Pyrolysis Oil and Upgrading

PNNL-22133 Prepared for the U.S. Department of Energy under Contract DE-AC05-76RL01830 Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: 2011 State of Technology and Projections to 2017 SB Jones JL Male February 2012 PNNL-22133 Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: 2011 State of Technology and Projections to 2017 SB Jones JL Male February 2012 Prepared for the U.S. Department of Energy under Contract DE-AC05-76RL01830 Pacific Northwest National Laboratory Richland, Washington 99352 Contents 1.0 Introduction ................................................................................................................................ 1 2.0 State of Technology for FY2011 ................................................................................................ 3 2.1 Feedstock and Feedstock Preparation ................................................................................ 3 2.2 Fast Pyrolysis ..................................................................................................................... 5 2.3 Upgrading ........................................................................................................................... 5 2.4 Hydrocracking .................................................................................................................... 7 2.5 Hydrogen Generation ......................................................................................................... 8 3.0 Progression to $2.32/gallon Minimum Fuel Selling Price (MFSP) in 2017 ............................... 9 4.0 Concluding Remarks ................................................................................................................ 13 5.0 References ................................................................................................................................ 14 Figures Figure 1. Block Diagram – 2017 Projection Design Case ................................................................. 1 Figure 2. Block Diagram – 2011 SOT Case ...................................................................................... 3 Figure 3. Block Diagram – Original Design Case Pyrolysis Section................................................. 3 Figure 4. Block Diagram – Updated Design Case Pyrolysis Section ................................................ 4 Tables Table 1. Pyrolysis Oil Characterization ............................................................................................. 5 Table 2. Stable Hydrocarbon Oil Production ..................................................................................... 6 Table 3. SOT Standalone Plant ........................................................................................................ 10 iii 1.0 Introduction In February 2009, the Pacific Northwest National Laboratory (PNNL) and the National Renewable Energy Laboratory (NREL) produced a report detailing the process design and economic analysis for the thermochemical conversion of biomass (wood) into gasoline and diesel (Jones et al 2009). The purpose of the design report is to establish a research goal benchmark case for renewable fuels production in the 2017 timeframe. Annual technical and cost targets have been established and documented in the DOE Biomass Program’s Multi-Year Program Plan. Progress towards the 2017 goals are assessed annually. The purpose of this report is to document the review of the 2011 state of technology (SOT) and any revisions to the projections to 2017 as reported in the November 2011 Biomass Multi-Year Program Plan (DOE 2011). This is a conceptual process design for converting biomass into fuels that achieves key technical targets in a specified year, assuming nth plant modeled capital and operating costs, and is calculated in constant 2007 dollars. As shown in Figure 1, the original 2017 design case flowsheet (Jones et al 2009) involves several process steps: Feedstock drying and size reduction (note that the figure shows the original design case flowsheet as modeled in 2009– updates to this flowsheet are discussed in Section 2) Conversion of wood into bio-oil via fast pyrolysis Upgrading the fast pyrolysis oil to a stable hydrocarbon oil by two-stage hydrotreating to remove oxygen Distillation of the stable hydrocarbon oil into gasoline and diesel products Hydrocracking the heavier- than- diesel fraction (‘heavies”) into additional gasoline and diesel. Combustion Exhaust Supplemental Natural Gas Steam Reforming Hydrogen Hydrogen Exhaust Vent Combustion 2-step Exhaust Hydrotreating Off-gas Stable Fast Gasoline Oil Drying and Pyrolysis Product Fast Size Oil Separation Diesel Reduction Pyrolysis Gasoline Heavies Hydrocracking Ash and Product Diesel Separation Wastewater Figure 1. 2017 Projection Design Case Block Flow Diagram 1 The purpose of the state of technology is to serve as an annual assessment of the progress toward the projected 2017 goals. It is based on the best publically available data, in terms of key technical parameters and nth plant modeled capital and operating costs. Thus it is not a calculation of the current commercial cost of production for the products for a pioneer plant. 2 2.0 State of Technology for FY2011 Figure 2 shows the simplified flow for the current state of technology. The diesel and heavier portion of the stable hydrocarbon oil requires further finishing in a hydrocracker. 2-step Hydrotreating Fast Stable Oil Pyrolysis Product Gasoline Fast Oil Separation Wood Pyrolysis Diesel + Heavies Hydrocracking Gasoline and Product Separation Diesel Figure 2. Block Diagram – 2011 SOT Case 2.1 Feedstock and Feedstock Preparation Based on work by the Oak Ridge National Laboratory (ORNL) and the Idaho National Laboratory (INL), it is assumed that wood is available at $82/dry short ton in 2011 (DOE 2011). At this price, the wood has been dried and sized and needs no further preparation prior to fast pyrolysis. The 2017 Design Case published in 2009 (shown in Figure 1) assumed that the feedstock arrives at the plant gate as 50% moisture wood chips. A portion of the conversion cost involved drying the feedstock to 7% moisture and reducing the wood size to 2 – 6 mm particles as shown in Figure 3. Battery Limits Offgas Sand Heater Exhaust Pyrolysis Vapors 50% Moisture Wood Chips CONDENSER CYCLONE To atmosphere 7% Moisture 2-6 mm wood flour Char & Sand Pyrolysis Oil DRYER GRINDER SAND HEATER Sand PYROLYZER Fluidizing Gas Figure 3. Block Diagram – Original Design Case Pyrolysis Section 3 INL has made significant advances in understanding feedstock preparation and its associated costs. Field drying and improved storage reduces the wood chip moisture content to 30% without the use of a dryer. As such, the current feedstock cost projections assume pyrolysis reactor throat ready feedstock that has been dried from 30% moisture to 10% moisture and ground to 2-6 mm particles outside of the battery limit of the conversion process. Thus the 2009-2011 SOT models and the 2012-2017 projection models were revised to reflect these changes. This is shown in Figure 4. Battery Limits Air BFW PREHEAT BOILER Offgas Sand Heater Exhaust Pyrolysis Vapors 30% Moisture Wood Chips CONDENSER Offgas to CYCLONE H2 Plant To atmosphere 10% Moisture 2-6 mm w ood flour Char & Sand Pyrolysis Oil DRYER SAND HEATER GRINDER Sand PYROLYZER Fluidizing Gas Figure 4. Block Diagram – Updated Design Case Pyrolysis Section The reduced need for drying allows all of the off-gas from the pyrolysis reactor to be sent to the hydrogen plant rather than the biomass dryer. This eliminates some of the need for supplemental natural gas and hence reducing green house gas (GHG) emissions. Additionally, some of the heat from the char burner can be recuperated for process needs in the conversion plant. Finally, commercial pyrolysis reactor costs have been published since the 2009 Design Case, allowing for a review of the pyrolysis reactor costs from publically available data. The summary of these changes and their impact on the conversion costs are: Capital cost changes: • Remove dryer and grinder costs from conversion (costs ↓) • Add heat recovery and compressed air costs (costs ↑) • Update pyrolysis reactor costs to use publically available commercial cost data (costs ↑) Operating cost changes • Reduced natural gas consumption because of availability of pyrolysis off-gas (costs ↓) • Removed duplicative power consumption for grinding (costs ↓) • Improved GHG footprint because of reduced need for natural gas in the hydrogen plant (GHG estimate work ongoing). The resulting net cost changes are within 10% of the 2017 Conversion Target. Thus the 2017 cost target remains unchanged. 4 2.2 Fast Pyrolysis Conventional non-catalyzed fast pyrolysis is already commercialized on a small scale. The largest circulating fluidized bed is 400 dry metric tpd unit as built by Ensyn (Envergent 2011). The 2011 case assumes a single 2000 dry metric tpd pyrolyzer and the associated economy of scale. Heat transfer limitations may make this degree of scale-up difficult to achieve and evaluation of multiple parallel units will be considered in future work. The assumed yields of gas, oil, water and char are shown in Table 1: Table 1. Pyrolysis Oil Characterization 2011 2017 Yields, lb/100 lb dry wood Oil 60 65 Water 11 10 Char & Ash 16 13 Gas 13 12 Key Research Areas for Conventional Fast Pyrolysis Oils: High oxygen content, storage instability, particulates and corrosiveness all contribute

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