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Feb 7, 2017 - Hydrothermal Liquefaction Biocrude Compositions Compared to. Petroleum Crude and Shale Oil. Jacqueline M. Jarvis,. †. Justin M. Billin...
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Hydrothermal Liquefaction Biocrude Compositions Compared to Petroleum Crude and Shale Oil Jacqueline M. Jarvis, Justin M. Billing, Richard T. Hallen, Andrew J. Schmidt, and Tanner M. Schaub Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.6b03022 • Publication Date (Web): 07 Feb 2017 Downloaded from http://pubs.acs.org on February 8, 2017

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Energy & Fuels

Hydrothermal Liquefaction Biocrude Compositions Compared to Petroleum Crude and Shale Oil Jacqueline M. Jarvis,1 Justin M. Billing,2 Richard T. Hallen,2 Andrew J. Schmidt,2 Tanner M. Schaub1,† 1Chemical

Analysis and Instrumentation Laboratory, College of Agricultural, Consumer and Environmental Sciences, New Mexico State University, 945 College Avenue, Las Cruces, NM 88003 USA

2Chemical

and Biological Processes Development Group, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 USA †To whom correspondence should be addressed. [email protected]

(Abstract) We provide a direct and detailed comparison of the chemical composition of petroleum crude oil (from the Gulf of Mexico), shale oil, and three biocrudes (i.e., clean pine, microalgae Chlorella sp., and sewage sludge feedstocks) generated by hydrothermal liquefaction (HTL). Ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) reveals that HTL biocrudes are compositionally more similar to shale oil than petroleum crude oil and that only a few heteroatom classes (e.g., N1, N2, N1O1, and O1) are common to organic sediment- and biomass-derived oils. All HTL biocrudes contain a diverse range of oxygen-containing compounds when compared to either petroleum crude or shale oil. Overall, petroleum crude and shale oil are compositionally dissimilar to HTL oils and >85% of the elemental compositions identified within the positive-ion electrospray (ESI) mass spectra of the HTL biocrudes were not present in either the petroleum crude or shale oil (>43% for negative-ion ESI). Direct comparison of the heteroatom classes that are common to both organic sediment- and biomass-derived oils shows that HTL biocrudes generally contain species with both smaller core structures and a lower degree of alkylation relative to either the petroleum crude or the shale oil. Three-dimensional plots of carbon number versus molecular double bond equivalents (with observed abundance as the third dimension) for abundant molecular classes reveal the specific relationship of the composition of HTL biocrudes to petroleum and shale oils to inform the possible incorporation of these oils into refinery operations as a partial amendment to conventional petroleum feeds.

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Keywords: ICR, FT-ICR, FTMS, Biocrude, Shale Oil, Petroleum

Hydrothermal

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Liquefaction,

HTL,

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Energy & Fuels



INTRODUCTION

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For economic, political, and environmental reasons, the development of

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alternative fuel sources has become imperative and the generation of liquid

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fuels derived from biomass is widely sought. Biomass provides hydrocarbon-

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rich molecules composed of carbohydrates, lignin, proteins, and lipids, all of

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which can be converted to fuel precusrors.1,2 Hydrothermal liquefaction (HTL)

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is a favorable thermochemical biomass conversion processes for wet biomass

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feedstocks.2,3

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without extensive drying makes HTL less energy intensive and therefore more

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economical viable than other thermochemical conversion techniques (e.g.,

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pyrolysis).3

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biomass feedstocks (e.g., algae, industrial wastes and sewage sludge) to

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produce cost-effective, non-petroleum fuel precursors.

The ability to convert high-moisture biomass into liquid fuels

Ultimately, HTL presents an opportunity to utilize a range of

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Through the HTL process, elevated temperature (280-370°C) and

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pressure (10-25 MPa) convert a biomass slurry (~5-35% dry solids) into a

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hydrocarbon-rich oil biocrude.1–3

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and energy recoveries of 60-78% have been reported.3 Ideally, HTL biocrude

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would be used as an amendment to petroleum in refinery operations to

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alleviate the demand for conventional fuels. However, biocrudes generally have

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high oxygen content (5-18%) and potentially high nitrogen content (0.3-8%),

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depending on feedstock3

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conventional petroleum fuels, and biocrude must be upgraded independently.

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Auspicious biocrude yields of 35-64 wt.%

that render this material largely immiscible with

Heterogeneous catalytic hydroprocessing is the forerunner for biocrude

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upgrading.

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with hydrodeoxygenation to reduce the oxygen content of wood HTL biocrudes

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to

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hydrodenitrogenation, and hydrodesulfurization have been shown to reduce the

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heteroatom content of microalgae-derived biocrude to 1-2% oxygen,