which are obtained in the pyrolysis of the lignin contained in lignocellulosic biomass. Given that a by-product (pyrolytic lignin) is obtained with similar properties to the lignin from wood pulping manufacturing, the perspectives for the viability of lignocellulosic biomass valorization are promising, which is essential for furthering its implementation in biorefinery processes. (C) 2009 Society of Chemical Industry