Upgrading Biomass Pyrolysis Vapors to Fungible Hydrocarbon Intermediates tcbiomass 2017 K. Magrini, J. Olstad, M. Jarvis, Y. Parent, B. Peterson, S. Deutch, K. Iisa, M. Sprague, G. Powell September 20, 2017 NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.
Outline Biomass Pyrolysis Vapor Phase (Ex-situ) Upgrading NREL Thermochemical Conversion Systems Project Goal and Technical Targets Pyrolyzer/DCR System Pilot Scale Pyrolysis Vapor Upgrading and Product Analysis Summary 2
Staged Multi-Scale Evaluation Improves Research Efficiency Process and catalyst evaluation at multiple scales: Improves research efficiency, thus reducing cost Provides data that is directly transferrable to industry partners Allows for a tiered catalyst and process development approach 3
Project Goal Seek, develop, evaluate and characterize ex-situ upgrading catalysts with biomass pyrolysis vapors at the small pilot scale to produce refinery compatible intermediates of: Catalyst performance targets Oxygen content < 10% Coking < 10% Carbon efficiency > 43% Fuel Cost $2.00 GGE (with feedstock) By 2022 4
Vapor Phase Upgrading: Cost and Technical Targets Feedstocks Pyrolysis Hot Vapor Analysis Vapor Phase Upgrading Hot Gas Filtration Vapor Feed to DCR Condensation Condensation Pyrolysis Oil Robust FCC-type upgrading catalysts Comprehensive vapor analysis Integrated pyrolysis/dcr system for VPU Results transfer to petroleum refining Upgraded Oil Hydrotreating Project rationale: Vapor phase upgrading a significant process cost component A. Dutta 5
Coupled Pyrolyzer DCR System motor BIOMASS FEED SYSTEM Pyrolyzer 1-3 kg/ biomass feed 8 hr run time Pyrolysis oil: 1-2 gal Analytics: on line GC, MBMS Total C detector FLUIDIZEDBED REACTOR FILTER Oil Analysis On-line: MBMS, NDIR, GC Off line: 2D GCTOFS, FID NMR, SIM DIS, TAN, CHNO, Oxygen analysis HOT PYROLYSIS GAS PRODUCT VAPORS REGENERATOR DCR Pyrolysis vapor feed (reduced contaminants) ~2 kg catalyst 8 hr 2 mass balance runs Upgraded oil: 1 liter Analytics: on line GC, NDIR, MBMS Continuous coke removal STRIPPER CONDENSER VENT LOCK HOPPER CHAR HANDLING AIR motor SCRUBBER/ SEPARATOR TOP PHASE MIDDLE PHASE LIQUID PRODUCT BOTTOM PHASE AIR motor QUENCHFLUID PUMP N2 STEAM LIQUID PRODUCT REACTOR OIL FEED SYSTEM 6
System Baseline Tests: VGO and E-Cat Define/replicate standard DCR upgrading tests to gasoline Property E-Cat ZSM-5 Mat (%) 75 TSA (m 2 /g) 194 181 MSA (m 2 /g) 42 19 ABD (g/cc) 0.82.84 PV (g/cc) 0.35.21 0-40 (wt-%) 2 21 0-80 (wt-%) 51 76 APS (µm) 79 61 Na (wt-%) 0.23 RE 2 O 3 (wt-%) 1.22 Ni (ppm) 25 V (ppm) 73 Al 2 O 3 (wt-%) 31.29 Fe (wt-%) 0.6 MgO (wt-%) 0.08 P 2 O 3 (wt-%) 0.14 3 CaO (wt-%) 0.01 7.4Å 5.5Å E-Cat and VGO are standard catalyst and feed for gasoline production FCC catalyst: crystalline zeolite (Y), matrix (am. alumina), binder (silica), and filler(kaolin) DCR product from VGO feed. Significant regions identified. VGO samples Property VGO API (⁰API) 24.7 Specific gravity 0.906 Refractive index 1.504 Density (g/ml) --- K factor 12.01 Ave. molecular wt. (g/mol) 430 Arom ring carbons (wt%) 17.6 Naphthenic ring carbons (wt%) 20.3 Paraffinic carbons (wt%) 62.1 Sulfur (wt%) 0.35 Basic nitrogen (wt%) 0.046 Total nitrogen (wt%) 0.14 Conradson carbon (wt%) 0.32 Zn (ppm) 0.1 7
Biomass Vapor Phase Upgrading Tests Diluent (N 2 ) Impact on VGO Upgrading with E-Cat Adding diluent N 2 and/or pyrolysis vapors impacts product chemistry likely due to: reduced contact time increase mass transfer resistance diluent effects For VGO/E-Cat upgrading adding N 2 reduces all compound group intensities: 1-Ring Naphthenic and Olefins 3-Ring Aromatics 2-Ring Aromatics 1-Ring Aromatics 2-Ring Naphthalene VGO + VGO E-Cat + Ecat Paraffin and Isoparaffins VGO + E-Cat + N 2 For VGO/E-Cat/ upgrading adding pyrolysis vapor enhances: 1-, 2-ring aromatics Iso-, paraffins Overall product composition differences are slight 1-Ring Naphthenic and Olefins 2-Ring Aromatics 3-Ring Aromatics 1-Ring Aromatics 2-Ring Naphthalene Paraffin and Isoparaffins Pyrolyzer conditions: 500 ⁰C, 35 psig, 2 second residence time 0.5 biomass/n 2, mixed hardwood feed. DCR conditions: 1 kg total feed, 1.8 kg catalyst, riser T= 520 ⁰C. 8
Pure Pyrolysis Vapor Upgrading - 2D GC of DCR Upgraded Hydrocarbons Catalyst Impact on Product Selectivity Replicate analyses via GCxGC TOFS VPU tests indicate best performing catalyst enhances toluene, xylene reduces phenolics, oxygenates Ga/P-ZSM-5 enhances aromatic production Catalyst ID Type Performance ZSM-5 ZSM-5 additive Enhanced olefins, aromatics Johnson Matthey CP758 Enhanced toluene and xylene, reduced phenolics P-ZSM-5 Phosphorus-stabilized ZSM-5 Enhanced olefins, aromatics Ga/P-ZSM-5 Gallium impregnated phosphorus-stabilized ZSM-5 Enhanced heavy HCs, phenolics 9
100% 80% 60% 40% 20% 0% 100% 80% 60% 40% 20% 0% 100% 80% 60% 40% 20% 0% Compound Classes Mixed hardwood JM CP783 VGO E cat Aromatic Hydrocarbons Mixed hardwood Mixed hardwood Oxygenates JM CP783 JM CP783 VGO E cat VGO E cat 2D GCGC TOFS CFP Product Analysis Unknown Oxygenates Aromatics Alkenes/Alkynes Alkanes 3+ Ring 2 Ring 1 Ring Ethers Acids Methoxies Phenols Furans Esters Carbonyls Alcohols Feedstock Impact: vs. Oak + Alkenes, aromatics, furans Oxygenates (carbonyls) Catalyst Impact: CP783 vs. CP758 (different zeolite/binder) + Unknowns, alcohols, esters, phenols, 1-, 2-ring ketones Furans, buta/enone 100% 80% 60% 40% 20% 0% Mixed hardwood Carbonyls JM CP783 VGO E cat 3-Ring Ketone 2-Ring Ketone 2-Ring Aldehyde 1-Ring Ketone 1-Ring Aldehyde Other 0-Ring Pentenone Buta/enone 10
NMR Oil Analysis of CFP and FP Oils 16 14 12 31 P NMR 13 C shows CFP Oils have: Reduced C=O, aliphatic C-O, methoxyl Relative % 10 8 6 4 2 Total OH mmol carboxylic OH mmol phenolic OH mmol aliphatic OH Enhanced aromatic C-H Slight impact of catalyst and feedstock 0 CP758-HW CP758-P CP783-P VGO FPO-P FPO-HW 220 200 13 C NMR 180 31 P shows CFP Oils have: Reduced aliphatic OH agree with 13 C Al. C-O result Slight impact of catalyst and feedstock Relative% 160 140 120 100 80 60 40 20 0 C=O Ar. C-O Ar. C-C Ar. C-H Al. C-O Methox Al. C-C HW FP Oil FP Oil VGO CP783-P CP758-P CP758-HW Carbon Type 11
Hydrotreated CFP Oil: 100% Biogenic Fuels DCR conditions: 550⁰C residence time ~1s, 15 psig (27 psia) Carbon efficiency: 30% with 500⁰C pine pyrolysis vapor at a 1:1 biomass:n 2 ratio. Hydrotreating: 400 o C LHSV 0.20h -1 for ~90 h DCR CFP oil Hydrotreated DCR CFP oil A Net Weight (g) Percent Volume Boiler Initial 51.53 100% 60 Lights 1.68 3% Gasoline (71-182) 23.91 46% Diesel (182-320) 20.20 39% Fraction Recovery 45.79 89% Total Recovery 49.97 97% Losses 1.57 3% B: 46% gasoline 39% diesel 12
Summary Reproducible operation of a coupled biomass pyrolysis DCR system was demonstrated with E-Cat and VGO : liquid products were analyzed via 2D GCTOFS, SIM DIS and NMR Vapors co-fed with VGO and E-Cat increased 1-, 2-ring aromatic and paraffin content of the upgraded product Adding ZSM-5 increased 1-, 2-ring naphthenic, olefin and paraffin product content Pure biomass vapor upgrading in the DCR with E-Cat and 2 types of Johnson Matthey H- ZSM5 HZSM-5 produces xylenes, C2 aromatics, less heavy HCs, reduced oxygenates E-Cat produces more heavy HCs (3 and 4 ring aromatics) and less light HCs Slight feedstock impact (oak, pine) Ga/HZSM-5 increased BTX Hydrotreated DCR CFP oil: 46% gasoline and 39% diesel (3 vol% loss) Upcoming Evaluate co-feeding vapors with VGO Feed single or dual feed CFP enhanced VGO Develop/test dual feed, independently heated nozzles (FP, CFP feeds with VGO) 13