Tracking renewable carbon in bio-oil/crude co-processing with VGO through 13C/12C ratio analysis

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

doi:10.1016/j.fuel.2020.117770

Cited by 16 publications

(29 citation statements)

References 32 publications

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“…During the course of this study taking place, the long-term stability and precision of the analytical protocol and the MAT253 mass spectrometer were monitored by analyzing NBS22 and yielded a standard deviation of ±0.013‰ over 12 months, indicating excellent long-term stability and high precision of the analytical protocol. 28 The mean δ 13 C value for NBS22 (−30.022 ± 0.013‰) is consistent with the recently assigned value of −30.02 ± 0.04‰ obtained from an international isotope reference material project. 38 ■ RESULTS AND DISCUSSION δ 13 C Results of Biodiesel Blending Experiment.…”

Section: ■ Methods and Experimentssupporting

confidence: 88%

“…The method used for high-precision δ 13 C analysis of bio-oil, biocrude, VGO, and their coprocessing products was described elsewhere. 28 Prior to the sample δ 13 C analysis, a δ 13 C zero-enrichment (aka reference on/off) test was carried out for approximately 2 h to ensure instrument stability. During the on/off test, the sample port in the Conflo IV was open to make sure the background CO 2 signal was stable.…”

Section: ■ Methods and Experimentsmentioning

confidence: 99%

“…We observed that VGO-only refining resulted in 13 C enrichment by 1.140‰ in liquid hydrocarbon products. 28 Renewable carbon% in a specific coprocessing product can be obtained by eq 6 (written for the example of liquid products)…”

Section: ■ Isotope-mixing Modelmentioning

confidence: 99%

“…Some of these products may favor incorporation of the lighter 12 C isotope in comparison to that of 13 C causing an isotopic fractionation. We observed that VGO-only refining resulted in 13 C enrichment by 1.140‰ in liquid hydrocarbon products . Renewable carbon% in a specific coprocessing product can be obtained by eq (written for the example of liquid products) where Δ (l)fos 13 and Δ (l)bio 13 represent the δ 13 C isotopic offset between the feedstock and liquid product for VGO and bio-oil, respectively.…”

Section: Isotope-mixing Modelmentioning

confidence: 99%

“…Compared to a multimillion-dollar AMS, an IRMS is a fraction of the cost. Stable carbon isotopic methods have been explored for qualitatively tracking renewable carbon in biofuel blends and bio-oil coprocessed products. − In this study, we report a quantitative approach to determine the renewable carbon contents in coprocessed products through high-precision stable carbon isotopic analysis and demonstrate a low detection limit comparable to the 14 C AMS method.…”

Section: Introductionmentioning

confidence: 99%

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Quantitative Determination of Biomass-Derived Renewable Carbon in Fuels from Coprocessing of Bio-Oils in Refinery Using a Stable Carbon Isotopic Approach

Wang

Magrini

et al. 2020

ACS Sustainable Chem. Eng.

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Increasing renewable carbon incorporation into conventional fuels through coprocessing with vacuum gas oil (VGO, a petroleum refining feedstock) is a critical step in biofuel development, scaling-up, adoption, and associated GHG reduction. Optimization of the coprocessing parameters maximizes incorporation of the renewable carbon in the fuel products. Quantitative determination of the renewable carbon content in the coprocessed products provides direct evaluation of these parameters. The coprocessing bio-oil with VGO through hydrocracking (HC) or fluid catalytic cracking (FCC) system resulted in carbon isotopic fractionation that prevented the direct use of the isotope-mixing model for quantifying the renewable carbon. Here, we report an algorithm of using a stable carbon isotope approach to quantify the renewable carbon content in coprocessing biofuel products through high-precision δ13C analysis. A controlled experiment carried out by blending a fossil diesel (−29.013‰) with a biodiesel (−30.099‰) at various blending levels up to 98.0/2.0 wt % is presented and has demonstrated the applicability of this approach. The carbon isotope fractionation factors for the bio-oil coprocessing were obtained by using a 14C-derived isotope-mixing model. The δ13C method was tested by coprocessing 13C-labeled biocrude and natural woody biomass-derived fast pyrolysis (FP) and catalytic fast pyrolysis (CFP) bio-oils with VGO. The results were verified by 14C accelerator mass spectrometry (AMS) method (ASTM-D6866) and compared with the yield mass balance method. Strong agreement between δ13C and 14C AMS methods demonstrated the applicability of the δ13C method to quantify renewable carbon content in coprocessing fuel products and guide the coprocessing optimization.

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Section: ■ Methods and Experimentssupporting

confidence: 88%

Section: ■ Methods and Experimentsmentioning

confidence: 99%

Section: ■ Isotope-mixing Modelmentioning

confidence: 99%

Section: Isotope-mixing Modelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Quantitative Determination of Biomass-Derived Renewable Carbon in Fuels from Coprocessing of Bio-Oils in Refinery Using a Stable Carbon Isotopic Approach

Wang

Magrini

et al. 2020

ACS Sustainable Chem. Eng.

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A comparison of methods used to track the ‘green molecules’ and determine the carbon intensities of co‐processed fuels

Dyk

O’Connor³

et al. 2023

Biofuels Bioprod Bioref

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Policies such as a low carbon fuel standard (LCFS) have incentivized oil refineries to lower the carbon intensity of their operations and the fuels they produce. Although an increasing number of refineries are co-processing biogenic feedstocks, determining the renewable content and carbon intensities of the co-processed fuels (and potential credits earned through policies such as a LCFS) has proven to be challenging. Various methods that might be used to track the green molecules and determine the carbon intensities of co-processed fuels were compared. Although the use of carbon 14 and mass balance have predominated, each of these methods has some advantages and disadvantages. To try to benefit from the strengths of each method, a combined direct (C14) and indirect (modified mass balance) approach was shown to give representative values. However, the quality and frequency of the information collected needs to be assured, as it can improve the quality of data needed to determine the carbon intensity of the final fuels.

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Advancing the application of bio-oils by co-processing with petroleum intermediates: A review

Han

Wang

Zeng

et al. 2021

Energy Conversion and Management: X

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Tracking renewable carbon in bio-oil/crude co-processing with VGO through 13C/12C ratio analysis

Cited by 16 publications

References 32 publications

Quantitative Determination of Biomass-Derived Renewable Carbon in Fuels from Coprocessing of Bio-Oils in Refinery Using a Stable Carbon Isotopic Approach

Quantitative Determination of Biomass-Derived Renewable Carbon in Fuels from Coprocessing of Bio-Oils in Refinery Using a Stable Carbon Isotopic Approach

A comparison of methods used to track the ‘green molecules’ and determine the carbon intensities of co‐processed fuels

Advancing the application of bio-oils by co-processing with petroleum intermediates: A review

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