Bio-Oil Upgrading and Stabilization

Transcription

1 Bio-Oil Upgrading and Stabilization Presented at the Kansas State University Bioenergy Symposium April 27, 2011 Alan Zacher Doug Elliott PNNL-SA-79097

2 Outline Fast pyrolysis bio-oil properties Bio-oil upgrading by catalytic hydrogenation Status of process development

3 Temperature Bio-Oil from Fast Pyrolysis Liquid intermediates from the flash degradation of hemicellulose, cellulose, and lignin Fast Pyrolysis, 450C < T < 550C, < 2 sec T As : Gas Oil As Δt H : Char Oil As Δt Q : Gas Oil Δt H Time Δt Q

4 Comparison of Wood-Derived Bio-oils and Petroleum Fuel Characteristic Fast pyrolysis Bio-oil Wet Dry Heavy petroleum fuel Water content, wt% Insoluble solids, % % Carbon, % Hydrogen, % Oxygen, % Nitrogen, % < Sulfur, % < Ash <0.1 HHV, MJ/kg Density, g/ml Viscosity, cp @50ºC 180@50ºC

5 Unwanted Characteristics of Bio-oil Attribute Problem Solution Low ph High viscosity Instability Solids content Alkali metals Water content Corrosion Handling, pumping Storage, phase separation, polymerization, viscosity increase Combustion problems, equipment blockage, erosion Deposition of solids in boilers, engines, and turbines Complex effect on heating value, viscosity, ph, homogeneity, etc. Adequate Materials Neutralization Hydroprocessing Add water or solvent Hydroprocessing Avoid heat Catalytic Stabilization Add Water or Diluents Liquid filtration Hot gas filtration Biomass pretreatment Hot gas filtration Catalytic upgrading Optimization of water content according to application

6 What Kind and Degree of Upgrading? First, determine final use Heavy boiler fuel Power turbine light fuel oil Diesel engine light fuel oil Refinery feedstock for liquid fuel production Recovery of chemical products Next, determine upgrading requirement Physical upgrading Solvent addition Filtration Separations Chemical/catalytic upgrading

7 Atmospheric and Vacuum Distillation PIPELINE Refinery Drop-in points for Bio-Oil Biomass Refinery-Ready Intermediates Research Areas Near-Fuels and Blendstocks Drop in Point #1: Pyrolysis Oil Drop in Point #2: Stable Oil Drop in Point #3: Fuels Blendstock Crude Oil Gas Light Naphtha Heavy Naphtha LGO VGO Atm. Res. Vac. Res. Reform FCC Alky/Poly HT/HC Coker Gasoline Jet Fuel Diesel Fuel Drop-In Fuels Existing Refinery Infrastructure

8 Conclusions from Non-isothermal Hydroprocessing of Bio-oil from Wood Residual oxygen content directly correlates with processing space velocity Gasoline range product yield directly correlates with processing space velocity Fast pyrolysis products (from different reactors and feed types) are similar with respect to hydrotreating and hydrotreating products

9 Pyrolysis Bio-oil Upgraded Products Percent oxygen Veba Oel Baldauf, W.; Balfanz, U. Veba Oel AG, Final Report JOUB-0015, 1992

10 Reactivity Scale of Oxygenated Groups Under Hydrotreatment Conditions 150ºC olefins 200ºC aldehydes ketones alcohols aliphatic ethers 250ºC aliphatic alcohols Thermal dehydration olefin 300ºC carboxylic groups phenolic ethers 350ºC phenols di-phenyl ether 400ºC dibenzofuran UCL E. Laurent & B. Delmon 1994

11 Catalytic Hydrogenation Development Early Work Based on petroleum processing technology Sulfided catalysts Exhaustive hydrogenation Liquid hydrocarbon fuel products Highly aromatic product High hydrogen consumption Present Work Optimized for bio-oil products Non-sulfided catalysts Directed hydrogenation Liquid fuel and chemical products Mixed hydrocarbon products Targeted hydrogen consumption Current Challenges Bed Fouling Catalyst Lifetime Hydrogen Consumption

12 Bench-Scale Continuous-Flow Catalytic Hydrogenation System H 2 bio-oil HT HC Zone 1 Zone 2 Gas Metering and Analysis C LHSV atm 1-10 m 3 H 2 /L bio-oil Fuel and Aqueous Product Recovered products are analyzed determine composition and value

13 Comparative Yields of Two-stage Processing versus Non-isothermal Processing HT/HC total Hydrotreating Hydrocracking Nonisothermal Mixed Wood dry oil yield, g/g aqueous yield, g/g C gas g/g H 2 consumption, L/L Corn Stover dry oil yield, g/g aqueous yield, g/g C gas g/g H 2 consumption, L/L Hot-filtered poplar dry oil yield, g/g aqueous yield, g/g C gas g/g H 2 consumption, L/L Elliott, et al. Environmental Progress & Sustainable Energy 28(3), ; 2009

14 Gasoline Analyses Hydroprocessed bio-oil (from mixed wood) Petroleum Gasoline Min Max Typical Paraffin, wt% Iso-Paraffin, wt% Olefin, wt% Naphthene, wt% Aromatic, wt% Oxygenate, wt% 0.8 The carbon recovery based on bio-oil was about 50%. Holmgren, J. et al. UOP LLC, NPRA national meeting, San Diego, March 2008.

15 Gasoline/Diesel Prospects Bioderived fuel from corn stover spinning band distillation 54% in gasoline range IBP-193 C Gasoline Octane number RON+MON/2=89 35% in diesel range C Cetane number % heavies >325 C likely partially converted feed from: Timothy Brandvold, UOP LLC, Pyrolysis Oil to Gasoline presented at the Thermochemical Portfolio Alignment and Peer Review April 15, 2009, Denver, CO

16 Jet Fuel Produced from Pyrolysis Oil Feed PNNL from product PNNL Product, hydrotreated Refined PNNL and product run over Density, g/ml Degree API Flash point, C Oxygen, mass % 0.13 < 0.02 Pyrolysis jet fuel was lightly treated to remove residual water and mixed with synthetic paraffinic kerosene (SPK) to produce a 100% biojet fuel wt% jet fuel distillate by batch vacuum distillation PHOTO: Boeing U-787, Ed Clark /september/sept09frontiers.pdf

17 UOP Integrated Biorefinery Demonstration Kapolei, Oahu, Hawaii $25 M DOE funded with industrial cost share UOP LLC, Ensyn, PNNL, Tesoro, and many others Integrated pyrolysis and hydroconversion Demonstrate fungibility within the petroleum refinery and determine fuel properties 1 ton/day = 4 bpd renewable gasoline, diesel, jet fuel Accelerate liquid transportation fuel production Detailed life cycle assessment and growth potential = Commercialization plan includes 4 RTP units and 1 upgrading unit to produce 50 million gallons of fuels annually

18 Distributed Pyrolysis and Centralized Bio-oil Processing Refinery Corn Stover P P P P P P Deoxygenate Biomass Pyrolysis Mixed Woods Stabilization Biocrude Other Refinery Processes Gasoline Diesel Jet Chemicals Holmgren, J. et al. UOP LLC, NPRA national meeting, San Diego, February 2008.

19 Conclusions Biomass conversion to liquid fuels via pyrolytic processes and catalytic hydroprocessing remains under development Process economics are promising in the current economic environment (Jones, et. al, 2009) Scale-up is envisioned in the near term Jones SB, et al Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case. PNNL Rev. 1, Pacific Northwest National Laboratory, Richland, WA.