Co-Processing Bio-oils In Refineries

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DOE Bioenergy Technologies Office (BETO)2021 Project Peer ReviewCo-Processing Bio-oils in RefineriesMarch 22, 2021SDI Project Peer ReviewKim Magrini, Huamin Wang, Zhenghua LiNREL, PNNL, LANLThis presentation does not contain any proprietary,confidential, or otherwise restricted informationCover art by NREL in ACS SustainableChem. Eng. 2020, 8, 2652 2664.

Project OverviewLeveraging existing refining infrastructure leverages billions US in CAPEX and 5 million bpd of crude refiningObjective: Accelerate adoption ofco-processing biomass-derivedfeedstocks with petroleum streamsin operating petroleum refineries toproduce biogenic carbon containingfuelsBiomassLiquefaction(FP, CFP, HTL)*BioIntermediatesFCCBio-oil, Bio-crudeCo-processingDeveloping bio-oil intermediatesfor insertion points with themost impactHydrotreatingHydrocarbonsas blendstock2 Bioenergy Technologies Office* FP: Fast pyrolysis oilCFP: Catalytic fast pyrolysis oilHTL: Hydrothermally liquefied bio crudeHTHCFCCHTOutcome: Foundational data for de-riskingco-processing Co-processing strategies torefiners Tools for biogenic carbon trackingImpact: Faster introduction ofrenewable fuels into thetransportation sector to reduceGHG by 2025

1 – ManagementAn interdisciplinary and collaborative effortWood, Herbac.WWTP Sludge, Algae21FP, CFP (NREL)HTL (PNNL)VGO BlendsBio-oil/Crude3FP, CFP oils toPNNL for HT5Bio-oil/Bio-crude PNNL HTL projects NREL CFP project3 Bioenergy Technologies Office3 Labs, 5 TasksFCCFuel Analysis(NREL)NREL, PNNL, LANLBiogenic TrackingHT/HC(PNNL)LANL, PNNL, NREL4Process TEA, LCA(PNNL, NREL)Catalyst Development Johnson Matthey WR Grace Haldor TopsoeC Analysis LLNL (14C) UC Irvine CEC, CARB* California AirResources Board,California EnergyCommissionAnalytical Developmentand StandardizationIAB, ENSYNExxon MobilHoneywell/UOPSuncorU. Brit. ColumbiaU. Of CalgaryWR Grace

1 - ManagementSignificant knowledge gaps for co-processing requires extensive R&DBio-IntermediatesBio-oil, Bio-crudeCo-processedFuelsFP, CFP, HTLJet, Diesel, GasolineKnowledge GapsCan bio-oil/crude feed quality,consistency be controlled?How can biogenic C incorporationinto fuels be maximized?Is biogenic C tracking and fuelcontent analysis deployable?If SuccessfulCo-processing impact to refinery processes and fuelquality is minimizedEconomic and environmental benefits to both refineries and bio-refineries are realized(GHG, RINs) Co-processing not currently practiced by refiners (pilot work ENSYN, Petrobras) Pilot scale work shows 1-10 wt% bio-oil feed is possible in FCC units Bench scale work shows woody and wastewater sludge HTL bio-oil feeds are possible in HT/HC units Theseknowledgegaps identified in collaboration with project’s Industrial Advisory Board4 BioenergyTechnologiesOffice

1 – ManagementRisk management and efficient communicationProject Management Monthly virtual meetings (LANL, PNNL,NREL, BETO); team meetings bi-weekly Process data, sample analysis, bio-oils andcatalysts shared with team. Relevant dataadded to shared database Quarterly milestones with explicit technicaltargets (i.e. 5 wt% biogenic C in FCC fuels) Go/No Go decision 2/2022 identifying andmitigating contaminant risks to process andcatalysts Bi-annual IAB progress review5 Bioenergy Technologies OfficeRisk Management (Process Driven) Catalyst deactivation by inorganics inbio-oil/bio-crudes is a major CP issue:contaminant risk will be evaluated, andmitigation processes developed (hot gasfiltration, guard beds) to removecontaminants pre-CP Plugging during FCC CP an issue:new nozzle designs and materials arereducing plugging Targeted catalyst development toimprove BC incorporation andaccurate/rapid biogenic carbonmeasurement underway

2 – ApproachExisting challenges and future work vetted by IABAdditional research needs vetted by IAB boarding meeting (2.12.2020) incorporated in the FY2021-2023 project planExisting challenges: A critical operability risk comprising long termprocess stability around catalyst deactivationand plugging during operation A regulatory risk comprising the need torapidly measure biogenic carbon andoxygenates in process streams and products A knowledge risk centered on the lack of coprocessing data including feedstockcompositions and contaminants, productcompositions, reaction kinetics of unique biocompounds, and associated TEA/LCA6 Bioenergy Technologies OfficeKey Research Areas: Quantify biomass contaminant impact tocatalyst stability (i.e. K, S) Track contaminants in bio-oils/bio-crudes Develop deployable biogenic carbon tracking Reactor model modification to improveprediction Process improvements assessed via TEA/LCAand refinery impact analysis

2 – ApproachDeveloping foundational data and providing co-processing (CP) strategiesTechnical Approach: accelerate adoption of CP biomass-derived feedstocks with petroleum streams in operatingpetroleum refineries by developing and publicizing foundational data for processing renewableintermediates and providing co-processing strategies through: Isotope tracking to determinebiogenic carbon in products andonline biogenic carbonmeasurement (refiner ask) FCC and HT/HC processdevelopment using refinerycompatible reactorsystems, innovativecatalysts, compositiontailored bio-oil feeds Refinery compatible, novelcatalyst development withindustrial partners for FCCand HT/HC7 BioenergyTechnologiesCPOffice pathwaysDEDADDAMDOC11C1210080Partial pressure, % Use model or isotopelabeled feeds to determineCP kinetics andmechanisms Novel 13C-labelled biomass CPto track biogenic species throughCP and in fuels60402000.00.20.41/SV, 100g cat h/mol DEDAD0.6 Searchable database offeedstock, process conditions andproduct compositions for refineruse Technoeconomic analysis andlifecycle analysis to assessprocess cost and GHG impact

3 – ImpactLeveraging billions of US (CAPEX) in 136 US refineries processing 5 million gallons of crude/dayFacilitating refiner adoption of co-processed biogenic hydrocarbon fuels via catalyst and co-processingpilot scale development for FCC and HT/HC can produce biogenic transportation fuels in the near term byusing existing refineries Project directly supports BETO’s mission totransform biomass into refinery integrablebiofuels (jet, diesel, gasoline):CP TEA for FCC estimates fuel cost of 3.16/GGE Addresses a critical need for conversionenabling technology development using theexisting refinery infrastructure - no CAPEXrequired Project metrics/technical targets aredefined/vetted by TEA and the IAB We work directly with catalyst and instrumentmanufacturers, refiners:8 Bioenergy Technologies OfficeProject deliverables are transferrable to refiners: Refinery compatible FCC, HT/HC bio-oilconversion catalysts developed with industryleaders Refinery co-processing conditions for FCC and CoHT/HC CP nozzles that reduce / eliminate plugging Accurate biogenic carbon measurement for RINsand GHG reduction On-line biogenic carbon and oxygenatemeasurement for process feedback and control Process kinetic models to predict CP performance

3 – ImpactLeveraging billions of US (CAPEX) in 136 US refineries processing 5 million gallons of crude/dayKey FindingOutcome and ImpactTailoring catalyst andprocess to enable coprocessing demonstrated Refinery compatible catalysts being developed with industrial partners andco-processing strategy being established The global refinery catalysts market size expected to grow from USD 4.0billion in 2020 and USD 4.7 billion by 2025Biogenic C incorporationinto fuels via FCC andHT/HC demonstrated 80% biogenic carbon incorporation into FCC and HT/HC co-processed fuelsachieved at bench and small pilot scales with up to 10vol% bio-oil co-feeds At 5M bpd crude refining in the US, 1 refinery can CP 3700 bpd of bio-oilCo-processing databasegenerated for refiner andresearcher use LabKey-based database of bio-oil compositions developed that will besearchable and published, similar to www.crudemonitor.US Potential users are refiners, catalyst manufacturers, researchersNew nozzle materials anddesign improve bio-oilfeeding in FCC CP New nozzle designs and materials reduce plugging during FCC coprocessing USPTO Application submitted February 2021 on anti-plugging nozzles9 Bioenergy Technologies Office

4 – Progress and OutcomeWe are addressing significant challenges for co-processing (5 tasks)Bio-IntermediatesBio-oil, Bio-crude FP, CFP (NREL)HTL (PNNL)Feed Quality/Consistency Bio-oil/crude propertiesand CP database Quantify and trackcontaminantsCo-processedFuelsFCC Co-processingNRELHT/HC Co-processingPNNLFY18-20FY21-23Biogenic C incorporation Demonstrate significant incorporation ofbiogenic C by FCC and HT/HCBiogenic carbon tracking Further improved isotope methods(δ13C and 14C LSC) Extend to other feed and unit ops Quick and inexpensive method forprecise on-line detection andaccurate fuel analysisImpact to refinery process Impact of co-processing to FCC and HT/HC chemistry and kinetics (S, Nremoval and distillate yield; actual feed and model systems) Impact to fuel quality Impact to catalyst (lifetime), H2 consumption, and reactor Modified reactor model10 Bioenergy Technologies OfficeFuel Analysis:Biogenic CLANL/PNNL/NRELBenefit to refinery and bio-refinery TEA and refinery impact analysis Continuous update andimprovement

4 – Progress and OutcomeJoint Database of Process Conditions, Catalysts, Feedstocks, Materials Data comprises process,operating, feed and productcompositions, BC content perrefinery pathway (FCC, HT/HC) Similar to petroleum databasehttp://www.crudemonitor.us/ Database is searchable, to belinked with FCIC feedstockdatabase (LabKey), and to bepublished for refiner use Potential users: 136 USrefineries, multiple catalyst andinstrument manufacturers,research community11 Bioenergy Technologies OfficeMockup of the final LabKey User Interface for the website of the publisheddatabase. Potentially link with the FCIC feedstock database.

4 – Progress and OutcomeCatalyst impact to fuel chemistry – co-processing in FCCTargeted FCC catalyst development produces bio-oils for varied refinery insertion pointsE-Cat100ProductsbyMS,GCMSProducts iidentifieddentifi ed by GCC%FCC of VGO, oakor CFPO, and 10%oak—90% VGOmixture over E-Catand JohnsonMatthey CP758 at550 C, productanalysis 40200OakVGOMixtureE-Cat co-processed product has: Enhanced aromatics, CO, CO2 Reduced alkanes12 Bioenergy Technologies Office

4 – Progress and OutcomeImpact to chemistry and fuel quality – co-processing in HT/HCCritical factors in bio-oil/bio-crude properties impacting co-processing chemistry andfuel quality determined, guiding catalyst/process/fuel blending modification in l (11310 ppm S) 5% woody CFP bio-oil70 ppm S155 ppm SVGO (2.5 wt.% S) 5% sludge HTL bio-crude0.05 wt.% S0.22 wt.%Stronger inhibition by sludge HTL biocrude than woody CFP bio-oil becauseof the high N content of the former13 Bioenergy Technologies OfficeDemonstrated HTpretreatment tomitigate N issues ofbio-crude and enableco-processing in HCDetailed kinetic study of HDN of bio-crudeprovide guidance on catalyst/parameter selectionFatty acid amide HDN100Partial pressure, %Competition between heteroatom(S, N, O) removal is critical duringco-processing in hydrotreating80OC HC11H23 C N 2 5C2H560C12H25 NC2H5C2H520C11H24 C12H25OH00.00.20.41/SV, 100 gcat*h/molImpact on fuel quality determinedC12H260.6

4 – Progress and OutcomeBiogenic carbon tracking method improvedCombing two inexpensive and deployable isotope methods couldpotentially meet refinery’s biogenic carbon analysis requirements13C/12CRatio Analysis14Cδ13C -30.099‰δ13C -29.013‰LSC (Liquid Scintillation counting) Direct LSC method Compared over threeinstrumentsFP oil,5.20%CFP oil,0.83% Developed analytical protocol and algorithm for highprecision analysis of δ13C and biogenic carbon content Demonstrated δ13C analysis can be used for onlinetrackingbiogenicC in the co-processing14 BioenergyTechnologiesOffice Feasible to accurately determine 1% biogeniccarbon in fuel Direct LSC could be an option for qualityassurance at co-processing facilities

4 – Progress and OutcomeHigh biogenic C incorporation demonstratedGo/No Go: Both FCC and HT/HC are viable co-processing pathways which meet/exceed theperformance target: 50% biogenic carbon incorporation at a blend level 5-20%Co-processing in FCCProduct IDVGO(vol %)CFP Oil(vol %)*% BC* inCFP Oil% BC in HCProductCo-processing in HT/HCWoody CFP bio-oil with VGOVGO10000V/C 99/19910.8naV/C 97/39733.0naV/C 95/59553.83.1Rcn. T, P 520 C, 25 psig; Feed rate 1.2 liter/hCP758 Johnson Matthey zeolite catalystPine CFP oil in VGO* Biogenic carbon measured by 14C analysisSimulated distillation showssimilar BP range (expected at thelow CFP concentrations) 80% biogenic carbon incorporation in fuelproducts for: Woody CFP bio-oils with VGO15 BioenergyTechnologiesOffice PotentialforMSW-derived biomass feedstocks 90% biogenic carbon incorporation in fuelproducts for: Woody CFP bio-oils with VGO Woody CFP bio-oils with straight run diesel Sludge HTL bio-crude with VGO

4 – Progress and OutcomeTEA and refinery impact analysisPreliminary analysis showed co-processing has potential to reduce biomass conversion cost forbiorefinery and benefit refinery by profitable feedstock and renewable carbon in fuel productTEA of FCC Co-Processing Bio-Oils Co-processing CFP oil withVGO in FCC produces fuelrange molecules and coproducts with a modeledMFSP as low as 3.16/GGE(2019 SOT 3.33/GGE).Note: MSFP considers capital andoperating costs for co-processing CFP oilto finished blendstocks and recovered coproducts. This includes catalyst make-up,plant utilities and hydrogen demands. Refinery Impact Analysis of Co-Processing BioOil/Bio-crude and VGO at Mild Hydrocracking Unit With on-going R&Ds, themodeled break-evenvalues of CFP bio-oil andHTL biocrude will begreater than theirmodeled MBSPs at 2022design casesBio-oil co-processing in FCC experiments show high relative olefins yields (propylene, butylene to alkylate), which helpeconomics and interest from refining industry. The break-even values of biomass intermediates depends highly on their potential impacts on petroleum refineries as wellas crude oil price and fuel demands Current evaluation of break-even values may subject to uncertainties from data gaps in long-term testing, potential impactsof co-processingon catalyst life, operating condition (temperature, H2 partial pressure, etc.)16 BioenergyTechnologies Office

SummaryProject Goal Accelerate adoption of co-processingbiomass-derived feedstocks withpetroleum streams in operatingpetroleum refineries to produce biogeniccarbon containing fuelsManagement Addressing major risks and efficientcommunication Interdisciplinary and collaborativeeffort with three national labs andpartnersApproach Developing foundational data andoffering co-processing strategies Combining multiple technologies andunique capabilities Progress reviewed and future workvetted by Industrial Advisory Board17 Bioenergy Technologies OfficeImpact Address a critical need for biomass conversion enablingtechnology development Project deliverables are transferrable to refinersProgress and Outcomes High biogenic C incorporation demonstrated (Go/No GoPassed) Impact to chemistry and fuel quality determined Biogenic carbon tracking method improved TEA and refinery impact analysis shows Benefit to refinery andbio-refinery Joint Database of Process conditions, catalysts, productcompositionsFuture Work Impact to catalyst stability Track Contaminants in bio-oils/bio-crudes Biogenic carbon tracking Reactor model modification TEA/LCA and refinery impact analysis

Quad Chart OverviewTimeline Project start date: 10/1/2020Project end date: 9/30/2023Active Project(FY21-23)FY20DOEFunding1,100 K (NREL)1,100 K (PNNL)510 K (LANL)2,000 K (NREL)2,050 K (PNNL)900 K (LANL)Project Partners* Johnson Matthey (catalystdevelopment) WR Grace (FCC operations) BETO: ChemCatBio, CCPC, ACSCBarriers addressedADO-G: Co-Processing withPetroleum RefineriesADO-H: Materials Compatibility, andEquipment Design and OptimizationFunding MechanismBETO Lab Call 201918 Bioenergy Technologies OfficeProject GoalTo accelerate adoption of co-processing biomassderived feedstocks with petroleum streams in currentpetroleum refineries by developing and broadlydisseminating foundational data for processing renewableintermediates, offering co-processing strategies, andaccurately measuring biogenic carbon in finished fuels.End of Project MilestoneThe end of project milestone will provide relevant coprocessing data for both pathways (FCC, HT/HC) thataddresses refiner risk on: Catalyst performance and potential deactivation fromcontaminants carried down in bio-oil/bio-crudefeedstocks Robust biogenic carbon and oxygenate measurementfor RFS determination LCA and TEA analyses per pathway A comprehensive database of co-processingparameters (catalyst, process conditions, feedstockand product compositions, associated analyticalmethods) for refiner use.

AcknowledgementsSDI Program: Liz Moore, Jim SpaethBob BaldwinEarl ChristensenKristiina IisaRebecca JacksonCalvin MukarakateJessica OlstadYves ParentBrady PetersonGlenn PowellReinhard SeiserMike SpragueAnne Starace19 Bioenergy Technologies OfficeHuamin WangMiki SantosaIgor KutnyakovCheng ZhuOliver GutierrezMatt FlakeYuan JiangSue JonesJal AskanderCharlie DollAndrew PlymaleCorinne DrennanZhenghua LiJames LeeDouglas WareThomas GeezaOleg MaltseveJacob HelperIndustrial CollaboratorsCasey Hetrick (BP America)Jeff Lewis (Equilibrium Catalysts)Gordon Weatherbee (WR Grace)Mike Watson, Andrew Heavers, Luke Tuxworth(Johnson Matthey)Larry Doyle, Chris Brown, Sean Murray (Zeton)Kevin Stup (Vacuum Analytics)

Project Acronyms and PathwaysBC:CFP:CP:E-Cat:FCC:FP:HC:HT:HTL:biogenic carboncatalytic fast pyrolysisco-processingequilibrium FCC refinery catalystfluid catalytic crackingfast pyrolysishydrocrackinghydrotreatinghydrothermal liquefactionFCCVGO Blendsbio-oilsFCCBiogenicFuelsHT/HC20 Bioenergy Technologies OfficeVGO Blendsbio-oil/CrudeHT/HCFuelCompositionBC Measurement

F2019 Reviewer Comments/ResponsesStrength: Good approach - collaboration between fossil and bio-refiners promisesto take advantage of the scale of economics achievable in the fossil industry whileproviding the benefits of bio-sourced carbon to a finished product. Success factorswell defined for incorporation of biogenic carbon in transportation fuels.Challenges of incorporating oxygenates in existing refinery operations welldescribed. Determination of how biogenic carbon reports throughout the refineryis useful for commodization of biogenic carbon. Good industry participation helpsensure efficiency of approach; helping to avoid "dead-ends" of investigation.ResponseWe thank the reviewers for their support21 Bioenergy Technologies Office

F2019 Reviewer Comments/ResponsesWeakness: Significant differences in process scale will likely impose highercosts on an established means of transportation fuel production. Goal is NOTproduction of 'biogenic fuels', but fuels with biogenic' content.ResponseOne approach is to ship bio-oils from their production facility to the refinersmuch as VGO is shipped. This approach may reduce any higher costsassociated with bio-oil scale of production. The ENSYN/Tesoro project shouldgenerate information on costs associated with bio-oil co-processing. We agreethat the terminology should be fuels with biogenic content22 Bioenergy Technologies Office

F2019 Reviewer Comments/ResponsesWeakness: The catalyst development work needs to be carefully thought through.The refineries will not likely change the existing FCC catalyst to blend 5% bio-oil.This FCC and ZSM-5 catalysts have been optimized for the last 50 years andbecause of huge risk, there will not be any appetite for change. However, bio-oilstabilization for HP/HC routes may benefit from advanced catalysts.Response:For FCC catalysts, the changes are minor and include "tweaking" existing HZSM-5properties to increase bio-oil conversion to be mixed with a refinery equilibriumcatalyst. Limited details on the tweaking are discussed because the catalystdevelopment work is being conducted with Johnson Matthey, a major refinery FCCcatalyst supplier. Note that baselining FCC co-processing with bio-oils and E-Catis being done to address the possibility that refiners will not use a modified additiveto their preferred catalyst23 Bioenergy Technologies Office

F2019 Reviewer Comments/ResponsesWeakness: Disruption of mature processes and existing operations is bound toincrease final cost of production.Response: A true statement but by using existing infrastructure and de-riskingthe addition of small amount of bio-oil co-feed, cost impact should be kept to aminimum and offset by RINs.24 Bioenergy Technologies Office

Additional Slides25

Publications, Patents, Presentations, Awards, and CommercializationPublications Stefano Dell’Orco, Earl Christensen, Kristiina Iisa, Anne Starace, Abhijit Dutta, Michael Talmadge, Kim Magrini and Calvin Mukarakate, “"On-line BiogenicCarbon Analysis Enables Refineries to Reduce Carbon Footprint during Co-processing Biomass- and Petroleum-derived Liquids", ACS AnalyticalChemistry, accepted February 15, 2021, ID: ac-2020-041085.R3 Charles G. Doll, Andrew E. Plymale, Alan Cooper, Igor Kutnyakov, Marie Swita, Teresa Lemmon, Mariefel V. Olarte, Huamin Wang. “Determination oflow-level biogenic gasoline, jet fuel, and diesel in blends using the direct liquid scintillation counting method for 14C content”. Fuel, 2021, 291, 120084. Huamin Wang, Pimphan A. Meyer, Daniel M. Santosa, Cheng Zhu, Mariefel V. Olarte, Susanne Jones, Alan H. Zacher. “Performance and technoeconomic evaluations of co-processing residual heavy fraction in bio-oil hydrotreating”, Catalysis Today, 2020, Doi: 10.1016/j.cattod.2020.08.035 Geeza, T.; Li, Z.; Maltsev, O.; Lee, J.; “Carbon Isotope Analysis of Co-Processed Biofuels Using a Continuous-Flow Isotope Ratio Mass Spectrometer,”Energy & Fuels, 2020, https://doi.org/10.1021/acs.energyfuels.0c02114. Zhenghua Li, Huamin Wang, Kimberly Magrini-Bair, James E. Lee, Thomas Geeza, Oleg Maltsev, Jacob Helper. “Quantitative Determination of Biomassderived Renewable Carbon in Fuels from Co-processing of Bio-oils in Refinery Using a Stable Carbon Isotopic Approach”. ACS Sustainable Chemistryand Engineering, 2020, 8, 47, 17565. Calvin Mukarakate, Kellene Orton, Yeonjoon Kim, Stefano Dell’Orco, Carrie A. Farberow, Seonah Kim, Michael J. Watson, Robert M. Baldwin, andKimberly A. Magrini, “Isotopic Studies for Tracking Biogenic Carbon during Co-processing of Biomass and Vacuum Gas Oil”, ACS Sustainable Chem.Eng. 2020, 8, 2652 2664. Zhenghua Li, Kimberly Magrini-Bair, Huamin Wang, Oleg V. Maltsev, Thomas J. Geeza, Claudia I. Mora, James E. Lee, “Tracking renewable carbon inbio-oil/crude co-processing with VGO through 13C/12C ratio analysis”, Fuel 275 (2020) 117770. Dutta, Abhijit, Iisa, Maarit K, Talmadge, Michael, Mukarakate, Calvin, Griffin, Michael B, Tan, Eric C, Wilson, Nolan, Yung, Matthew M, Nimlos, Mark R,Schaidle, Joshua A, Wang, Huamin, Thorson, Michael, Hartley, Damon, Klinger, Jordan, and Cai, Hao. Ex Situ Catalytic Fast Pyrolysis of LignocellulosicBiomass to Hydrocarbon Fuels: 2019 State of Technology and Future Research. United States: N. p., 2020. Web. doi:10.2172/1605092. Huamin Wang, Kim Magrini, Zhenghua Li, Co-processing biomass thermal liquefaction bio-oil/bio-crude in refineries, IEA Bioenergy Task 34 PyNe 44newsletter, July 2019, 2019/07/PyNe44 final.pdf.

Publications, Patents, Presentations, Awards, and CommercializationMilestone ReportsQ1FY21: Finalize the documents required for a direct funding opportunity (DFO). This project will use a DFO to call for participation of biogenic carbon instrumentdevelopers to identify and advance biogenic carbon tracking technology for co-processing application. In Q1, the call for proposal and the language for CRADA will be inplace for announcing the DFO in Q2 or Q3. (Task 3, NREL, PNNL, and LANL).Q4FY20: Document Optimized Co-processing Results for FCC (NREL) and HT/HC Pathways (PNNL)Q4FY20: Publish free and searchable online database w/physiochemical characterization of relevant oils, fractions and products, and document process relevant data forpotential FCC and HC/HT refinery insertion and integration. Steering Committee to serve as reviewers before submission. Final TEA/LCA analysis to be included in thepublication.Q3FY20: HT/HC: Complete determination of the fuel quality for co-processing CFP bio-oil and/or sludge HTL bio-crude with VGOQ2FY20: Isotopic Biogenic Carbon Determination of Co-processed FCC and HT/HC FuelsQ2FY20: FCC: Catalyst Evaluation, Down Select and Scale Up for FCC CP Verification (with Johnson Matthey); HT: Catalyst and process parameters for co-processing intwo-step HT-HC for sludge bio-crude.Q1SFY20: Conduct Bi-Annual ISC Face to Face Meeting to Review ProgressQ4FY19: Technoeconomic Analysis of FCC and HT/HC Co-processing Assessed for MFSP (minimum fuel selling price)Q4Y19: FCC: Develop a catalyst or catalyst combination for co-processing FP or CFP/VGO mixtures that targets 5wt% biogenic carbon incorporation efficiency (targetolefins). These results will be used to measure improvements in FY2020 catalyst performance for biogenic carbon incorporation and lifetime and documented in a draftfor journal article.Q4FY19: Identify opportunities for reduced coke formation in zeolite catalysts for Catalytic Fast Pyrolysis. (joint with WBS 2.3.1.314)Q3FY19: Demonstrate improved carbon efficiency for zeolite CFP by recycling tail gas in the DCR using metal-modified zeolite catalysts.Q3FY19: Biogenic Carbon Determination of Co-processed FCC and HT/HC FuelsQ3FY19: FCC: Complete Initial Micro Scale Catalyst Screening Tests to Identify Best Co-Processing PerformersQ2FY19: FCC: Establish Catalyst Composition and Morphology to Baseline Co-Processing (post-use) Induced Changes; HT/HC: Establish baseline for kinetic study usingmodel compounds for co-processing with a commercial catalyst.

Publications, Patents, Presentations, Awards, and CommercializationMilestone Reports2/28/2019 Go/No-Go: Identify the viable co-processing pathway(s) (i.e., bio-oil type and refinery processing unit) compared with baseline FCC processing ofraw bio-oil: Proposed decision metrics (to be finalized with industrial steering committee) include for FCC and HT: maximize biogenic carbon content indistillate products to achieve a 50% biogenic carbon incorporation at a given blend level in the 5 to 20% range. Minimize yield loss. Maintain yields for distillatefuels at no less than 90% of baseline values (maximum 10% yield loss). Data to be generated at the micro- and/or DCR scale for FCC and lab-scale forHT/HC.Patents“K. Magrini, P. Peterson, C. Engtrakul, N. Wilson, “CATALYTIC HOT-GAS FILTRATION OF BIOMASS PYROLYSIS VAPORS”, US Patent ApplicationNo.16/940,190, July 27, 2020.K. Magrini, J. Olstad, Y. Parent, “SYSTEMS AND METHODS FOR PRODUCING FUEL INTERMEDIATES”, US Patent Application No.16/869,101, May 7,2020.K. Magrini, M. Sprague, R. Seiser, Z. Abdullah, NREL ROI-20-76 “Feed nozzle designs and materials that reduce/eliminate coking/plugging during coprocessing bio-oils with petroleum feedstocks to biogenic hydrocarbon fuels” filed March 23, 2020. USPTO patent application filed February 2021.CommercializationNREL/Johnson Matthey CRADA to develop refinery compatible biomass conversion catalysts3-Phase project with Chevron to assess co-processing with their feedstocks and catalysts (200K)MOU-19-523: K. Magrini and D. Chiaramonte, Memorandum of Understanding finalized with the University of Florence, Florence, IT for developing productsfrom biomass pyrolysis streams. Hosted Stefano Dell’Orco from February-July 2020 for doctoral work in thermochemical biomass conversion.

Publications, Patents, Presentations, Awards, and CommercializationPresentationsR. Seiser, J. Olstad, K. Magrini, R. Jackson, B. Peterson, E. Christensen, M. Talmadge, A. Dutta, “Co-Processing Catalytic Fast Pyrolysis Oil in an FCC Reactor”,accepted for oral presentation at the European Biomass Conference and Exhibition, April 26-29, 2021, Marseille, FR.Kim Magrini, Jess Olstad, Brady Peterson, Rebecca Jackson, Yves Parent, “Feedstock and Catalyst Impact on Bio-Oil Production and FCC Co-Processing to Fuels”,accepted for oral presentation at the European Biomass Conference and Exhibition, April 26-29, 2021, Marseille, FR.Zhu, C.; Santosa, M.; Wang, H.; “Co-processing bio-crudes with petroleum gas oil in hydrotreating: Kinetics of heteroatom removal,” oral presentation, 2020, TCS 2020virtual meeting.Yeonjoon Kim, Seonah Kim, Anne Starace, Earl Christensen, Kellene Orton, Calvin Mukarakate, Kim Magrini, Carrie Farberow, “Hydrogen transfer to mitigate phenoliccoke formation during co-processing of bio-oil with vacuum gas oil over Y zeolite”, 2020 Thermal & Catalytic Sciences Virtual Symposium (2020 TCS), October 5–7,2020.Braden Peterson, Chaiwat Engtrakul, Matthew Coats, Michael Griffin, Jessica Olstad, Yves Parent, Kim Magrini, “ Pyrolysis Vapor and Bio-oil Preconditioning via Ex SituHydrodeoxygenation and Alkylation Using a Heteropolyacid Catalyst”, 2020 Thermal & Catalytic Sciences Virtual Symposium (2020 TCS), October 5–7, 2020.K. Magrini-presenter, J. Olstad, B. Peterson, Y. Parent, M. Sprague, R. Jackson, “SCR Industrial Advisory Board and F2F Meeting: FCC Co-Processing”, February 12,2019, Richland, WA.K. Magrini-presenter, J. Olstad, B. Peterson, Y. Parent, S. Deutch, A. Stara

Pilot scale work shows 1-10 wt% bio-oil feed is possible in FCC units Bench scale work shows woody and wastewater sludge HTL bio-oil feeds are possible in HT/HC units These knowledge gaps identified in collaboration with project's Industrial Advisory Board. Bio-Intermediates. Bio-oil, Bio-crude. FP, CFP, HTL. Co-processed Fuels

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