Production of Transportation Fuels by Co-processing Biomass-Derived Pyrolysis Oils in a Petroleum Refinery Fluid Catalytic Cracking Unit

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1 Stanley J. Frey R&D Fellow November 5, 2015 Production of Transportation Fuels by Co-processing Biomass-Derived Pyrolysis Oils in a Petroleum Refinery Fluid Catalytic Cracking Unit TCBiomass2015 Chicago, IL 2015 by UOP LLC, A Honeywell Company. All rights reserved. UOP

2 1 Co-processing Subjects: Refiner motivation Implementation plan Highlights of work done to make this pathway - Acceptable to regulators - Technically reasonable to refiners - Economically attractive UOP

3 Mil gals US EPA RFS2 Program Requirements Driving Interest in Co-processing 2 Increasing cellulosic biofuel mandates and costs 300 RFS2 Cellulosic Volumes $2.00 Cellulosic Waiver Historical Prices (set by EPA) Actual Mandate $1.80 $1.60 $1.40 $1.20 $1.56 $1.13 Calculated $ $ mil YTD PIRA Projected $0.80 $0.60 $0.40 $0.20 $0.78 $0.42 $0.49 $ $ UOP

4 FCC Co-Processing Overview 3 Standard FCC Unit Operation Co-processing RFO in FCC LPG LPG Gasoline Gasoline LCO LCO RFO VGO UCO VGO UCO 100% petroleum based products sent downstream Partially renewable products sent downstream UOP Utilize Existing Refinery Assets & Infrastructure

5 RTP & FCC Co-Processing Technology Partnership 4 Leading licensor of FCC process technology Supplies basic engineering design for RTP unit Developer of RTP technology Significant technical resources to support refinery post-project implementation Supplies RTP unit with full warrantees and guarantees Developer of projects producing RFO for refiner Contracts with refiner for RFO supply UOP

6 RTP Processing Second Generation Residues to Energy 5 Rapid Thermal Processing biomass conversion to green fuel Energy densification relative to biomass High yield of liquid product (65 75 Wt-% depending on feedstock) Agriculture Residues and Purpose-grown Biomass Fuel Oil Substitution RTP Green Fuel TM Electricity Production Upgrade to Transport Fuels UOP A highly efficient biomass-to-liquid-fuel pathway

7 RFO Co-processing - Why it Makes Sense 6 Compliance solution controlled by the refiner Utilize existing refinery infrastructure Low oil prices increase cellulosic value Easy to implement Produces renewable gasoline & diesel blendstocks Generate cellulosic RINs at the refinery Produce pipeline-compatible biofuels with existing FCC equipment Eliminate dedicated blending infrastructure without blendwall limits Cellulosic RIN value inversely related to crude prices Minor capital costs for storage & feed injection equipment UOP provides injection equipment & operations assistance UOP

8 Co-Processing Project Pathway RFO produced by outside project developer and delivered to refinery Refiner co-processes RFO with VGO in FCC unit to produce partially renewable fuel blendstocks Refiner generates cellulosic RINs at the refinery based on renewable volume blend 7 RTP Unit RTP Green Fuel (or) Pyrolysis Oil (or) Renewable Fuel Oil (RFO) Refiner co-processes RFO with VGO in FCC unit to produce partially renewable fuel blendstocks RFO produced by outside project developer and delivered to refinery Partially Renewable Fuel to Refinery Pool UOP

9 Co-processing Development 8 Multi-year development program for commercialization Lab and pilot plant testing Proof of concept trial EPA Fuel and Facility registration Two 30 day commercial refinery trials in 1H 2016 Deployment expected in 2H 2016 Current Status Concept Selection Pilot Plant Trial Commercial Injection Design Proof of Concept Commercial Trial EPA Part 79 EPA Part Day Commercial Trial Technology Deployment Completed two trials in commercial FCC units In discussion with numerous US refining companies for extended trial in 2016/2017 Currently reviewing multiple refinery partners for commercial trial site UOP

10 Biologically Sourced Feedstocks Characteristics of Concern 9 High oxygen content Acid number typically higher than that found in petroleum Metals higher and different type than found in refinery streams Petroleum: Ni and V Biofeeds: Alkali metals and phosphorus, silicon Chlorides typically present in biological feedstocks some very high Unsaturated hydrocarbons UOP

11 Addressing the Concerns 10 Oxygenates Acid conversion virtually complete in FCC riser Oxygenates in FCC naphtha same as those already seen in petroleum-only FCC operation LCO and heavier cuts no perceptible change in oxygenates Alkali metal effects Studied deactivation at lab scale Economic alkali metal management techniques developed Chlorides Chlorides are possible source of concern in all FCC units Review of operations and equipment before co-processing allows trouble-free operation Unsaturated hydrocarbons Method of operation avoids fouling issues commonly associated with pyrolysis oil at high temperature Commercial proof of concept trial indicated trouble-free injection UOP These measures and others address refiners concerns

12 Mono-Aromatic Wt-% Olefins & Naphthenes Wt-% Important fuel properties virtually unchanged in commercial trial Naphtha Olefins & Naphthene with 1 vol-% RTP Green Fuel Addition Before RTP Green Fuel added 8 hours of RTP Green Fuel Addition 16 hours of RTP Green Fuel addtion UOP C 6 C 7 C 8 C 9 C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 C 21 C 22 C 23 C 24 C 25 C 26 Naphtha Mono-Aromatics by Carbon Number after 1 vol-% Pyoil Addition Before RTP Green Fuel Added After 8 hours of RTP Green Fuel Addition After 16 hours of RTP Green Fuel Addition C 6 C 7 C 8 C 9 C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 C 21 C 22 Bulk chemical composition of FCC products similar to petroleumonly feed

13 Co-Processing pilot plant yields result in promising economic projections 12 ~15 MM of Cellulosic (D 3 & D 7 ) RINs can be generated 2.25 LV% addition of RFO to BPSD FCC Recent circulating pilot plant test program for a US refiner showed the following process benefits: $/bbl RFO calculated benefits in 2015 (@1.64$/RIN) $/bbl RFO calculated benefits in 2016 (@2.55$/RIN) Example RTP Green Fuel FCC Yields (Marginal Wt-% of RTP Green Fuel) Gasoline + LCO Dry Gas + LPG + Bottoms H2O CO + CO2 Coke Source: UOP LLC UOP

14 Learn More RE&C Overview Video: 13 Green Jet Video: Green Diesel Video: Revamps Video: RTP Video: UOP

15 UOP RENEWABLE ENERGY & CHEMICALS 14 THANK YOU UOP is committed to providing technology options that enable our customers to produce the highest quality renewable fuels UOP

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