Top Value Added Chemicals from Biomass

1 Top Value Added Chemicals from Biomass Volume I Results of Screening for Potential Candidates from Sugars and Synthesis Gas Produced by the Staff at Pacific Northwest National Laboratory (PNNL) National Renewable Energy Laboratory (NREL) Office of Biomass Program (EERE) For the Office of the Biomass Program T. Werpy and G. Petersen, Editors Department of Energy Energy Efficiency and Renewable Energy Bringing you a prosperous future where energy is clean, abundant, reliable, and affordable Top Value Added Chemicals From Biomass Volume I: Results of Screening for Potential Candidates from Sugars and Synthesis Gas Produced by Staff at the Pacific Northwest National Laboratory (PNNL) and the National Renewable Energy Laboratory (NREL) T. Werpy and G. Petersen, Principal Investigators Contributing authors: A.

2 Aden and J. Bozell (NREL); J. Holladay and J. White (PNNL); and Amy Manheim (DOE-HQ) Other Contributions (research, models, databases, editing): D. Elliot, L. Lasure, S. Jones and M. Gerber (PNNL); K. Ibsen, L. Lumberg and S. Kelley (NREL) August 2004 National Renewable Energy Laboratory NOTICE This report was prepared as an account of work sponsored by an agency of the United States government. Neither the United States government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States government or any agency thereof.

3 The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States government or any agency thereof. Available electronically at Available for a processing fee to Department of Energy and its contractors, in paper, from: Department of Energy Office of Scientific and Technical Information Box 62 Oak Ridge, TN 37831-0062 phone: fax: email: Available for sale to the public, in paper, from: Department of Commerce National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 phone: fax: email: online ordering: Printed on paper containing at least 50% wastepaper, including 20% postconsumer waste Acknowledgement: The authors gratefully acknowledge the support andassistance from NREL staff members S. Bower, E. Jarvis, M. Ruth, and A.

4 Singh andreview by Paul Stone and Mehmet Gencer, independent consultants from thechemical industry as well as specific input and reviews on portions of the report by T. Eggeman of Neoterics International and Brian Davison of Oak Ridge NationalLaboratory. iiiTable of Contents Executive Summary ..1 1 Background ..3 2 3 Overall 4 Initial Screening to the Top 5 Selected Sugar-derived Chemicals ..13 6 Syngas Results Top Products ..17 7 Pathways and Challenges ..18 8 Moving 9 Top 12 Candidate Summary Four Carbon 1,4-Diacids (Succinic, Fumaric, and Malic) ..22 2,5-Furan dicarboxylic acid (FDCA)..26 3-Hydroxy propionic acid (3-HPA) ..29 Aspartic acid ..31 Glucaric acid ..36 Glutamic acid ..39 Itaconic Levulinic acid ..45 Sorbitol (Alcohol Sugar of Glucose) ..58 Xylitol/arabinitol (Sugar alcohols from xylose and arabinose).

5 61 10 Catalog of Potential Chemicals and Materials from Biomass ..65 ivBibliography .. 66 References Used to Develop Catalog for Potential Biobased Products .. 66 References for Assigning chemical and Biochemical Pathways .. 66 Tables Table 1 Biorefinery Strategic Fit Criteria .. 6 Table 2 Top Candidates from the First Screen .. 8 Table 3 Down Selection Top 30 Results .. 12 Table 4 The Top Sugar-derived Building Blocks .. 13 Table 5 Sugar Transformation to 3-HPA .. 14 Table 6 Reductive Transformation 3HP to 1,3 PDO via catalytic dehydrogenation .. 14 Table 7 Dehydrative Transformation 3-HPA to acrylic acid via catalytic dehydration .. 14 Table 8 Pathways to Building Blocks from 19 Table 9 Pathways to Building Block From Sugars [Four Carbon 1,4 Diacids (Succinic, Fumaric, and Malic] .. 22 Table 10 Family 1: Reductions [Primary Transformation Pathway(s) to Derivatives Four Carbon 1,4-Diacids (Succinic, Fumaric, and Malic)].)

6 22 Table 11 Family 2: Reductive Aminations [Primary Transformation Pathway(s) to Derivatives - Four Carbon 1,4-Diacids (Succinic, Fumaric, and Malic)] .. 22 Table 12 Family 3: Direct Polymerization [Primary Transformation Pathway(s) to Derivatives - Four Carbon 1,4-Diacids (Succinic, Fumaric, and Malic] .. 23 Table 13 Pathways to Building Block From Sugars [ 2,5-Furan dicarboxylic Acid (FDCA)] 26 Table 14 Family 1: Reduction [Primary Transformation Pathway(s) to Derivatives: 2,5-Furan dicarboxylic Acid (FDCA)] .. 26 Table 15 Family 2: Direct Polymerization [Primary Transformation Pathway(s) to Derivatives: 2,5-Furan dicarboxylic Acid (FDCA)] .. 27 Table 16 Pathways to Building Block from Sugars (3-HPA).. 29 Table 17 Family 1: Reductions [Primary Transformation Pathway(s) to Derivatives (3-HPA).. 29 Table 18 Family 2: Dehydration [Primary Transformation Pathway(s) to Derivatives (3-HPA).)]]

7 29 Table 19 Pathways to Building Block - Aspartic Acid .. 31 Table 20 Family 1: Reductions [Primary Tansformation Pathway(s) to Derivatives Aspartic Acid .. 32 Table 21 Family 2: Dehydration - [Primary Tansformation Pathway(s) to Derivatives Aspartic Acid] .. 32 Table 22 Family 3: Direct Polymerization [Primary Tansformation Pathway(s) to Derivatives Aspartic 32 Table 23 Pathway to Building Block From Sugars [Glucaric Acid] .. 36 Table 24 Family 1 - Dehydration [Primary Transformation Pathway(s) to Derivatives Glucaric Acid] .. 36 Table 25 Amination and Direct Polymeriation [Primary Transformation Pathway(s) to Derivatives Glucaric Acid] .. 36 vTable 26 Pathways to Building Block From Sugars [Glutamic Acid].. 39 Table 27 Family 1: Reductions [Primary Transformation Pathway(s) to Derivatives Glutamic Acid].]]

8 39 Table 28 Pathways to Building Block from Sugars [Itaconic Acid].. 42 Table 29 Family 1: Reductions [ Primary Transformation Pathway(s) to Derivatives Itaconic Acid] .. 42 Table 30 Family 2: Direct Polymerization [ Primary Transformation Pathway(s) to Derivatives Itaconic Acid] .. 42 Table 31 Pathways to Building Block From Sugars [Levulinic Acid].. 45 Table 32 Family 1: Reductions [Primary Transformation Pathways(s) to Derivatives Levulinic Acid].. 45 Table 33 Family 2: Oxidations [Primary Transformation Pathways(s) to Derivatives Levulinic Acid].. 45 Table 34 Family 3: Condensation [Primary Transformation Pathways(s) to Derivatives Levulinic Acid].. 46 Table 35 Pathways to Building Block from Sugars [Pathways to Building Block From Sugars 3-Hydroxybutyrolactone] .. 49 Table 36 Family 1: Reductions [Primary Transformation Pathway(s) to Derivatives 3-Hydroxybutyrolactone].

9 49 Table 37 Family 2: Direct Polymerization [Pimary Transformation Pathway(s) to Derivatives 3-Hydroxybutyrolactone] .. 50 Table 38 Pathways to Building Block [Glycerol] .. 52 Table 39 Family 1: Oxidation [Primary Transformation Pathway(s) to Derivatives [Glycerol].. 52 Table 40 Family 2: Bond Breaking (Hydrogenolysis) [Primary Transformation Pathway(s) to Derivatives [Glycerol].. 52 Table 41 Family 3: Direct Polymerization [Primary Transformation Pathway(s) to Derivatives [Glycerol].. 53 Table 42 Preliminary Economic Screening of the Glycerol 56 Table 43 Preliminary Economic Screening of the Glycerol Potential (Continued).. 57 Table 44 Pathways to Building Block [Sorbitol] .. 58 Table 45 Family 1: Dehydration [Primary Transformation Pathway(s) to Derivatives Sorbitol] .. 58 Table 46 Family 2: Bond Cleavage (hydrogenolysis) [Primary Transformation Pathway(s) to Derivatives - Sorbitol].]]]

10 58 Table 47 Family 3: Direct Polymerization [Primary Transformation Pathway(s) to Derivatives - Sorbitol] .. 59 Table 48 Pathways to Building Block From Sugars [ Xylitol/arabinitol].. 61 Table 49 Family 1: Oxidations [Primary Transformation Pathway(s) to Derivatives Xylitol/arabinitol] .. 61 Table 50 Family 2: Bond Cleavage (hydrogenolysis) [Primary Transformation Pathway(s) to Derivatives Xylitol/arabinitol].. 62 Table 51 Family 2: Direct Polymerization [Primary Transformation Pathway(s) to Derivatives Xylitol/arabinitol].. 62 viFigures Figure 1 Visual Representation of Overall Selection 5 Figure 2 An Example of a Flow-Chart for Products from Petroleum-based Feedstocks .. 10 Figure 3 Analogous Model of a Biobased Product Flow-chart for Biomass Feedstocks .. 11 Figure 4 Star Diagram of 3-Hydroxypropionic Acid.