Tracking Renewable Carbon in Bio-Oil/Crude Co-Processing with VGO through 13C/12C Ratio Analysis

Li, Zheng-Hua; Magrini-Bair, Kimberly; Wang, Huamin; Maltsev, Oleg V.; Geeza, Thomas J.; Mora, Claudia I.; Lee, James E.

doi:10.1016/j.fuel.2020.117770

Tracking Renewable Carbon in Bio-Oil/Crude Co-Processing with VGO through 13C/12C Ratio Analysis

Journal Article · Fri May 08 04:00:00 EDT 2020 · Fuel

DOI:https://doi.org/10.1016/j.fuel.2020.117770· OSTI ID:1677491

Li, Zheng-Hua; ; Wang, Huamin; Maltsev, Oleg V.; Geeza, Thomas J.; Mora, Claudia I.; Lee, James E.

Biomass-derived pyrolosis oil (aka. Bio-oil) contains high oxygen and other heteroatoms that prevent it from being directly used as a conventional fuel due to its thermal instability, non-volatility and corrosivity. Co-processing the bio-oil with vacuum gas oil (VGO, a petroleum refining feedstock) leverages the existing petroleum refining infrastructure which significantly reduces Capex for the bio-oil pathway. Increasing renewable carbon incorporation into conventional fuels is a critical step in biofuels development and adoption. To take advantage of this approach, a fast, economic and accurate method with a potenial online monitoring capability is needed for tracking the renewable carbon through processing and then using the information to guide optimization of the co-processing parameters to maximize renewable carbon incorporation in fuel products. Here, we have developed a high-precision analytical protocol that enables accurate 13C/12C ratio analysis for bio-oil/crude samples. Our study demonstrates that high-precision 13C/12C ratio analysis can be a viable way to track renewable carbon incorporation in bio-oil co-processing products including the feedstock derived from C3 plants and guide the optimization of the co-processing parameters. Comparison of d13C with radiocarbon (14C) results obtained by an accelerator mass spectrometer (AMS) reveals a significant correlation (R2 = 0.998) and confirms d13C applicability for tracking renewable carbon in co-processing systems. Because C4 plant-derived bio-oils (-13‰) possesess more distinct d13C values than C3 plant-derived bio-oils (-26‰) relative to VGO (~-30‰), the use of C4 plant-derived feedstock will greatly increase the renewable C traceability through 13C/12C ratio analysis in bio-oil co-processing.

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 1677491

Report Number(s):: NREL/JA-5100-78096; MainId:32005; UUID:c567c4b6-8f3d-42da-aba4-c9ffc3a258cc; MainAdminID:18696

Journal Information:: Fuel, Journal Name: Fuel Vol. 275

Country of Publication:: United States

Language:: English

References (30)

Quantification and classification of cotton biodiesel content in diesel blends, using mid-infrared spectroscopy and chemometric methods Máquina, Ademar Domingos Viagem; Sitoe, Baltazar Vasco; Buiatte, José Eduardo Fuel, Vol. 237 https://doi.org/10.1016/j.fuel.2018.10.011	journal	February 2019
Carbon isotopes characterize rapid changes in atmospheric carbon dioxide during the last deglaciation Bauska, Thomas K.; Baggenstos, Daniel; Brook, Edward J. Proceedings of the National Academy of Sciences, Vol. 113, Issue 13 https://doi.org/10.1073/pnas.1513868113	journal	March 2016
Quantification of soybean biodiesels in diesel blends according to ASTM E1655 using mid-infrared spectroscopy and multivariate calibration Gontijo, Lucas Caixeta; Guimarães, Eloiza; Mitsutake, Hery Fuel, Vol. 117 https://doi.org/10.1016/j.fuel.2013.10.043	journal	January 2014
Discriminant analysis of biodiesel fuel blends based on combined data from Fourier Transform Infrared Spectroscopy and stable carbon isotope analysis dos Santos, Victor Hugo J. M.; Ramos, Alessandro S.; Pires, Jéssica P. Chemometrics and Intelligent Laboratory Systems, Vol. 161 https://doi.org/10.1016/j.chemolab.2016.12.004	journal	February 2017
The fate of bio-carbon in FCC co-processing products Fogassy, Gabriella; Thegarid, Nicolas; Schuurman, Yves Green Chemistry, Vol. 14, Issue 5 https://doi.org/10.1039/c2gc35152h	journal	January 2012
Biodiesel content determination in diesel fuel blends using near infrared (NIR) spectroscopy and support vector machines (SVM) Alves, Julio Cesar L.; Poppi, Ronei J. Talanta, Vol. 104 https://doi.org/10.1016/j.talanta.2012.11.033	journal	January 2013
Bomb Produced ¹⁴ C Content in Tree Rings Grown at Different Latitudes Dai, Kai-Mei; Fan, C. Y. Radiocarbon, Vol. 28, Issue 2A https://doi.org/10.1017/S003382220000744X	journal	January 1986
New Bomb Pulse Radiocarbon Records from Annual Tree Rings in the Northern Hemisphere Temperate Region Quarta, G.; D'Elia, M.; Valzano, D. Radiocarbon, Vol. 47, Issue 1 https://doi.org/10.1017/S0033822200052164	journal	January 2005
Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements: Caffeines, n -Alkanes, Fatty Acid Methyl Esters, Glycines, l -Valines, Polyethylenes, and Oils Schimmelmann, Arndt; Qi, Haiping; Coplen, Tyler B. Analytical Chemistry, Vol. 88, Issue 8 https://doi.org/10.1021/acs.analchem.5b04392	journal	March 2016
Influence of earlywood–latewood size and isotope differences on long-term tree-ring δ13C trends Li, Zheng-Hua; Leavitt, Steven W.; Mora, Claudia I. Chemical Geology, Vol. 216, Issue 3-4 https://doi.org/10.1016/j.chemgeo.2004.11.007	journal	March 2005
Carbon Isotope Constraints on the Deglacial CO2 Rise from Ice Cores Schmitt, J.; Schneider, R.; Elsig, J. Science, Vol. 336, Issue 6082 https://doi.org/10.1126/science.1217161	journal	March 2012
Calibration sets selection strategy for the construction of robust PLS models for prediction of biodiesel/diesel blends physico-chemical properties using NIR spectroscopy Palou, Anna; Miró, Aira; Blanco, Marcelo Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 180 https://doi.org/10.1016/j.saa.2017.03.008	journal	June 2017
Expansion of C4 ecosystems as an indicator of global ecological change in the late Miocene Cerling, Thure E.; Wang, Yang; Quade, Jay Nature, Vol. 361, Issue 6410 https://doi.org/10.1038/361344a0	journal	January 1993
Evolution of the stable carbon isotope composition of atmospheric CO ₂ over the last glacial cycle Eggleston, S.; Schmitt, J.; Bereiter, B. Paleoceanography, Vol. 31, Issue 3 https://doi.org/10.1002/2015PA002874	journal	March 2016
Co-processing raw bio-oil and gasoil in an FCC Unit Pinho, Andrea de Rezende; de Almeida, Marlon B. B.; Mendes, Fabio Leal Fuel Processing Technology, Vol. 131 https://doi.org/10.1016/j.fuproc.2014.11.008	journal	March 2015
Retrospective Birth Dating of Cells in Humans Spalding, Kirsty L.; Bhardwaj, Ratan D.; Buchholz, Bruce A. Cell, Vol. 122, Issue 1 https://doi.org/10.1016/j.cell.2005.04.028	journal	July 2005
CFD simulations of catalytic hydrodeoxygenation of bio-oil using Pt/Al ₂ O ₃ in a fixed bed reactor Subramanyam, Malladi D.; Gollakota, Anjani R. K.; Kishore, Nanda RSC Advances, Vol. 5, Issue 110 https://doi.org/10.1039/C5RA14985A	journal	January 2015
Carbon isotope compositions of terrestrial C3 plants as indicators of (paleo)ecology and (paleo)climate Kohn, M. J. Proceedings of the National Academy of Sciences, Vol. 107, Issue 46 https://doi.org/10.1073/pnas.1004933107	journal	November 2010
Micro-scale analysis of tree-ring δ18O and δ13C on α-cellulose spline reveals high-resolution intra-annual climate variability and tropical cyclone activity Li, Zheng-Hua; Labbé, Nicole; Driese, Steven G. Chemical Geology, Vol. 284, Issue 1-2 https://doi.org/10.1016/j.chemgeo.2011.02.015	journal	May 2011
Co-processing bio-oil in the refinery for drop-in biofuels via fluid catalytic cracking Stefanidis, Stylianos D.; Kalogiannis, Konstantinos G.; Lappas, Angelos A. Wiley Interdisciplinary Reviews: Energy and Environment, Vol. 7, Issue 3 https://doi.org/10.1002/wene.281	journal	December 2017
A new spectrophotometric method for determination of biodiesel content in biodiesel/diesel blends Silva, Marcos A. A.; Correa, Renan A.; Tavares, Maria G. de O. Fuel, Vol. 143 https://doi.org/10.1016/j.fuel.2014.10.048	journal	March 2015
Alternative method to quantify biodiesel and vegetable oil in diesel-biodiesel blends through 1 H NMR spectroscopy Shimamoto, Gustavo G.; Bianchessi, Luis F.; Tubino, Matthieu Talanta, Vol. 168 https://doi.org/10.1016/j.talanta.2017.03.027	journal	June 2017
Determination of biodiesel content in biodiesel/diesel blends using NIR and visible spectroscopy with variable selection Fernandes, David Douglas Sousa; Gomes, Adriano A.; Costa, Gean Bezerra da Talanta, Vol. 87 https://doi.org/10.1016/j.talanta.2011.09.025	journal	December 2011
Biobased carbon content quantification through AMS radiocarbon analysis of liquid fuels Haverly, Martin R.; Fenwick, Scott R.; Patterson, Fredd P. K. Fuel, Vol. 237 https://doi.org/10.1016/j.fuel.2018.10.081	journal	February 2019
In-situ upgrading of biomass pyrolysis vapors: Catalyst screening on a fixed bed reactor Stefanidis, S. D.; Kalogiannis, K. G.; Iliopoulou, E. F. Bioresource Technology, Vol. 102, Issue 17 https://doi.org/10.1016/j.biortech.2011.06.032	journal	September 2011
Classification of Fuel Blends Using Exploratory Analysis with Combined Data from Infrared Spectroscopy and Stable Isotope Analysis Santos, Victor Hugo J. M. dos; Ketzer, João M. M.; Rodrigues, Luiz F. Energy & Fuels, Vol. 31, Issue 1 https://doi.org/10.1021/acs.energyfuels.6b01937	journal	December 2016
Fast pyrolysis oil from pinewood chips co-processing with vacuum gas oil in an FCC unit for second generation fuel production Pinho, Andrea de Rezende; de Almeida, Marlon B. B.; Mendes, Fabio Leal Fuel, Vol. 188 https://doi.org/10.1016/j.fuel.2016.10.032	journal	January 2017
Green Oil Production by Hydroprocessing Chen, Song International Journal of Clean Coal and Energy, Vol. 01, Issue 04 https://doi.org/10.4236/ijcce.2012.14005	journal	January 2012
Coprocessing of Catalytic-Pyrolysis-Derived Bio-Oil with VGO in a Pilot-Scale FCC Riser Wang, Chenxi; Li, Mingrui; Fang, Yunming Industrial & Engineering Chemistry Research, Vol. 55, Issue 12 https://doi.org/10.1021/acs.iecr.5b03008	journal	March 2016
Isotope-abundance variations of selected elements (IUPAC Technical Report) Coplen, Tyler B.; Böhlke, John Karl; De Bièvre, P. Pure and Applied Chemistry, Vol. 74, Issue 10 https://doi.org/10.1351/pac200274101987	journal	January 2002

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