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Refinery Integration – Preliminary Techno-economics
1
CORINNE DRENNANEnergy and Environment [email protected]
California Air Resources Board – Public Meeting on Pathway Carbon Intensity and Evaluation13 December 2016
PNNL-SA-122971
What are the impacts of leveraging existing refining infrastructure for biofuel cost reduction?
Overview of project goals
December 28, 2016 2
How do we manage the broad range of potential intermediates and significant variability of technical information?
Overview of technical approach
December 28, 2016 3
What do we have to work with?
Overview of available literature and data
December 28, 2016
4
PNNL-SA-xxxx
What comprises fast pyrolysis oils?
A quick overview
December 28, 2016 55
500-640 FAcids: 2.5Phenols: 0.4Unidentified: 21
640-1051 F: no data
Biocrudes are expected to be similar, and highly-dependent upon feedstock
Source: Christiansen, 2012
0102030405060708090
100
C5-160 F 160-360 F
Wt.
%
Boiling Range
Partially Hydrotreated Pyrolysis Oil Compounds
Olefins
Aromatics
Naphthenes
Isoparaffins
Paraffins0
102030405060708090
100
360-500 F
Wt.
%
Boiling Range
Partially Hydrotreated Pyrolysis Oil Compounds
Phenols
Ketones
Esters
Aromatics
Alkanes
Alcohol
Boiling Range Wt. % Category
C5 - 160 F 5.8 Light
160 - 360 F 21.6 Naphtha
360 - 500 F 20.5 Kerosene
500 - 640 F 18.9 Diesel
640 - 1051 F 33.2 Gas oil
What can we learn from the fossil sector?
20 years with non-traditional feedstocks
December 28, 2016 6
Three relevant areas and ‘lessons learned’:Oil shale/tight oil: relatively high oxygen content
Co-processing in FCC produces too little coke to meet heat requirementsBio-oil produces higher coke synergistic opportunity
High-TAN crudes: corrosion potential & possible mitigationProcess studies for bio-oil co-processing should consider impact on all downstream and supporting unit operations, including waste water treatment
Coal liquids:Refining coal-derived liquids was not significantly more expensive than petroleum streamsValue of liquids to refiner depends on refinery type (e.g., conventional –vs-heavy oilSignificant work in ‘graded’ approaches to increasing reactor severity via operating temperature and catalyst activity
How might models be used to investigate co-processing opportunities?
Process model development
December 28, 2016 7
Generic models of three major refining processes (AspenPlus)Fluid catalytic cracker (FCC)HydrocrackerHydrotreater
ASPEN HYSYS HBEDHydro-desulfurizationHydro-denitrogenationHydrocrackingRing-openingSaturation
But, how to leverage the petroleum correlations AND treat bio-oils/biocrude?
How do we make the best use of existing data and simulation technologies?
Model development methodology
December 28, 2016 8
Three Types of Entities:1. Oxygenated Compounds (Bio-derived intermediates)2. Pseudocomponents (for Petroleum Distillates)3. Kinetic Lumps (Associated with the HBED)
Bio-derivedIntermediates
ASPEN PLUS(RPLUGwithKinetics)
Property Method -HCRSRK
MassFractionDistribution
ASPEN Properties
RYIELDReactor
Assay HBEDHydroprocessorModelPseudocomponents
Kinetic Lumps
Kinetic Lumps
Spreadsheetbased onBoilingPoints
PseudocomponentsDistillationColumn
RefiningReactorTransition(Cutter Block)
PureComponents
Property Method – Peng Robinson
1. Model bio-based intermediates in AspenPlus, and import into HYSYS
2. Model petroleum HT and bio-based intermediates separately
3. Utilize HBED to model hydroprocessingunits
4. Convert kinetic lumps from petroleum HTs to pseudo-components
5. Fractionation system
Preliminary model assessment comparing 100% VGO with 10% and 20% bio oils
December 28, 2016 9
Bio oil co-processing impacts on FCC operations
Bio-Oil Blend Naphtha & Distillate
Yield
Naphtha & Distillate Quality
Heavy Diesel Yield
Coke Yield
Bio oil co-processing impacts on HCK operations
FCC considerations • CO2 and water in fuel gas• Coke constraintsHCK considerations • Several-fold increase in H2
consumption• Effects on heavy gas oil fraction
How do you assess the value of a bio-derived intermediate to a refiner?
Preliminary bio oil breakeven values
December 28, 2016 10
At WTI prices ~$40/bbl, breakeven values are $35-$60/bbl
At WTI prices ~$100/bbl, breakeven values are $90-$125/bbl
How do you assess the production cost to the bioenergy stakeholder?
Preliminary effective MSPs
December 28, 2016 11
At WTI prices ~$40/bbl, effective MSPs are $3-4/gge
At WTI prices ~$100/bbl, effective MSPs are < $3/gge
What is next?
Significant data gaps exist
December 28, 2016 12
ExperimentalAnalytical methods for full characterizationBroad range of processing variationsPhysico-chemical assays for describing bio oilsPhysical property dataKinetic dataThermophysical properties
Modeling, economic, and sustainability analysesMay economics be improved via lower blend ratios?Additional intermediatesLevel of upgrading and fractionation required for refinery insertion?What are the cost and sustainability implications of transporting intermediates?
Acknowledgements
December 28, 2016 13
Pacific Northwest National Laboratory Team• Sue Jones• Mark Bearden• Yunhua Zhu• Steve Phillips• Asanga Padmaperuma• Lesley Snowden-Swan
National Renewable Energy Laboratory Team• Mary Biddy• Michael Talmadge
• ASPENTECH• Energy Efficiency and Renewable Energy – Bioenergy
Technologies Office
PNNL-SA-12342
