DOE Bioenergy Technologies Office (BETO) 2015 Project Peer Review

Refinery Integration 4.1.1.31 NREL 4.1.1.51 PNNL

March 24, 2015 Analysis and Sustainability Mary Biddy Sue Jones NREL PNNL

This presentation does not contain any proprietary, confidential, or otherwise restricted information Goal Statement

Leveraging existing refining infrastructure potentially reduces costs for biofuel production but we first need to understand the impacts

GOALS: Model bio-intermediates insertion Crude Oil points to better define costs & ID opportunities, technical risks, information gaps, research needs Publish results Review with stakeholders

Biomass

Bio-refinery Bio-intermediates

Liquefaction C12+ Lipids Oils Olefins

Petroleum Refinery Picture courtesy of 2 http://www.bantrel.com/markets/downstream.aspx Quad Chart Overview

Timeline Barriers Barriers addressed Start: October 1, 2012 (PNNL only) At-A lack of transparent and Start: October 1, 2014 (NREL+PNNL) reproducible analysis At-C Inaccessibility and unavailability End: September 30, 2016 of data Completion: 50% for joint project Tt-S Petroleum Refinery integration of starting in 2014 Bio-Oil intermediates Budget Partners

DOE Total Costs FY 13 FY 14 Total Partners: Funded FY 10 – Costs Costs Planned For joint portion of project: FY 12 Funding NREL (44%), PNNL (56%) (FY 15 -16) External Reviewers: NREL $0 $0 $128k $422k Refining catalyst vendor (2) Refinery #1 modeling contact (2) PNNL $65k $195k $228k $487k Refinery #2 modeling contact Refining industry independent contractor

3 Project Overview History: Joint Lab FY14 start - builds on previous work at both labs NREL refinery blending models for the NABC PNNL high level survey of refinery integration potential (AOP project FY12- 13) Complements separate NREL AOP project for refinery blending Context: Economic deployment of biofuel Understand how bio-fuels can replace entire barrel of oil Understand how existing infrastructure can best be used Objective: FCC and HCK model development to understand impacts, opportunities and gaps Develop first-of-a-kind process models to enable consistent modeling framework for economic and sustainability assessments Understand and review current state of technology and information ID risks, research needs, and cost drivers Review with key industrial stakeholders Publish results and findings 4 Approach (Technical)

Detailed Process Excel for Estimate Model in Raw Material Feedstock Composition Aspen Plus Accounting Of Bio-Oil (VGO/Bio-oil mix) Value to a Refiner Operating Conditions Flow rates Cost Conversion Yields $ Product Yield (LPG/Naphtha/Distillate/Heavy Oil) BBL Potential Challenges & Risk Mitigation Consistent and appropriate assumptions: defined technical basis and economic assumptions at start of project & reviewed with BETO Data availability: engage researchers at both labs + literature data to estimate yields and product distribution Meaningful cost impacts: estimate value of bio-oil relative to crude oil from a refiner’s perspective when considering quality, yield and process 5 impacts Approach (Technical)

Critical success factors: Stakeholder Review 4 separate refining related entities agreed to assist with project FCC catalyst vendor (2 contacts from same company: 1 with refining technologies and renewables expertise; 1 with expertise in FCC evaluations focusing on catalysts and feedstocks) Refiner #1 (2 contacts from same company – one with FCC expertise and one with HCK expertise) Refiner #2 (17 years in refining processes modeling research) Retired refiners now working as independent consultants FY14: Sent the FY14 report document to all and Aspen models to those interested Compiled feedback for use in revising models and methods (details in upcoming slides)

6 Approach (Management)

Approach structure Joint NREL and PNNL effort to leverage capabilities at both labs Project Management Plan (PMPs) indicating scope, budget, schedule Annual Operating Plans (AOPS) prepared prior to each fiscal year Details quarterly milestones and deliverables (see additional slides) Go/No-go point May 2015 to assess project value and direction FY15-16 AOP passed Merit Review July 2014 Quarterly reporting to BETO (written and regularly scheduled calls) Potential Challenges and Risk Mitigation Researcher proximity: we have regularly scheduled calls & data exchanges Data compatibility: use same software platforms & exchange models for cross-check review Critical success factors Engage stakeholders Make results public 7 Deliver product on-time, on-budget Technical Progress & Results: intermediates Currently Identified Bio-Oil Intermediates*

HTL=hydrothermal liquefaction; LE= lipid extracted; HYP=hydropyrolysis; CPO=catalytic pyrolysis; HDO=hydrodeoxygenation Petroleum Intermediates 52 references: literature and VGO Vaccuum gas oil VBGO gas oil experimental data AGO Atmospheric gas oil Initial Intermediates chosen: DAO De-asphalter oil • Partially hydrotreated pyrolysis oil (fair LCO FCC light cycle oil amount of information available regarding HCO FCC heavy cycle oil FCC co-processing; some hydroprocessing Resid Residual oil data) H+LCGO Heavy coker gas oil, light cycle gas oil • VGO as conventional feed 8 Technical Progress & Results: HCK Model

Fuel Modeled reactor, gas Hydrogen Gas separation and H2 Recycle recycle, product

separation Acid Gas Removal Fuel Reactor Pure compounds H2S Gas Stripper used (versus pseudo-

components) Fuel Gas Naphtha Stoichiometric Kerosene Reactor Model

Make-up High Diesel Low Aspen model Hydrogen Pressure Pressure Separator flowsheet shown in Separator Gas Oil Heavy Diesel

additional slides Fractionator Sour water

9 Technical Progress & Results: HCK Model

100% VGO feed model Back blended distilled products curves* in Excel to estimate HCK effluent Model check: Compared resulting utilities and HCK model product distillation compared to literature * Parkash Refining Processes Handbook, 2003

Blended feed models Used best judgment for HCK products of blended feed based on experience with hydrotreating pyrolysis oils; some lit on HCK of VGO with vegetable oils 90/10 wt% and 80/20 wt% VGO/bio-oil Consistent throughput and reactor inlet temperature for all three cases

10 Technical Progress & Results: FCC Model

Modeled reactor, gas separation and H2 Fuel Gas Flue Gas to Fractionation recycle, product Boiler Reactor separation To light Regenerator Pure compounds finishing used (versus pseudo- To heavy gasoline Makeup finishing components) Catalyst Distillate Stoichiometric Light Cycle Model Oil Reactor Air Medium Aspen model Pressure Steam flowsheet shown in Heavy Cycle additional slides Gas oil or Resid Oil

11 Technical Progress & Results: FCC Model

100% VGO feed model Back blended distilled products distillation curves* in Excel to estimate FCC effluent Model check: Compared resulting utilities and FCC model product distillation compared to literature * Parkash Refining Processes Handbook, 2003 Blended feed models Overall yields are based on published literature for comparable blends of partially upgraded bio-oil for FCC products Oxygen removal is either through the formation of water or CO2 and the yields are consistent with recent experimental results (60-70% of oxygenated species converted) 90/10 wt% and 80/20 wt% VGO/bio-oil Consistent throughput and reactor inlet temperature for all three cases 12 Technical Accomplishments

Fuel Hydrogen Gas HCK Recycle

Acid Gas Removal Fuel Reactor H2S Gas Stripper

Fuel Gas Naphtha

Kerosene

Make-up High Diesel Low Hydrogen Pressure Pressure Separator Separator Gas Oil Heavy Diesel

Fractionator Sour water

Developed first of a kind process models for hydrocracker and fluidized catalytic cracker units Developed baseline models for traditional petroleum vacuum gas oil (VGO) Introduced partially upgraded pyrolysis oil at 10wt% and 20wt% blend Performed preliminary economic analysis to estimate the value of bio-oil to a refiner based on set price of crude and process impacts 13 Technical Accomplishments: Key Milestone

Completed report summarizing process design and assumptions and economic analysis of integrating upgraded bio-oil in refinery FCC and HDO processes Report provided to 4 different external key petroleum refining stakeholder organizations. Feedback received from 5 total

independent reviewers. 14 Technical Accomplishments: Industrial Assistance General comments: Reduce flowrates (or add capital) for blended feeds to account for process constraints such as FCC coke make HCK hydrogen availability Heating value vs. volume swell Re-evaluate co-product basis (gasoline & diesel fraction, vs offgas, LPG) and consider a range of values Consider fixed costs: labor, maintenance, depreciation in addition to variable costs Unit specific comments FCC: heat balance methods; consider higher catalyst loss HCK: losses to light material; catalyst deactivation (increase cost or reduce throughput; consider heavy oil hydrocracker Feedback on sensitivities Vary crude prices Capital expenses to accommodate 20 wt% bio-oil Re-consider 100% conversion of oxygenates and discount products accordingly Coke production in both units Other variable costs such as waste water treatment, gas clean-up, additional wastes Feedback on data gaps Bio-oil and petroleum miscibility Metallurgy impacts Effect of oxygenates on pump seals Feedback on data sources: parallels with other work Oil shale and tight oil pilot work Vegetable oil/triglyceride cc-processing work Coal liquid co-processing work 15 Project Relevance Project directly contributes to BETO goals per 11/2014 MYPP: “The market potential of bio-oils as a feedstock for petroleum refineries is largely unknown. There is a need to gather information to understand the technical risks and to illustrate the economics and sustainability of integration so that refineries will consider the bio-oil intermediate an acceptable refinery feedstock.” (Thermochemical Conversion) “Convey the results of analytical activities to a wide audience, including DOE management, Congress, the White House, industry, other researchers, other agencies, and the general public” (Analysis and Sustainability) Positive impact on commercial biofuel viability: Determine bio-fuel production cost reduction opportunities Determine realistic estimates of how much biomass could potentially be co- refined and the impact on the Renewable Fuels Standards (RFS) Target Audience: BETO and industrial stakeholders Engage key stakeholders in the industry for their review and feedback on underlying assumptions, and share their insight on the issues of risk and technical information needs for risk assessment

Feed results to related BETO projects (experimental and analysis) 16 Identify data gaps needed for further consideration to BETO conversion platform Project Relevance

Expected outcomes and applications Understand & review current state of technology and information available to integrate biomass derived intermediates into existing petroleum refineries Begin to assess if refinery integration will be successful in the future in terms of economics, sustainability and technical risks. Assess cost requirements from the refiner’s perspective Identify the technical risks, research needs and primary cost drivers in using biomass derived intermediates in petroleum refinery hydrocracker and fluid catalytic cracker units Given the underlying uncertainty in the current data, identify which data gaps are critical to address in the near term to understand the cost implications and/or risk for refinery integration Help identify specific properties favorable for integration as well as properties that may limit the ability to integrate biomass intermediates and estimate the economic implications of meeting these desired properties

17 Future Work FY15: Continue model updates per reviewer feedback; leverage Aspen HYSYS capabilities in addition to AspenPlus Begin to identify data needs for Life-Cycle Analysis (LCA) Continue stakeholder reviews Stakeholder Dissemination: Present work to date at AIChE Spring Meeting Go/no-Go in May to determine whether to continue on or change course Key Milestone: Complete draft journal manuscript of co-processing information to date FY16: Expand models to consider co-processing of distilled bio-oil in hydrotreaters Potentially work with ANL regarding sustainability assessments Investigate supply chain integration (biomass type, location, proximity to petroleum refineries) Continue stakeholder reviews Key Milestone: Summary white paper Project ends: Not the last word, results feed into a bigger picture (Refinery Blend 18 LP model for example) Summary Overview: Begin to understand co-processing issues Approach: Iterative, NREL & PNNL share inputs & review results with external experts Technical Accomplishments/Progress/Results FY14: Completed preliminary FCC and HCK cost and performance models with external review FY15: received external review feedback & began incorporation Conducting on-going literature search Preparing data requests Relevance: by assessing use of existing infrastructure, this project aligns with BETO’s mission to reduce biofuel production costs Future work: Go/No-go, journal draft, sensitivity analysis, sustainability analysis Status since 2013 Review: PNNL FY12-13 AOP project had review from one retired refiner. Peer reviewers recommended bringing in additional expertise. Joint NREL/PNNL project started in FY14 and added multiple industrial assistance. 19 Acknowledgements

Bioenergy Technologies Office – Alicia Lindauer

NREL TEAM PNNL TEAM Mary Biddy Sue Jones Michael Talmadge Mark Bearden Yunhua Zhu Steve Phillips Asanga Padmaperuma

April 1, 2015 20 Additional Slides

Response to reviewers comments Publications and presentations Project milestones Modelling detail example Abbreviations and acronyms

21 Responses to Previous Reviewers’ Comments

2013 Peer Review of PNNL AOP project from FY12-13: “Broader engagement with more refineries and with downstream stakeholders is a key factor to make this and follow-up efforts worthwhile” “Needs much more collaboration with industry and labs” Response: Per reviewer recommendations, PNNL partnered with NREL to leverage previous and ongoing work at both labs and also increased the number of industry contacts from 1 to 4 separate entities (6 reviewers total)

Go/No-Go Reviews: scheduled for May 31, 2015

22 Publications and Presentations PNNL FY12-13 work Publications: Freeman C. J.; Jones, S. B.; Padmaperuma, A. B. et al Initial Assessment of U.S. Refineries for Purposes of Potential Bio-Based Oil Insertions, April 2013, PNNL-22432 Presentations: 2013. Freeman, C. J.; Jones, S. B.; Padmaperuma, A. B. et al Initial Assessment of U.S. Refineries and the Potential for Bio-Based Oil Insertions” Presented to the Bioenergy Technologies Office March 22, 2013 2013. "Opportunities for Biomass-Based Fuels and Products in a Refinery - A Preliminary Investigation" Presented by Corinne Valkenburg (Invited Speaker) at Biomass 2013, Washington, DC on August 1, 2013. PNNL-SA-97258 2014. "Preliminary assessment of potential bio-based oil insertions to US refineries" Presented by Asanga Padmaperuma at 2014 Spring Meeting and 10th Global Congress on Process Safety, New Orleans, LA on March 31, 2014. PNNL-SA- 101771 2014. "Initial Perspectives on Biomass and Bio-oils in Existing Infrastructure." Presented by Corinne Drennan (Invited Speaker) at Bio-oil Co- processing Workshop, New Orleans, LA on May 23, 2014. PNNL-SA-102992.

NREL/PNNL FY14-17 work Presentation planned for AIChE Spring meeting (April 2015) Publication draft planned for Q4FY15

23 Milestones and Metrics

Title/Description Due Date Completed Define conventional feedstocks and up to 5 bio-intermediate streams to feed hydrocracker and FCCU processes (joint PNNL/NREL) Dec-13 On-time Complete base Aspen models for the 2 refinery processes (joint PNNL/NREL) to include a stoichiometric based reactor, heat integration and product separation and summarize in a brief (joint PNNL/NREL Mar-14 On-time Complete co-processing cost estimates for at least two intermediates (oils with different oxygen contents) Jun-14 On-time Complete reviewed hydrocracker models with 2-3 process configurations (PNNL), FCC models with 2-3 process configurations (NREL) and report (PNNL/NREL) summarizing model assumptions, and outcomes identifying gaps, potential issues and opportunities for co-processing. - ML/DL). Sep-14 On-time Revise models (HCK PNNL and FCC NREL primary focus) to incorporate industrial/stakeholder reviewer feedback from FY14 and new literature/ experimental data leading towards the Q2 deliverable and summarize in a brief to BETO Dec-14 On-time Define and use models (HCK PNNL primary focus; FCC NREL primary focus) to collect sustainability metrics (e.g. GHG emissions, net fossil energy consumption) that are relevant to BETO's economic and sustainability goals, and summarize in a brief to BETO Mar-15 Go/No-Go decision: Model Utility May-15 Joint NREL-PNNL publication including a literature review of refinery integration data, and key economic results with a focus on data gaps, roadblocks and opportunities for bio-fuel cost reduction Sep-15 Consider alternative biomass derived feedstocks for co-processing, potentially produced from hydrothermal liquefaction or via fermentation, and develop hydrotreating model. Develop list of sustainability metrics to be collected and summarize in a brief to BETO Dec-15 Complete base and co-feed hydrotreater models from Q1 FY16 and summarize in a brief to BETO Mar-16 Complete biomass availability on a county level and proximity analysis to existing petroleum refineries for current and future scenarios; leverage HCK, FCC and hydrotreater model outputs. Summarize in a brief Jun-16 24 Final deliverable: NREL, PNNL ANL white paper draft for publication Sep-16 24 Aspen HCK and Gas separation

717

2630 163 2.25% hy drogen chemical consum ption (by wt) 2207 735492 2730 107221

2051(IN) 2051 421 750 750 2630 2615 2615

894345 894345 752041

SEP2209 R2201-2 204 2208 2210 2210-1 HYDROCRACKER 2690 HEATER SEP

51632 HE2208 1283 MX2206 2110 2565 2210(IN) 750 2210-4 752041 2615

Hydrogen 2210-2 142304

1017 776 QR2201-2 2550 2565

750 894345 894345

2565 HX2213B

Tempe rature (F) 2210-3 142304 2212 Press ure (ps ia ) 2211 2212(OUT )

Ma s s Flow R ate (lb/hr) Duty (M MB tu/hr) 77 MIX2207 77 -244 2635 VGO 15 735492 735492 Q2213 P-2205

2205 2200(IN) 2200 HX2213A

2422(IN) 2422 MIX2335

2390 TO AMINE CONTACTOR

2320

2051(OUT ) 2051 C2320

2323

2326 2321

SEP2312 HEX2340 KO DRUM 2342 HEX2302 SEP2311 2319 S EP FLH2315 HEX2345 2335 S EP P = 150 PSIG 2334 DEA ABSORBER 2333 2302 CW FLH2345 2301 2312 2327 2332 FLH2310 HEX2301A 2315 OILY WATER 2325 2212 2212(IN) MIX2313 2343 FLH2314 T 2330 2338 V2313 HEX2301B 2322 P = 550 PSIG 2313 2316 2329 2311 2328 2336

SEP2313 MIX2337 2314 MIX2330 W ATER S EP 2318 H2S STRIPPER P2337 2337 2344 2310 STEAM 2324

2341 P2301 SOUR WATER MIX2315 MIX2345 2317 2330 V2345 25 SOUR WATER 2331 2340(OUT ) Q2301

2339 2340 Aspen HCK Product Separation

2422 2422(OUT )

11 2419 FLH2410 HEX2411

2420 CONDENSATE SEP2410 2421 2408

2

P2420 2404-1

2423 NAPHTHA

T 2410

14

2425 HEX2403B 10 STEAM (150 psig) GEN. T 2430 P2413 2416 HEX2409 2407 HEX2410 Q2403 2417 P2415 2426 9 HEX2404B 8 2406 SEP2420 KEROSENE 2418 2427 5 7 P2414 HEX2401A HEX2402A HEX2403

2340 2401 1 2402 2403 SEP2430 2340(IN) HEAT ER T 2420 HEX2403A HEX2401B 13 2413 2414 2428 HEX2408

6 2480 P2412 DIESEL

15 2415 STEAM 4 2410 2411

P2411 2409 2405 HEX2405 HEX2402B HEAVY DIESEL STEAM (10 psig) GEN.

HEX2404A HEX2406 2412

3

Q2401

26 Abbreviations and Acronyms

ANL: Argonne National Laboratory AOP: Annual operating plan BETO: Bioenergy Technologies Office BBL: Barrel FCC: Fluidized catalytic cracker GGE: Gasoline gallon equivalent HCK: Hydrocracker LCA: Life-cycle analysis MFSP: Minimum fuel selling price MYPP: Multi-year program plan NABC: National Advanced Biofuels Consortium NREL: National Renewable Energy Laboratory PMP: Project management plan PNNL: Pacific Northwest National Laboratory VGO: Vacuum gas oil

April 1, 2015 27