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«Prepared for the U.S. Department of Energy under Contract DE-AC05-76RL01830 Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, ...»

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PNNL-18284

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:

A Design Case

SB Jones JE Holladay

C Valkenburg DJ Stevens

CW Walton C Kinchin

DC Elliott S Czernik

February 2009

PNNL-18284

Production of Gasoline and Diesel

from Biomass via Fast Pyrolysis,

Hydrotreating and Hydrocracking:

A Design Case SB Jones1 JE Holladay1 C Valkenburg1 DJ Stevens1 C Kinchin2 CW Walton DC Elliott1 S Czernik2 February 2009 Prepared for the U.S. Department of Energy under Contract DE-AC05-76RL01830 Pacific Northwest National Laboratory Richland, Washington 99352 Pacific Northwest National Laboratory National Renewable Energy Laboratory Executive Summary The President has established a goal to supply 35 billion gallons per year of renewable and alternative fuels by 2017. This goal is addressed in part by the U.S. Department of Energy (DOE) Office of Biomass Program‟s (OBP‟s) Thermochemical Platform multiyear program plan to “convert biomass to fuels, chemicals and power via thermal and chemical processes such as gasification, pyrolysis and other nonbiochemical processes” (DOE 2008).

In recent years, the Biomass Program completed technoeconomic evaluations of both biological and thermochemical pathways for converting biomass to ethanol. These “design case” studies provided a detailed basis for understanding the current state of various conversion technologies for producing fuel ethanol. The studies also helped identify technical barriers for which research and development could potentially lead to significant cost improvements. Consistent assumptions for items such as plant lifetimes, rates of return, and other factors were used in all cases so the various processes could be compared.

At present, the use of biomass resources to produce infrastructure-compatible fuels is appealing.

Hydrocarbon biofuels can potentially be used without significant changes to the current fuel distribution and utilization infrastructure, including pipelines, pumping stations, and vehicles. Given the relatively short time between now and 2017, the goal of 35 billion gallons per year of renewable fuels will be more readily met if hydrocarbon biofuels are part of the fuel mix.

The purpose of this design case study is to evaluate a processing pathway for converting biomass into infrastructure-compatible hydrocarbon biofuels. This design case investigates production of fast pyrolysis oil from biomass and the upgrading of that bio-oil as a means for generating infrastructure-ready renewable gasoline and diesel fuels. Other options for pyrolytic processes and upgrading steps exist, but they were not evaluated in this study. Likewise, gasification pathways that could be used to produce hydrocarbons are not addressed here. This study has been conducted using the same methodology and underlying basis assumptions as the previous design cases for ethanol.

The overall concept and specific processing steps were selected because significant data on this approach exists in the public literature. The analysis evaluates technology that has been demonstrated at the laboratory scale or is in early stages of commercialization. The fast pyrolysis of biomass is already at an early stage of commercialization, while upgrading bio-oil to transportation fuels has only been demonstrated in the laboratory and at small engineering development scale. Advanced methods of pyrolysis, which are under development, are not evaluated in this study. These, may be the subject of subsequent analysis by OBP.

The plant is designed to use 2000 dry metric tons/day of hybrid poplar wood chips to produce 76 million gallons/year of gasoline and diesel.

The processing steps include:

1. Feed drying and size reduction

2. Fast pyrolysis to a highly oxygenated liquid product

3. Hydrotreating of the fast pyrolysis oil to a stable hydrocarbon oil with less than 2% oxygen

4. Hydrocracking of the heavy portion of the stable hydrocarbon oil iii

5. Distillation of the hydrotreated and hydrocracked oil into gasoline and diesel fuel blendstocks

6. Hydrogen production to support the hydrotreater reactors.

Note that the Idaho National Laboratory (INL) is working on feedstock logistics that will eliminate the need for drying and size reduction at the plant. That is, the “as received” feedstock to the pyrolysis plant will be “reactor ready”. This development will likely further decrease the cost of producing the fuel.

The capital cost for a standalone “nth” plant is $303 million (2007 basis). At a 10% return on investment (ROI), the minimum fuels (gasoline + diesel) selling price is $2.04/gal ($1.34/gal ethanol equivalent basis).

An important sensitivity is the possibility of co-locating the plant with an existing refinery. In this case, the plant consists only of the first three steps: feed prep, fast pyrolysis, and upgrading. Stabilized, upgraded pyrolysis oil is transferred to the refinery for separation and finishing into motor fuels. The offgas from the hydrotreaters is also transferred to the refinery, and in return the refinery provides lower-cost hydrogen for the hydrotreaters. This reduces the capital investment to $188 million and the minimum fuel selling price to $1.74/gal ($1.14/gal ethanol equivalent basis).





Production costs near $2/gal (in 2007 dollars) and petroleum industry infrastructure-ready products make the production and upgrading of pyrolysis oil to hydrocarbon fuels an economically attractive source of renewable fuels. The study also identifies technical areas where additional research can potentially lead to further cost improvements.

iv Acronyms and Abbreviations

AR As received Btu British thermal units CFB circulating fluid beds DOE U.S. Department of Energy gal gallon HDS hydrodesulfurized HTS high temperature shift LHV lower heating value MFSP minimum fuel product selling price MM Million mm millimeter(s) mtpd metric tons per day MWth megawatts thermal OBP Office of the Biomass Program PSA pressure swing adsorption ROI return on investment tpd tons per day TPEC total purchased equipment cost

v Contents

Executive Summary

Acronyms and Abbreviations

1.0 Introduction

2.0 Analysis Approach

3.0 Feedstock and Plant Size

4.0 Process Overview

4.1 Fast Pyrolysis Oil Upgrading

5.0 Process Design

5.1 Feed Handling and Fast Pyrolysis

5.2 Hydrotreating to Stable Oil

5.3 Hydrocracking and Product Separation

5.4 Hydrogen Production

5.5 Cooling Water and Utilities

5.6 Process Yields and Consumptions

6.0 Process Economics

6.1 Capital Costs

6.1.1 Pyrolysis Unit

6.1.2 Pyrolysis Oil Hydrotreating and Hydrocracking

6.1.3 Hydrogen Generation

6.1.4 Balance of Plant

6.2 Operating Costs

6.3 Minimum Fuel Selling Price

7.0 Economic and Technical Sensitivities

7.1 Co-location with a Refinery

7.2 Financial and Market Sensitivities

7.3 Research Sensitivities

8.0 Conclusions and Recommendations

9.0 References

Appendix A Design Case – Stand-Alone Heat and Material Balance

Appendix B Equipment Cost Details

vii Figures

Figure 4.1.

Block Diagram of Overall Design

Figure 4.2.

Typical Product Yields from Different Modes of Wood Pyrolysis

Figure 5.1.

Block Diagram of Fast Pyrolysis

Figure 5.2.

Block Diagram of Bio-Oil Upgrading

Figure 5.3.

Block Diagram of Hydrocracking and Product Separation

Figure 5.4.

Block Diagram of Hydrogen Production

Figure 7.1.

Block Diagram of Pyrolysis and Upgrading Plant Co-located with a Refinery........... 7.1 Figure 7.2. Financial/Market Sensitivities

Figure 7.3.

Research Sensitivities

Tables

Table 5.1.

Feedstock and Processing Assumptions

Table 5.2.

Product Characterization

Table 5.3.

Hydrotreating Conditions

Table 5.4.

Hydrotreating Product Yields

Table 5.5.

Hydrocracking Conditions

Table 5.6.

Process Water Demands

Table 5.7.

Overall Yields and Consumption

Table 5.8.

Carbon Balance

Table 6.1.

Pyrolysis Unit Literature Capital Cost

Table 6.2.

Total Project Investment Cost for the Design Case Stand-Alone Plant

Table 6.3.

Total Project Investment Factors

Table 6.4.

Operating Cost Assumptions

Table 6.5.

Economic Parameters

Table 6.6.

Project Economics for the Stand-Alone Design Case Plant

Table 7.1.

Comparison of Integrated and Standalone Facilities

–  –  –

In recent years, the Biomass Program completed technoeconomic evaluations of both biological and thermochemical pathways for converting biomass to ethanol. These “design case” studies provided a detailed basis for understanding the current state of various conversion technologies for producing fuel ethanol. The studies also helped identify technical barriers where research and development could potentially lead to significant cost improvements. Consistent assumptions for items such as plant lifetimes, rates of return, and other factors were used in all cases so the various processes could be compared.

At present, the use of biomass resources to produce infrastructure-compatible fuels is appealing.

Hydrocarbon biofuels can potentially be used without significant changes to the current fuel distribution and utilization infrastructure, including pipelines, pumping stations, and vehicles. Given the relatively short time before 2017, the goal of 35 billion gallons of renewable fuels will be more readily met if hydrocarbon biofuels are part of the fuel mix.

The purpose of this design case study is to evaluate a processing pathway for converting biomass into infrastructure-compatible hydrocarbon biofuels.

This design case investigates fast pyrolysis oil production from biomass and the upgrading of that bio-oil as a means for generating infrastructure-ready renewable gasoline and diesel fuels. The overall concept and specific processing steps were selected because significant data on this approach exist in the public literature. Other options for pyrolytic processes and upgrading steps exist, but they were not evaluated in this study. One example of alternative processing options is hydrothermal pyrolysis followed by other upgrading steps. Likewise, gasification pathways can be used to produce hydrocarbons, but those are also not addressed here. These and other options may be addressed in future studies.

The design case presented here represents a goal case targeting performance potentially available between now and 2015. This analysis evaluates technology that has been demonstrated at the laboratory scale or is in early stages of commercialization. The fast pyrolysis of biomass is already at an early stage of commercialization, while the upgrading of the bio-oil to transportation fuels has only been demonstrated in the laboratory and at small engineering development scale. As such, the analysis does not reflect the current state of commercially-available technology but includes advancements that are potentially achievable by 2015.

The study has been conducted using the same methodology and underlying basis assumptions as the previous design cases for ethanol. It allows a basis for comparison with other research and development projects targeting the DOE objectives and lastly, provides a benchmark for the status of the pyrolysis program.

1.1

2.0 Analysis Approach The approach used is similar to that employed in previous conceptual process designs and associated design reports (Aden et al. 2002, Spath et al. 2005, Phillips et al. 2007). Process flow diagrams are based on literature information and research results; these data were then used to build a process model in CHEMCAD©, a commercial process flow sheeting software tool. The capital costs were taken from literature sources or were obtained from Aspen ICARUSTM software after being sized using the CHEMCAD© heat and material balances. The capital and operating costs were assembled in a Microsoft Excel© spreadsheet. A discounted cash flow method was used to determine the minimum product selling price.

–  –  –

The plant capacity is 2000 metric tons/day (mtpd) of bone dry wood. The plant is assumed to be an established (“nth”) plant design, rather than a first of its kind.

3.1

4.0 Process Overview

A simplified block diagram of the overall design is given in Figure 4.1. The processing steps include:

1. Feed drying and size reduction

2. Fast pyrolysis to a highly oxygenated liquid product

3. Hydrotreating of the fast pyrolysis oil to a stable hydrocarbon oil with less than 2% oxygen

4. Hydrocracking of the heavy portion of the stable hydrocarbon oil

5. Distillation of the hydrotreated and hydrocracked oil into gasoline and diesel fuel blendstocks

6. Steam reforming of the process off-gas and supplemental natural gas to produce hydrogen for the hydrotreating and hydrocracking steps.

Figure 4.1. Block Diagram of Overall Design

Feed Handling and Preparation: The biomass feedstock is dried from its as-received moisture level to less than 10% to minimize water in the fast pyrolysis product liquid. It is then ground to 2-6 mm particle size to yield sufficiently small particles, ensuring rapid reaction in the pyrolysis reactor.



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