Subscriber access provided by University of Colorado Boulder
Article
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
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Energy & Fuels is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 47
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45
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.
ACS Paragon Plus Environment
Energy & Fuels
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
46 47 48 49
Keywords: ICR, FT-ICR, FTMS, Biocrude, Shale Oil, Petroleum
Hydrothermal
2 ACS Paragon Plus Environment
Page 2 of 47
Liquefaction,
HTL,
Page 3 of 47
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
50
Energy & Fuels
■
INTRODUCTION
51
For economic, political, and environmental reasons, the development of
52
alternative fuel sources has become imperative and the generation of liquid
53
fuels derived from biomass is widely sought. Biomass provides hydrocarbon-
54
rich molecules composed of carbohydrates, lignin, proteins, and lipids, all of
55
which can be converted to fuel precusrors.1,2 Hydrothermal liquefaction (HTL)
56
is a favorable thermochemical biomass conversion processes for wet biomass
57
feedstocks.2,3
58
without extensive drying makes HTL less energy intensive and therefore more
59
economical viable than other thermochemical conversion techniques (e.g.,
60
pyrolysis).3
61
biomass feedstocks (e.g., algae, industrial wastes and sewage sludge) to
62
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
63
Through the HTL process, elevated temperature (280-370°C) and
64
pressure (10-25 MPa) convert a biomass slurry (~5-35% dry solids) into a
65
hydrocarbon-rich oil biocrude.1–3
66
and energy recoveries of 60-78% have been reported.3 Ideally, HTL biocrude
67
would be used as an amendment to petroleum in refinery operations to
68
alleviate the demand for conventional fuels. However, biocrudes generally have
69
high oxygen content (5-18%) and potentially high nitrogen content (0.3-8%),
70
depending on feedstock3
71
conventional petroleum fuels, and biocrude must be upgraded independently.
72
Auspicious biocrude yields of 35-64 wt.%
that render this material largely immiscible with
Heterogeneous catalytic hydroprocessing is the forerunner for biocrude
73
upgrading.
74
with hydrodeoxygenation to reduce the oxygen content of wood HTL biocrudes
75
to
76
hydrodenitrogenation, and hydrodesulfurization have been shown to reduce the
77
heteroatom content of microalgae-derived biocrude to 1-2% oxygen,
