Kees Hogendoorn

Hydrodeoxygenation of pyrolysis oil fractions: process understanding and quality assessment through co-processing in refinery units

Hydrodeoxygenation (HDO) of pyrolysis oil fractions was studied to better understand the HDO of whole pyrolysis oil and to assess the possibility to use individual upgrading routes for these fractions. By mixing pyrolysis oil and water in a 2:1 weight ratio, two fractions were obtained: an oil fraction (OFWA) containing 32 wt% of the organics from the whole oil and an aqueous fraction water addition (AFWA) with the remaining organics. These fractions (and also the whole pyrolysis oil as the reference) were treated under HDO conditions at different temperatures (220, 270 and 310 °C), a constant total pressure of 190 bar, and using 5 wt% Ru/C catalyst. An oil product phase was obtained from all the feedstocks; even from AFWA, 29 wt% oil yield was obtained. Quality parameters (such as coking tendency and H/C) for the resulting HDO oils differed considerably, with the quality of the oil from AFWA being the highest. These HDO oils were evaluated by co-processing with an excess of fossil feeds in catalytic cracking and hydrodesulfurisation (HDS) lab-scale units. All co-processing experiments were successfully conducted without operational problems. Despite the quality differences of the (pure) HDO oils, the product yields upon catalytic cracking of their blends with Long Residue were similar. During co-processing of HDO oils and straight run gas oil in a HDS unit, competition between HDS and HDO reactions was observed without permanent catalyst deactivation. The resulting molecular weight distribution of the co-processed HDO/fossil oil was similar to when hydrotreating only fossil oil and independent of the origin of the HDO oil.

Analytical Solution for facilitated transport across a membrane

An analytical expression for the facilitation factor of component A across a liquid membrane is derived in case of an instantaneous reaction A(g)+B(l)AB(l) inside the liquid membrane. The present expression has been derived based on the analytical results of Olander (A.I.Ch.E. J. 6(2) (1960) 233) obtained for the enhancement factor for G–L systems with bulk. The analytical expression for the facilitation factor allows for arbitrary diffusivities of all species involved and does not contain any simplification or approximations. The facilitation factor starts from the value of unity, goes through a maximum and then reduces back to unity as the equilibrium constant is increased. The maximum facilitation factor occurs at higher values of the equilibrium constant as the ratio of the permeate-complex over carrier diffusivity is reduced whereas the maximum facilitation factor occurs at the same value of the equilibrium constant for all values of DA/DB (ratio of the permeate over carrier diffusivity). A similar behavior is seen for the flux of A as a function of the equilibrium constant. The facilitation factor remains constant with changes in the film thickness whereas the flux of A reduces with an increase in the thickness of the film. A linear increase of the facilitation factor and flux of A are seen with increasing initial carrier concentration.