Catalytic conversion of biomass-derived oils to fuels and chemicals
Adjaye, John Deheer
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Experimental and kinetic modeling studies were carried out on the conversion a wood-oil obtained from high pressure liquefaction of aspen poplar wood to liquid hydrocarbon fuels and useful chemicals in a fixed bed micro-reactor using HZSM-5 catalyst. Similar experiments were conducted using silicalite, H-mordenite, H-Y and amorphous silica-alumina catalysts. Preliminary vacuum distillation studies showed that the wood-oil was made up of volatile and non-volatile fractions. A maximum yield of 62 wt% volatiles at 200 °C, 172 Pa was obtained. The volatile fraction consisted of over 80 compounds. These compounds were comprised of acids, alcohols, aldehydes, ketones, esters, ethers, furans, phenols and some hydrocarbons. The characteristics of the oil showed that it was unstable with time, i.e., its physical properties and chemical composition changed with time probably due to the reaction of free radicals or the oxidative coupling of some of the wood-oil components. However, when the oil was mixed with tetralin, the stability improved. Upgrading studies were first conducted over inert berl saddles in the presence and absence of steam (i. e. non-catalytic treatment/blank runs). Yields of hydrocarbons were between 16 and 25 wt% of the wood-oil. High residue fractions of between 32 to 56 wt% were obtained after processing. Some portions of wood-oil formed a carbonaceous material (char or coke) when exposed to the experimental temperatures. The chars (coke) fraction increased with temperature from 4.7 to 12.5 wt% when processing with steam and 8.0 to 20.4 wt% when processing without steam. Catalytic upgrading studies were first carried out using HZSM-5 catalyst in the presence and absence of steam. The results showed that approximately 40 to 65 wt% of the oil could be converted to a hydrocarbon-rich product (i.e. desired organic liquid product (distillate). This contained about 45 to 70 wt% hydrocarbons with selectivities ranging between 0.47 to 0.88. This fraction was highly aromatic in nature and consisted mainly of benzene, toluene, xylene (BTX compounds) and other alkylated benzenes within the gasoline boiling point range. The yield and selectivities were strong functions of the process time and temperature. A comparison between the two processes, i.e. upgrading in the presence and absence of steam, showed that about 30 to 45 % reduction in coke formation and 5 to 18 wt% increase in organic distillate could be achieved when processing in the presence of steam. These changes were probably due to changes in the rates of cracking, deoxygenation, aromatization and polymerization reactions resulting from the competitive adsorption processes between steam and wood-oil molecules in addition to changes in contact time of molecules. However, the selectivity for hyqrocarbons decreased in the presence of steam. Yields of organic distillate fractions of between 72 to 93 wt% and hydrocarbon yields and selectivities of 44 to 51 wt% and 0.93 to 1.13, respectively, were obtained when wood-oil volatile fraction was upgraded over HZSM-5 after separation from the non-volatile fraction by vacuum distillation. The spent HZSM-5 catalyst could be easily regenerated and reused with little change in its performance. The yields and selectivities for hydrocarbons when upgrading with the other catalysts were between 9 and 22 wt%, and 0.12 and 0.29, respectively for silicalite, 16 and 28 wt%, and 0.22 and 0.28, respectively for H-mordenite, 15.5 and 21 wt%, and 0.17 and 0.21, respectively for H-Y and S.5 and 26.2, and 0.13 and 0.36, resrectively for silica-alumina. Compared to HZSM-5 (yield between 34 and 43 wt%, selectivity of 0.66 to O.SS) these yields and selectivities were much lower. These experiments also showed that the pore size, acidity and shape selectivity of the catalyst influenced the distribution of hydrocarbons in terms of the carbon number. The yield and selectivity of H-mordenite and H-Y (large pore zeolites) were mostly for kerosene range hydrocarbons (C9 to C15) and for silicalite and HZSM-5 (medium pore zeolites) for gasoline range hydrocarbons. The hydrocarbon fraction from amorphous silica-alumina did not show any defined distribution. The performance followed the order: HZSM-5> H-mordenite> H-Y> Silicalite, Silica-alumina. With the aid of model compound reactions involving acetic acid methyl ester, propanoic acid, 4-methylcyclohexanol, methylcyclopentanone, 2-methylcyclopentanone, methoxybenzene, ethoxybenzene, phenol, 2-methoxy-4-(2-propenyl) phenol, a synthetic and wood-oil volatile, two reaction pathways were proposed to explain the chemical steps through which the final products of upgrading were obtained. Also, reaction pathways were proposed for each chemical group. These experiments showed that the final products were formed probably through cracking, deoxygenation, olefin formation, oligomerization, hydrogen and hydride transfer, cyclization, isomerization, alkylation and polymerization reactions. Rate models were derived based upon the two reaction pathways and the power law rate model. The rates of formation of products followed the general order: Organic distillate> Hydrocarbons> Residue> Coke> Gas >Aqueous Fraction. Estimates of the values of the kinetic parameters showed that the rate constants ranged between 10-6 (aqueous fraction) and 1.81 (volatile fraction), activation energies between 6.7-76.0 x 10 3 KJ/Kmol and reaction orders from 0.7 (gas formation) to 2.5 (residue formation). Two mathematical models were derived based on the integral reactor design equation and on the two reaction pathways. This was used to estimate the yield of products. The models predicted the experimental results fairly accurately. Model discrimination showed that the model based on coke and residue formation from both volatile and non-volatile fractions of the wood-oil best predicted the experimental results. Hydrocarbon selectivity relations which were based on coke, residue and combined coke and residue as undesired products were also derived. Application of these relations showed that lower temperatures and concentrations were most appropriate for higher hydrocarbon selectivity. However, this was at the expense of higher conversions.
DegreeDoctor of Philosophy (Ph.D.)
SupervisorBakhshi, Narendra N.
CommitteePostlethwaite, John; Esmail, Mohamed; Cassidy, Richard
Copyright DateFebruary 1993
catalytic conversion; biomass; fuels; chemicals