National Renewable Energy Laboratory

Biomass Gasification Overview
Presented by Richard L. Bain
January 28, 2004
Operated for the U.S. Department of Energy by Midwest Research Institute • Battelle

Office of the Biomass Program
Goals
Reduce U.S. dependence upon foreign sources of petroleum Realization of the Industrial Biorefinery

Mission
To foster research and development on advanced technologies to transform our abundant biomass resources into clean, affordable, and domestically-produced biofuels, biopower, and high-value bioproducts for improving the economic development and enhancing the energy supply options of the U.S.

The Unique Role of Biomass While the growing need for sustainable electric power can be met by other renewables…

Biomass is the only renewable that can meet our demand for carbon-based liquid fuels and chemicals

Research Focus for the Biorefinery
Advanced Biomass R&D

Sugar Platform
Residues

Sugar Feedstocks

Biomass

Combined Heat & Power
Clean Gas

Fuels, Chemicals, & Materials

Integrated Industrial Biorefineries

Thermochemical Platform

Conditioned Gas

Systems Integration

Thermochemical Platform Costs for SynGas Intermediate Impact of Overcoming Technical Barriers 20 Reference: Hamelink and Faaij (2001) 18 16 Cost of Production ($/GJ) Without Integrated Demonstrations 14 12 10 8 6 4 2 0 Pioneer Plant Costs With Integrated Demonstrations Base 550 tpd Nth plant Feed Handling Thermochemical Conversion Gas Conditioning Sensors & Controls Process Integration .

3 1.7 0.90 30 2.000 2025 4.17 0.g.99 0.70 30 2.26 0.90 0. LHV) Corre sponding H2 cost ($/kg) j product. e .98 1.1 1.000 2015 5.20 30 550 2010 6 1.3 0.30 30 550 2005 8.6 1.000 2020 5.16 1..Performance Specific Program Goals Ye a r Minim um Synga s Se lling Price ($/GJ.08 0.54 30 4. m e tha nol ($/ga l) Fe e dstock cost ($/dry ton de live re d) Pla nt size (dry tons/da y) 2003 9 2.60 30 2.000 2030 4.000 Feed Preparation/Gasification: 10% reduction in product cost by 2010 Gas Cleanup: 20% reduction in product cost by 2010 System Integration: 10% reduction in product cost by 2010 Strategic Fit .65 30 2.

Wet Gasification . Liquefaction.Biomass Thermochemical Conversion For Fuels and Chemicals Gasification Cleanup Synthesis PRODUCTS • Hydrogen • Alcohols • FT Gasoline • FT Diesel • Olefins • Oxochemicals • Ammonia • SNG Biomass Pyrolysis Conversion or Collection Purification • Hydrogen • Olefins • Oils • Specialty Chem Other Conversion * Separation Purification • Hydrogen • Methane • Oils • Other * Examples: Hydrothermal Processing.

Black Liquor is the lignin-rich by-product of fiber extraction from wood in Kraft (or sulfate) pulping. chemicals. or fuels. heat. The industry burns black liquor in Tomlinson boilers that 1) feed back-pressure steam turbines supplying process steam and electricity to mills. . It can be used as a solid fuel. 2) recover pulping chemicals (sodium and sulfur compounds) for reuse. or converted into liquid or gaseous forms for the production of electric power.Basic Definitions Biomass is plant matter such as trees. agricultural crops or other biological material. grasses.

53 11.61 6310 52.25 4.48 6.18 0.05 <0.04 0.20 --0.10 0.18 0.82 0.77 2.21 11.01 <0.96 13.33 32.01 1.02 0.05 41.61 4971 Corn Stover Chicken Litter Black Liquor Ele mental Ash Ana lysis.05 0.01 35.79 0.80 8382 4.45 1.05 --0.79 0.08 1.07 51.39 0.02 0.71 0.71 0.65 0.62 0.14 19.05 4.Representative Biomass & Black Liquor Compositions Poplar Proximate (w t% as rece ived) Ash Volatile Ma tter Fix ed Carbon Moisture HHV.87 1.25 0.16 43.10 39.12 2. w t% as rece ive d Carbon Hydrogen Nitrogen Sulfur Oxygen (by diff) Chlorine Ash 47.85 0.24 4.39 0.01 .01 1.05 5.72 2.29 0.99 13.75 75.14 0.08 0.65 58.26 6.06 7782 18.11 9.08 0.05 <0. Dry (Btu/lb) Ultimate.96 34.75 32.01 8.01 0.64 0.59 14 <0.23 6.16 81. w t% of fuel a s re ceive d Si Fe Al Na K Ca Mg P As (ppm) 0.22 0.00 5.01 <0.91 1.98 5.82 0.

02 16.900 .530.01 0.16 68. Btu/lb Wood Biomass 2 Coal 1 Coal 2 Rosebud.001-0.79 4.0 0-0.12 6.2 5.5 7.Representative Biomass and Coal Properties Biomass 1 Name Classification Proximate Analysis.81 11.58 4.1-2 50-53 5.79 9.16 40.6 10.684 83.6 8.8 2.18 0.8 12. Dry.4-1.1 38-44 0-0.1 0.3 0. MT sub B Tar Sands Athabasca Bitumen Red Corn Cob Grundy.93 68.08 9.16 0.84 39. wt% Dry Moisture Volatile Matter Fixed Carbon Ash Ultimate Analysis. No 4 HvBb 25-60 77-87 13-21 0. IL.64 0.9.47 17.99 0.61 1. 80 -4 45 5.340 8.1-2 1.8-7.02 49.050 16 ca.93 0. wt % Dry C H N Cl O S Ash H/C Atomic Ratio HHV.39 4.3 .5 0 4 1.4 -42.4 -0.400 19.76 13.6 45.5 1.47 13.

Pyrolysis • Basic Definitions Thermal conversion (destruction) of organics in the absence of oxygen • In the biomass community. with char. this commonly refers to lower temperature thermal processes producing liquids as the primary product • Possibility of chemical and food byproducts Gasification • Thermal conversion of organic materials at elevated temperature and reducing conditions to produce primarily permanent gases. water. and condensibles as minor products • Primary categories are partial oxidation and indirect heating .

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2 MPa ENSYN Dynamotive BTG Fortum Chemrec (Air) Low (300-600°C) Medium (700-850°C) Temperature High (900-1200°C) .Thermochemical Conversion Of Biomass and Black Liquor Dry Ash Product Bio-Oil Changing World Technologies Gas Product: PNNL Wet Gasification (CH4/H2) GTI (O2) Carbona (O2) HTW O2) Foster Wheeler (O2) Syngas Slag Chemrec (O2) Noell High Pressure 10-25 MPa Feed: Biomass 1.3 MPa Feed: Biomass MTCI-also Black Liquor FERCO (Indirect) MTCI (Indirect) Pearson (Indirect) TUV (Indirect) For CHP:TPS (Air) Carbona (Air) Lurgi (Air) Foster Wheeler (Air) EPI (Air) Prime Energy (Air) 2 – 3 MPa Feed: Black Liquor Low Pressure 0.

Technical Barrier Areas Biomass Residues Dedicated Crops Hydrogen & Bioproducts Fuels & Chemicals Export Electricity Feed Processing & Handling Gasification & Pyrolysis Gas Conditioning & Separation Syngas Utilization Heat & Power Generation Biorefinery Residues Feed Processing and Handling Gasification / Conversion Gas Cleanup and Catalytic Conditioning Syngas Utilization Process Integration Process Control. and Optimization Critical Issues . Sensors.

Vessel design .Storage .Metals .Catalytic Conversion .Bed behavior/agglomeration • Mill Integration .Stability .Steam .Tars .Halogen management • Sensors and Controls .Alkali management .Gasifier Design • Gas Cleanup & Conditioning .Ash .Transportation • Oil Properties .Feed modification • Gasification .Non-condensing Cleanup • Syngas Utilization .Toxicity .Carbon management .Condensing Cleanup .Use in Petroleum Refineries Black Liquor Gasification • Containment .Biomass Thermochemical Conversion Primary Technical Barriers Gasification • Feed Pretreatment .Sulfur management .Acidity • Oil Commercial Properties .Refractories .Commercial Specifications .Cleanliness requirements .Gas composition • Process Integration • Sensors and Controls Pyrolysis • Oil Handling .Causticizing • Fuels Chemistry .Power .Tar & Heteroatom chemistry .Feeder reliability .

Representative Gasification Pathways Biomass Low Pressure Gasification Shift Conversion Compression Feed Preparation & Handling Oxygen CO2 Product High Pressure Gasification Hot Gas Cleanup Reforming Compression Acid Gas Removal Synthesis LP Indirect Gasification Cold Gas Cleanup Compression & Reforming LP Indirect Gasification Catalytic Conditioning & Reforming Compression .

Water Pyrolysis C + CO2 = 2CO C + H2O = CO + H2 C + O2 = CO2 4H + O2 = 2H2O Reduction Combustion Ash C + O2 = CO2 4H + O2 = 2H2O C + CO2 = 2CO C + H2O = CO + H2 Pyrolysis Gas. Tar.Biomass Biomass Cyclone Freeboard Gas. Tar. Water Ash Fluid Bed Combustion Reduction Ash Air Plenum Biomass Air/Steam Air Updraft Gasifier Downdraft Gasifier Flue Gas Fluid-Bed Gasifier Gasifier Primary Cyclone Secondary Cyclone Fly Ash Biomass Biomass Char Furnace Recycle Gas N2 or Steam Air/Steam Bottom Ash Air Entrained Flow Gasifier Circulating Fluid-Bed Gasifier .

Community Power Corporation’s BioMax 15 Modular Biopower System .

FERCO GASIFIER. VT 350 TPD .BURLINGTON.

Denmark TAR CRACKER GASIFIER BIOMASS FUEL FEEDING GAS COOLER ASH GAS COOLER GAS TANK STACK HEAT RECOVERY POWER AIR GAS ENGINE(S) ASH HEAT .Carbona Project: Skive.

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Typical Gas Heating Values Gasifier Inlet Gas Product Gas Type Product Gas HHV MJ/Nm Partial Oxidation Partial Oxidation Indirect Air Oxygen Steam Producer Gas Synthesis Gas Synthesis Gas Natural Gas Methane 7 10 15 38 41 3 .

Gas composition versus reactor type Gas ifie r FERCO Carbona Prince ton M ode l Type Age nt Be d M ate rial Fe e d Gas Com pos ition H2 CO CO2 N2 CH4 C2+ GCV . M J/Nm 3 26.8 9.2 Indire ct CFB s te am olivine w ood chips Air FB air s and w ood pe lle ts Indire ct FB s te am none black liquor PFB O2/s te am alum ina w ood chips IGT .2 19.0 9.3 21.4 41.4 17.1 11.4 39.2 15.8 11.0 4.08 0.9 27.70 23.2 13.2 2.6 5.9 4 16.2 13.6 0.1 0.2 38.1 2 14.1 28.4 29.

4 3.12 11.7 27.77 11.95 Indire ct FB s te am s ilica w ood chips Fre e Univ of Brus s e ls Air FB air s ilica w ood chips Univ of Zaragos a Dow ndraft air none w ood chips Updraft air none w ood chips PFB O2/s te am alum ina w ood chips USEPA IGT .17 18 Diff 5-7 3 16 21.5 22.11 15 .3 NA 10 14.5 14.07 28.9 4.2 4 9 .21 1.8 11.88 27.4 44.9 NA 19.Gas composition versus reactor type Gas ifie r Te ch Univ V ie nna Type Age nt Be d M ate rial Fe e d Gas Com pos ition H2 CO CO2 N2 CH4 C2+ 31.4 2.8 12.8 28.

Gasifier Types-Advantages and Disadvantages G asifier Updraft A dvantages M ature for heat Sm all scale applications Can handle high m oisture No carbon in ash Sm all scale applications Low particulates Low tar Large scale applications Feed characteristics Direct/indirect heating Can produce syngas Large scale applications Feed characteristics Can produce syngas Can be scaled Potential for low tar Can produce syngas D isadvantages Feed size lim its High tar yields Scale lim itations Producer gas Slagging potential Feed size lim its Scale lim itations Producer gas M oisture sensitive M edium tar yield Higher particle loading Dow ndraft Fluid Bed Circulating Fluid Bed M edium tar yield Higher particle loading Large am ount of carrier gas Higher particle loading Potentially high S/C Particle size lim its Entrained Flow .

59 17.50 1.24 1.96 11.77 5.97 13.20 0. ppmv Ammonia. ppm-m/v K cond. ppmv Cl cond.86 0.06 0.96 0.67 17.73 4.56 4. ppm-m/v Tot org. Contaminant Yields Hybrid Poplar 33.31 0.91 12.62 323-396 760 max 486 max 208 max 2320 max 1442-1472 Mixed Woods 31.93 64-72 290 max 0 10 max 2060 max 37 Switchgrass 24. C cond ppm-m/v Cyanide.47 14.99 36.Typical Gas. vol % CO CO2 CH4 C2H4 Benzene Toluene H2/CO H2S.41 1. ppm-m/v + - .35 0.31 39.01 36-63 339-369 4 max 7 max 2480 max ND H2.82 31.

CH4 CO. H2O Tertiary Processes PNA’s. Aromatics. Aromatics CO. & Oxygenates Olefins. H2. H2. CO2. CO2. aromatics) High P Low P Solid Phase Biomass Charcoal Coke Soot High P Pyrolysis Severity . H2O Low P Liquid Phase Primary Liquids Condensed Oils (phenols. H2O. CO. CO2. H2O Primary Vapors Secondary Processes Light HCs. CO2.Primary Processes Vapor Phase CO. H2.

Mixed Oxygenates 400 o Phenolic Ethers 500 o Alkyl Phenolics 600 o Heterocyclic Ethers 700 o PAH 800 o Larger PAH C 900 o C C C C C C o n v e n tio n a l F la s h P y r o ly s is (4 5 0 .T e m p e r a tu r e F la s h P y r o ly s is (6 0 0 .5 0 0 oC ) A c id s A ld e h y d e s K e to n e s F u ra n s A lc o h o ls C o m p le x O x y g e n a te s P h e n o ls G u a ia c o ls S y r in g o ls C o m p le x P h e n o ls * A t th e h ig h e s t s e v e r ity .T e m p e r a tu r e S te a m G a s ific a tio n (9 0 0 . n a p h th a le n e s s u c h a s m e th y l n a p h th a le n e a r e s tr ip p e d to s im p le n a p h th a le n e . 1988) .1 0 0 0 oC ) N a p h th a le n e * A c e n a p h th y le n e P h e n a n th r e n e F lu o r a n th e n e P y re n e A c e p h e n a n th r y le n e B e n z a n th r a c e n e s B e n z o p y re n e s 226 M W PAH s 276 M W PAH s Chemical Components in biomass tars (Elliott.6 5 0 oC ) Benzenes P h e n o ls C a te c h o ls N a p h th a le n e s B ip h e n y ls P h e n a n th r e n e s B e n z o fu r a n s B e n z a ld e h y d e s C o n v e n tio n a l S te a m G a s ific a tio n (7 0 0 .8 0 0 oC ) N a p h th a le n e s A c e n a p h th y le n e s F lu o r e n e s P h e n a n th r e n e s B e n z a ld e h y d e s P h e n o ls N a p h th o fu r a n s B e n z a n th r a c e n e s H i. H i.

methanol.Gasification Applications • Heat • District heating • Plant steam • Institutional heating • Combined heat and power • Pulp and paper industry • District heating/electricity • Electricity only • Cofiring .ash segregation • Integrated gasification combined cycle • Synthesis gas • Oxygenates . ethanol. DME. • Fischer-Tropsch Liquids • Hydrogen • Methane • Chemicals . etc.

Biorefinery Utilities Applications .

University of Arkansas • Hydrocarbon fuels • Methane • Fischer Tropsch • Iron based . Dow.ethanol • Dow.Examples of Conversion Processes • Oxygenates • Methanol. Pearson Technologies • Biochemical (fermentation) • Mississippi State University.Synthesis Gas . Mobil MTG • Mixed alcohols • Snamprogetti/Topsoe.Sasol Synthoil • Cobalt based . IFP/Idemitsu • Modified Fischer Tropsch . DME. Lurgi.Shell middle distillate synthesis (SMDS) • Hydrogen • Methane steam reforming • High and low temperature shift • H2 separation .

Co. CaO) hom Co ologa tion Al2O3 d l 2O pe /A do nO li3 /Z 3 ka r 2O Cu l 2O Al /C .R O h. A O nO O/ Zn u/Z /Co C O Cu oS 2 M 3 zeolites Methanol MTO MTG U ect Dir Olefins Gasoline Rh sis se e th yn DME M100 M85 DMFC NH3 H2 Ethanol Aldehydes Alcohols . Co ca CH rbon y 3O H latio Co +C n . Ni Mixed Alcohols Acetic Acid Fischer-Tropsch H2O WGS Purify N2 over Fe/FeO (K2O.Waxes Diesel Olefins Gasoline MTBE isobutylene acidic ion exchange Fe. Al2O3. Ru Formaldehyde Ag i-C4 Isosynthesis ThO2 or ZrO2 Syngas CO + H2 ) os 3 ) 4 (Bu Ox CO ) 3P 3) 3 o( CO Ph HC o( )(P HC h(CO R Cu/ZnO .

BIOMASS FEED PREP GASIFICATION CLEANUP & CONDITIONING SYNGAS Ethanol From Biomass Thermochemical Syngas – Biochemical Ethanol BIOCONVERSION SEPARATION ETHANOL .

Oxygen.C11) Oligomerization Isomerization Hydrogenation High T FTS )1) CO + 3H2 CH4 + H2O (Methanation) CnH2n+2 + nH2O (Paraffins) )2) )3) )4) nCO + (2n+1)H2 nCO + 2nH2 nCO + 2nH2 Gasoline CnH2n + nH2O (Olefins) CnH2n+1OH + (n-1)H2O (Alcohols) . Natural Gas. or Biomass Gasifier Gas Cleanup and Conditioning Particulate Removal Wet Scrubbing Catalytic Tar Conversion Sulfur Scrubbing WGS etc. Steam Coal. Clean syngas H 2 and CO Diesel CFB or FFB(Fe) Reactor Olefins (C3 .Fischer Tropsch Synthesis Low T FTS Slurry (Co) or Tubular (Fe) Reactor Waxes (> C20) Hydrocracking Air.

Simplified Methanol Synthesis Process Flow Diagram Steam.47 kJ/mol CO2 + 3H2 CO + H2O Preferred Stoichiometry: (H2 – CO2)/(CO + CO2) = 2 .67 kJ/mol ∆Hr = -41.64 kJ/mol ∆Hr = -49. O2 Natural Gas Desulphurization syngas (CO/CO2/H2) Compressor Methanol Converter Steam Reforming BioSyngas Cooling and Distillation Methanol Purge Gas CO + 2H2 syngas recycle loop CH3OH CH3OH + H2O CO2 + H2 ∆Hr = -90.

for CHP Non extracting .GT and IGCC applications Stirling engines Fuel cells .Prime Movers Steam turbines Extracting .electricity only Small to large scale IC engines 5 kW to 2 MW Control of NOx and CO Turbines Microturbines Gas Turbines .Heat and Power .

Why Biomass + Fuel Cells? Good temperature and pressure match Attractive fuel gas characteristics Allows penetration of fuel cells into markets without natural gas distribution networks High efficiency maximizes biomass conversion to electricity .reduces biomass demand for energy production Fossil carbon substitution .

Fuel Cells are "Reverse" Electrolysis .

Fuel Cell Schematic Electrolyte (Ion conductor) Depleted fuel Out O2 PEMS PAFC MCFC SOFC Fuel In Anode Cathode H2 H + Depleted Oxidant Out H2O O2 H2O O2 CO3= CO2 O2 1000ºC Oxidant In 80ºC 200ºC H2 H2 CO2 H2O H2 H2 O H+ 650ºC O= .

C. Output .Cyclone Gas Cleanup Freeboard Product Gas Exhaust Ash Fluid Bed Biomass Plenum Air/Steam Compressor Cooling Air Isothermal Pre-reformer HRSG Fluid-Bed Gasifier Carbonate Fuel Cells A C Process Water DC/AC Inverter Air Burner A.

ammonia. ash • Residual carbon control • Integrated process specific species • Gas separations • Process integration • Prime mover systems • Catalytic syngas conversion • Sensors and controls • LCA and TE modeling . water • Particulates.Research and Development Areas (not all-inclusive) • Feed characterization • Materials handling • Storage • Conveying • Moisture control • Comminution • Feeding • Gasification • Kinetics • Phase equilibria • CFD modeling • Gas cleanup • Tar.

NREL Facilities MBMS Engine Testing Gasification (TCUF) TMBMS Emissions Monitoring .

Fluidized Bed Reactor Cyclones Superheated Steam Char Aqueous Effluent .Thermochemical Process Development Unit (TCPDU) Base Configuration Biomass Feed Thermal Cracker Blower Coalescing Filter Hopper/Feeder Scrubber Wet scrubbed Syngas Settling Tank Controller 8-in.

2 biomass feed rate (kg/h) 10.TCPDU Process Conditions and Product Gas Composition TCPDU process parameters 11-Feb-03 to 28-Feb-03 steam feed rate (kg/h) 20.16 ± 0.68 ± 0.1 ethane 0.methylanthracene? .04 propylene 0.flourene .04 1.5 ± 0. w/ steam and N2) benzene 1732 ± 165 toluene 715 ± 89 cresol 216 ± 44 naphthalene 327 ± 33 phenanthrene 72 ± 7 78 8e+4 78 .pyrene/flouranthene .cresol 116 . N2.acenaphthalene .styrene 108 .2 ± 0.0 ± 0.toluene 94 .5 ± 0.indene 128 .8 ethylene 4.4 carbon dioxide 23.9±10% Averaged mass spectrum (TMBMS) of tars from indirect wood gasification 1e+5 Average gas composition from indirect wood gasification in TCPDU 2/11 to 2/28/03 GC analysis of Port 3 (vol.4 methane 15.benzo(a)flourene 6e+4 4e+4 91.anthracene/phenanthrene .0 ± 0.1 ± 0.2 carbon monoxide 26.9 ± 1.benzene 91.04 1-butene 0.methylnaphthalenes .6 ± 0.32 ± 0.7 ± 1.07 acetylene 0.8 material balance 98.47 ± 0.92 94 116 128 2e+4 104 108 142 152 166 178 125 150 175 192 202 216 200 0 75 100 .9 fluid bed T (ºC) 615 ± 1 thermal cracker T (ºC) 775 ± 2 product gas flow rate (kg/h) 8.phenol 104 .naphthalene 142 152 166 178 192 202 216 . %.and steam-free) hydrogen 26.92 .1 H2/CO ratio Tar concentrations by TMBMS (ppmv.

2001 Gas Flow Rate 0.) Difference Mass Spectrum (catalyst outlet-inlet) showing destruction of biomass gasifier tars 5000 0 -5 0 0 0 p y re n e to lu e n e n a p h th a le n e -1 0 0 0 0 -1 5 0 0 0 benzene -2 0 0 0 0 50 75 100 125 150 175 200 225 m /z .6 hr-1 0.4 kg/hr 7-18 kg/hr 30 cm pilot-scale reformer – April 2002 WHSV (weight of feed/hr / weight of catalyst) 1.16-0.48 hr-1 Temperature 700-900°C 850°C 25000 CO 20000 2 (/1 0 ) 15000 10000 Intensity (arb.35-0.Experimental Approach 5 cm bench-scale reformer – March.

Contract placed Expected Installation delivery complete Catalyst testing 1/03 4/03 6/03 Tar Reformer 11/03 12/03 Scrubber 2/04-9/04 Cyclones .Project Status RFP issued Response received Revise scope to reduce cost.

axis) 500 80 75 0 0 1 2 3 4 5 6 7 time-on-srteam (h) .100 850 C benzene o 825 C o 800 C o 775 C o 750 C o 80 % conversion 60 40 m ethane Methane and benzene breakthrough vs. 20 0 0 1 2 3 4 5 6 7 tim e-on-stream (h) 105 850 C o 825 C o 800 C o 775 C o 750 C o 2000 100 total tar benzene slip (ppmv) 95 1500 % conversion 90 1000 Total tar conversion and benzene slip for NREL-1Catalyst during temperature ramp experiments 85 benzene slip (rt. time-on-stream for temperature ramp experiments with NREL-1 catalyst.

/anthr. cresol 750 775 800 825 850 2FBR tem perature ( o C) Steady State conversion of several tar species and methane for NREL-1 catalyst .NREL-1 Tem perature Ram p 100 80 % conversion 60 40 20 0 m ethane benzene toluene naphthalene phenan.

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