Sunday, June 3, 2007

Top Value Added Chemicals from Biomass. Part I

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 |Editors: T. Werpy and G. Petersen, Editors
[Golden, CO :; National Renewable Energy Laboratory, 2004]

Executive Summary
This report identifies twelve building block chemicals that can be produced from sugars via biological or chemical conversions. The twelve building blocks can be subsequently converted to a number of high-value bio-based chemicals or materials. Building block chemicals, as considered for this analysis, are molecules with multiple functional groups that possess the potential to be transformed into new families of useful molecules. The twelve sugar-based building blocks are 1,4-diacids (succinic, fumaric and malic), 2,5-furan dicarboxylic acid, 3-hydroxy propionic acid, aspartic acid, glucaric acid, glutamic acid, itaconic acid, levulinic acid, 3-hydroxybutyrolactone, glycerol, sorbitol, and xylitol/arabinitol.

Building Blocks
***1,4 succinic, fumaric and malic acids
***2,5 furan dicarboxylic acid
***3 hydroxy propionic acid
***aspartic acid
***glucaric acid
***glutamic acid
***itaconic acid
***levulinic acid
***3-hydroxybutyrolactone
***glycerol
***sorbitol
***xylitol/arabinito

The synthesis for each of the top building blocks and their derivatives was examined as a two-part pathway. The first part is the transformation of sugars to the building blocks. The second part is the conversion of the building blocks to secondary chemicals or families of derivatives. Biological transformations account for the majority of routes from plant feedstocks to building blocks, but chemical transformations predominate in the conversion of building blocks to molecular derivatives and intermediates. The challenges and complexity of these pathways, as they relate to the use of biomass derived sugars and chemicals, were briefly examined in order to highlight R&D needs that could help improve the economics of producing these building blocks and derivatives. Not surprisingly, many of the transformations and barriers revealed in this analysis are common to the existing biological and chemical processing of sugars.

The final selection of 12 building blocks began with a list of more than 300 candidates. The shorter list of 30 potential candidates was selected using an literative review process based on the petrochemical model of building blocks, chemical data, known market data, properties, performance of the potential candidates and the prior industry experience of the team at PNNL and NREL. This list of 30 was ultimately reduced to 12 by examining the potential markets for the building blocks and their derivatives and the technical complexity of the synthesis pathways. A second-tier group of building blocks was also identified as viable candidates. These include gluconic acid, lactic acid, malonic acid, propionic acid, the triacids, citric and aconitic; xylonic acid, acetoin, furfural, levoglucosan, lysine, serine and threonine. Recommendations for moving forward include examining top value products from biomass components such as aromatics, polysaccharides, and oils; evaluating technical challenges in more detail related to chemical and biological conversions; and increasing the suites of potential pathways to these candidates.

Table of Contents
Executive Summary ..... 1
1 Background ..... 3
2 Objective ..... 4
3 Overall Approach ..... 5
4 Initial Screening to the Top 30 ..... 6
5 Selected Sugar-derived Chemicals ..... 13
6 Syngas Results – Top Products ..... 17
7 Pathways and Challenges ..... 18
8 Moving Forward ...... 20
9 Top 12 Candidate Summary Bios ..... 21
9.1 Four Carbon 1,4-Diacids (Succinic, Fumaric, and Malic)..... 22
9.2 2,5-Furan dicarboxylic acid (FDCA)..... 26
9.3 3-Hydroxy propionic acid (3-HPA) ..... 29
9.4 Aspartic acid ..... 31
9.5 Glucaric acid ..... 36
9.6 Glutamic acid ..... 39
9.7 Itaconic acid ..... 42
9.8 Levulinic acid ..... 45
9.9 3 Hydroxybutyrolactone ..... 49
9.10 Glycerol ..... 52
9.11 Sorbitol (Alcohol Sugar of Glucose) ..... 58
9.12 Xylitol/arabinitol (Sugar alcohols from xylose and arabinose) ..... 61
10 Catalog of Potential Chemicals and Materials from Biomass .....65
Bibliography ..... 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 Sugars ...... 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)] ..... 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) ..... 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 Acid ..... 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
Table 26 Pathways to Building Block From Sugars [Glutamic Acid] ..... 39
Table 27 Family 1: Reductions [Primary Transformation Pathway(s) to Derivatives – Glutamic Acid] ..... 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] ..... 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 Potential ..... 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] ..... 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

Figures
Figure 1 Visual Representation of Overall Selection Strategy ..... 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 ..... 15
Figure 5 Succinic Acid Chemistry to Derivatives ..... 23
Figure 6 Simplified PFD of Glucose Fermentation to Succinic Acid ..... 24
Figure 7 Derivatives of FDCA ..... 27
Figure 8 Derivatives of 3-HPA ..... 30
Figure 9 Aspartic Acid Chemistry to Derivatives ..... 33
Figure 10 Derivatives of Glucaric Acid ..... 37
Figure 11 Glutamic Acid and its Derivatives ...... 40
Figure 12 Itaconic Acid Chemistry to Derivatives ..... 43
Figure 13 Derivatives of Levulinic Aid ..... 47
Figure 14 3-HBL Chemistry to Derivatives ..... 51
Figure 15 Derivatives of Glycerol ..... 54
Figure 16 Sorbitol Chemistry to Derivatives ..... 59
Figure 17 Chemistry to Derivatives of Xylitol and Arabinitol ..... 63


Principal Investigators: T. Werpy and G. Petersen,
Contributing authors: A. 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)

Source [http://www1.eere.energy.gov/biomass/pdfs/35523.pdf]

Thanks to Marc C. Reid, The Green Chemistry Technical Blog, for the HeadsUp on this report.

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