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ARS Home » Northeast Area » Wyndmoor, Pennsylvania » Eastern Regional Research Center » Sustainable Biofuels and Co-products Research » Research » Publications at this Location » Publication #366923

Research Project: Farm-Scale Pyrolysis Biorefining

Location: Sustainable Biofuels and Co-products Research

Title: Cleanup and conversion of biomass liquefaction aqueous phase to C3-C5 olefins over ZnxZryOz catalyst

item DAVIDSON, STEPHEN - Pacific Northwest National Laboratory
item FLAKE, MATTHEW - Pacific Northwest National Laboratory
item LOPEZ-RUIZ, JUAN - Pacific Northwest National Laboratory
item COOPER, ALAN - Pacific Northwest National Laboratory
item Elkasabi, Yaseen
item TOMASI, MORGANO - Karlsruhe Institute Of Technology
item LEBARBIER, DAGLE - Pacific Northwest National Laboratory
item ALBRECHT, KARL - Archer Daniels Midland
item DANGLE, ROBERT - Pacific Northwest National Laboratory

Submitted to: Catalysts
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 11/1/2019
Publication Date: 11/6/2019
Publication URL:
Citation: Davidson, S.D., Flake, M., Lopez-Ruiz, J.A., Cooper, A.R., Elkasabi, Y.M., Tomasi, M.M., Lebarbier, D.V., Albrecht, K.O., Dangle, R.A. 2019. Cleanup and conversion of biomass liquefaction aqueous phase to C3-C5 olefins over ZnxZryOz catalyst. Catalysts. 9(11):1-15.

Interpretive Summary: Corn stalks, horse litter, and other types of agricultural waste (“biomass”) can be converted into oils that resemble petroleum, using a high-temperature process that breaks down biomass in the absence of oxygen (termed “pyrolysis”). The oils can be refined to produce liquid fuels. At the same time, pyrolysis produces an additional water-rich product that is contaminated with miscellaneous chemicals (about 10-20%), making it difficult to use without further treatment. The rate of conversion of these chemicals into useful products can be increased by catalysts that effectively work in a high-temperature water environment. This work used a specific catalyst to convert water-rich waste products into higher-value chemicals. All of the chemicals found in the water product successfully converted into two main products: isobutene, a light petrochemical used to make many high-volume chemicals and materials, and carbon dioxide. It was found that more butene could be produced by use of the suitable type of gas that was fed to the reactor. These results have important applications for increasing the economic viability of a biorefinery, such that the wastes produced can be converted into useful marketable products.

Technical Abstract: The viability of using a previously studied ZnxZryOz catalyst for the direct production of olefins from aqueous phase bio-oil feedstocks was explored. In this work, we looked at three different bio-mass derived aqueous phases: hydrothermal liquefaction of cornstover, fluidized bed fast pyrolysis of horse litter, and screw pyrolysis of wood pellets. While overall composition varied for each feedstock, the main components for each were the carboxylic acids, acetic acid and propionic acid. Expanding on a previously reported clean up process, a continuous liquid-liquid extraction process was developed instead of a batch process. Complete conversion of the carboxylic acids over the ZnxZryOz catalyst was achieved for all feedstocks. The main product for all feedstocks was isobutene, followed by CO2. While all feedstocks were able to be converted, the content of non-participating carbon was found to increase deactivation of the ZnxZryOz catalyst. The effect of gas environment was also studied. By changing the carrier gas from N2 to H2, the selectivity to propene was increased while selectivity to isobutene decreased.