IHS Chemical Process Economics Program Report 290 Bio-Butadiene By Dipti Dave and Susan Bell December 2014 ihs.com/chemical
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PEP Report 290 Bio-Butadiene By Dipti Dave and Susan Bell December 2014 Abstract The global butadiene market, with current annual production at about 11 million MT and valued at $30-40 billion, is slated to grow at 4.1% per year through 2016. Approximately two-thirds of the butadiene produced is used in synthetic rubber manufacturing. This growth is primarily based on increased demand via derivative expansion and rapid economic growth, particularly in Asia. High crude oil prices and low natural gas prices in the U.S. have caused petrochemical companies to shift from oil-based naphtha cracking to natural gas-based ethane cracking, and have resulted in reduced butadiene supply. This has spurred interest in on-purpose butadiene production both from conventional feedstocks and renewable feedstocks. Meanwhile, there has been great interest in green tires, which are manufactured from synthetic rubber derived from bio-based monomers such as bio-isoprene and bio-butadiene. Indeed, the bio-butadiene area is particularly active with companies including Genomatica and Cobalt Technologies announcing their plans to commercialize in the next five years. IHS Chemical Process Economics Program (PEP) has reviewed the latest patents and selected open literature made available by the companies mentioned above. Comparative process design and economics are provided for the production of 220 million lb/yr (100,000 ton/yr) of bio-based 1,3-butadiene. These bio-processes will be compared to the dominant, conventional process for butadiene production to understand its feasibility. This report is of interest to biochemical companies, Asian chemical companies in expansion mode, global petrochemical companies seeking to reduce their environmental footprint and polymer/plastic/rubber industries that rely on butadiene as a raw material. December 2014 iii 2014 IHS
Contents 1. Introduction... 1 Background... 1 Bio-Based Production Routes... 2 Feedstock Properties... 3 Cobalt Technologies Process... 3 Genomatica Indirect Process... 4 Genomatica Direct Process... 4 Product Properties... 5 Report Overview... 5 2. Summary... 6 Introduction... 6 Global Butadiene Demand... 7 Global Butadiene Growth... 8 Technologies Covered... 8 Cobalt Process Technology... 8 Process Sections... 9 Chemistry Cobalt Process... 9 Genomatica Indirect Process Technology... 10 Genomatica Direct Process Technology... 11 Existing Conventional Butadiene Technology... 12 Feedstock Pricing... 12 Effect of Glucose Cost... 12 Economic Summaries: Production Costs... 14 Cobalt Process at Different Glucose Feedstock Costs... 18 Genomatica Indirect Process at Different Glucose Feedstock Costs... 18 Genomatica Direct Process at Different Glucose Feedstock Costs... 19 Conclusion... 19 3. Industry status... 20 Introduction... 20 Uses... 21 Butadiene Demand... 23 Butadiene Supply... 26 Crude C 4... 27 Butadiene... 28 Prices... 30 Mixed C 4 s... 30 1,3 Butadiene... 31 Specifications... 34 C 4 Stream... 34 1,3 Butadiene... 35 December 2014 iv 2014 IHS
Plant Capacity... 37 New Capacity... 43 Bio-Butadiene developments... 44 4. Technology review... 45 Introduction... 45 Cobalt Technologies' Bio-Butanol... 45 Manufacturing of bio-butanol by different routes... 45 Cobalt Immobilized Cell Bioreactor... 46 Bioreactor concept nomenclature... 47 Cobalt Technologies Fermentation Flow Scheme... 48 Product Recovery... 49 1,3-Butadiene Production by an Indirect technology... 50 Fermentation... 51 Conversion Pathways to 1,3-BDO... 51 1,3-BDO Recovery... 55 1,3-BDO Dehydration to 1,3-Butadiene... 56 1,3-Butadiene Recovery and Purification... 57 1,3-Butadiene Production by a Direct Technology... 57 Fermentation... 58 1,3-Butadiene Recovery and Purification... 62 By-Product Recovery... 63 5. Cobalt Process for Bio-Butadiene... 64 Introduction... 64 Cobalt Technology... 64 Process Sections... 64 Chemistry... 65 Basis for Design and Evaluation... 65 Process Description... 68 Section 100 and 200 Media Preparation and Fermentation... 69 Section 300 Separation and Recovery... 70 Section 400 Dehydration of Butanol... 70 Section 500 & 600 Oxidative Dehydrogenation of Butenes & Butadiene Extraction... 71 Stream Flows... 71 Major equipment and utilities summary... 74 Process discussion... 77 Heat-Exchanger Sizing... 78 Product Recovery... 79 Offsite Storage... 79 Environmental... 79 Cost estimates... 80 Fixed-Capital Costs... 81 December 2014 v 2014 IHS
Production Costs... 81 Effect of Glucose Cost... 88 6. Economic Evaluation of Bio-Based 1,3-Butadiene Production by an Indirect Route via 1,3 Butanediol... 92 Introduction... 92 1,3-Butadiene Production by an Indirect Route... 92 Fermentation... 93 Conversion Pathways to 1,3-BDO... 93 1,3-BDO Recovery... 98 1,3-BDO Dehydration to 1,3-Butadiene... 98 1,3-Butadiene Recovery and Purification... 100 Process Description... 100 Section 100 Fermentation... 107 Section 200 BDO Recovery... 108 Section 300 Butadiene Production... 108 Cost Estimates... 109 Capital Costs... 109 Production Costs... 112 Effect of Glucose Cost... 115 7. Economic Evaluation of Bio-Based 1,3-Butadiene Production by a Direct Route... 118 Introduction... 118 1,3-Butadiene Production by a Direct Route... 118 Fermentation... 119 1,3-Butadiene Recovery and Purification... 123 By-Product Recovery... 123 Process Description... 124 Section 100 Fermentation... 132 Section 200 Butadiene Recovery and Purification... 132 Section 300 By-Product Recovery... 132 Cost Estimates... 133 Capital Costs... 133 Production Costs... 136 Effect of Glucose Cost... 139 Appendix A: Patent Summary Tables... 143 Appendix B: Design and cost bases... 154 Design Conditions... 154 Cost Bases... 154 Capital Investment... 154 Project Construction Timing... 156 December 2014 vi 2014 IHS
Available Utilities... 156 Production Costs... 156 Effect of Operating Level on Production Costs... 157 Appendix C: Cited references... 158 Appendix D: Patent references by company... 163 Appendix E: Process Flow Diagrams... 165 Tables Table 1.1: Butadiene Content from Steam Cracking Various Feedstocks... 2 Table 1.2: Typical Glucose Properties... 3 Table 1.3: Typical Specifications Of Butadiene... 5 Table 2.1: Global Regional Average forecast Growth Rate 1,3-Butadiene, 2013-2018... 8 Table 2.2: Bio-Butadiene Production Main Reactions... 9 Table 2.3: Production Costs of bio-based 1,3-butadiene Base Production Processes... 15 Table 2.4: Production Costs of 1,3-Butadiene At Different Glucose Feedstock Costs... 18 Table 2.5: Production Costs of 1,3-Butadiene At Different Glucose Feedstock Costs... 18 Table 2.6: Production Costs of 1,3-Butadiene At Different Glucose Feedstock Costs... 19 Table 3.1: Regional forecast demand growth rates of 1,3-butadiene, 2013-2018... 24 Table 3.2: U.S. Ethylene Fresh Feed Slate Second Half 2011... 26 Table 3.3: Typical composition ranges for low 1,3-butadiene C 4 streams... 35 Table 3.4: Raffinate-3 Sales Specification... 35 Table 3.5: Example of a 1,3-butadiene product specification... 36 Table 3.6: Typical specifications of butadiene... 37 Table 3.7: Plants World capacity of butadiene C 4 extraction plants... 38 Table 3.8: World capacity of on-purpose butadiene plants... 43 Table 3.9: New Announced New butadiene construction... 43 Table 4.1: Genomatica s Fermentation Patents... 51 Table 4.2: Direct Fermentation Patents... 59 Table 5.1: 1,3 Bio-Butadiene Production Main Reactions... 65 Table 5.2: Cobalt Technology Design Basis and Assumptions... 66 Table 5.3: Cobalt Technologies... 72 Table 5.4: Bio-Butadiene By Cobalt Technologies: Major Equipment... 74 Table 5.5: Bio-Butadiene Utilities Summary... 76 Table 5.6: Summary Of Major Process Waste Streams... 80 Table 5.7: Relation Between Base Capacity And Product Value... 82 Table 5.8: Bio-Butadiene Total Capital Investment... 83 Table 5.9: Bio-Butadiene Capital Investment By Section... 84 Table 5.10: Bio-Butadiene Production Costs... 86 December 2014 vii 2014 IHS
Table 5.11: Production Costs of 1,3-Butadiene At Different Glucose Feedstock Costs Basis: 100,000 ton/yr 1,3-Butadiene... 91 Table 6.1: Genomatica s Fermentation Patents... 93 Table 6.2: Bio-Based 1,3-Butadiene Production by an Indirect Route via 1,3-Butanediol: Design Bases and Assumptions... 101 Table 6.3: Bio-Based 1,3-Butadiene Production by an Indirect Route via 1,3-Butanediol: Stream Flows... 103 Table 6.4: Bio-Based 1,3-Butadiene Production by an Indirect Route via 1,3-Butanediol: Major Equipment... 105 Table 6.5: Bio-Based 1,3-Butadiene Production by an Indirect Route via 1,3-Butanediol: Utilities Summary... 107 Table 6.6: Bio-Based 1,3-Butadiene Production by an Indirect Route via 1,3-Butanediol: Total Capital Investment... 110 Table 6.7: Bio-Based 1,3-Butadiene Production by an Indirect Route via 1,3-Butanediol: Capital Investment by Section... 111 Table 6.8: Summary of Major Liquid Waste Streams... 112 Table 6.9: Bio-Based 1,3-Butadiene Production by an Indirect Route via 1,3-Butanediol: Production Costs... 113 Table 6.10: Production Costs of 1,3-Butadiene At Different Glucose Feedstock Costs... 117 Table 7.1: Direct Fermentation Patents... 119 Table 7.2: Bio-Based 1,3-Butadiene Production by a Direct Route: Design Bases and Assumptions... 125 Table 7.3: Bio-Based 1,3-Butadiene Production by a Direct Route: Stream Flows... 126 Table 7.4: Bio-Based 1,3-Butadiene Production by a Direct Route: Major Equipment... 129 Table 7.5: Bio-Based 1,3-Butadiene Production by a Direct Route: Utilities Summary... 131 Table 7.6: Bio-Based 1,3-Butadiene Production by a Direct Route: Total Capital Investment... 134 Table 7.7: Bio-Based 1,3-Butadiene Production by a Direct Route: Capital Investment by Section... 135 Table 7.8: Summary of Major Liquid Waste Streams... 136 Table 7.9: Bio-Based 1,3-Butadiene Production by a Direct Route: Production Costs... 137 Table 7.10: Production Costs of 1,3-Butadiene At Different Glucose Feedstock Costs... 142 Table A-1: Bio-Based Butadiene Production by Cobalt: Fermentation Patents Patent Summary... 144 Table A-2: Bio-Based Butadiene Production by an Indirect Route: Dehydration Patents Patent Summary... 149 Figures Figure 1.1: Typical Steam Cracker C 4 Flow to Produce Crude Butadiene... 1 Figure 1.2: Typical Extractive Distillation Butadiene Recovery From Crude C 4 s and Purification... 2 Figure 1.3: Block Flow Diagram Bio-Based Butadiene Production by Cobalt Route... 4 Figure 1.4: Block Flow Diagram Bio-Based Butadiene Production by Genomatica Indirect Route... 4 Figure 1.5: Block Flow Diagram Bio-Based Butadiene Production by Genomatica Direct Route... 4 Figure 2.1: Butadiene Price Forecast... 7 Figure 2.2: 2014 Global Butadiene Demand... 7 Figure 2.3: Block Flow Diagram for Cobalt Process... 9 December 2014 viii 2014 IHS
Figure 2.4: Simplified Flow Diagram: Bio-based 1,3-Butadiene Production by an Indirect Route via 1,3-BDO... 10 Figure 2.5: Simplified Flow Diagram: Bio-based 1,3-Butadiene Production by a Direct Route with Formic Acid as a By-Product... 12 Figure 2.6: United States Corn Price... 13 Figure 2.7: Estimated United States Glucose Price... 14 Figure 2.8: Capital Cost Economic Comparison... 16 Figure 2.9: Production Costs Economic Comparison... 17 Figure 3.1: 2014 Global Butadiene Demand... 21 Figure 3.2: Global commodity synthetic rubber production... 22 Figure 3.3: Distribution of Butadiene Uses... 23 Figure 3.4: Global Consumption Growth 2013 2018 by End Use... 24 Figure 3.5: Regional butadiene demand... 25 Figure 3.6: Change in Regional crude C 4 production index... 28 Figure 3.7: Utilization Butadiene extraction Plant capacity utilization by region... 29 Figure 3.8: Crude C 4 price history by region... 30 Figure 3.9: Global Crude C4 Trade... 31 Figure 3.10: Butadiene Spot Price History by Region... 32 Figure 3.11: North American butadiene and butane price history... 34 Figure 3.12: Distribution of Butadiene Extraction Plant Capacity... 42 Figure 4.1: Bioreactor Concept Diagram... 47 Figure 4.2: Bioreactor Zones... 48 Figure 4.3: Fermentation Section Scheme with Immobilized Bioreactor... 49 Figure 4.4: Simplified Flow Diagram: Bio-based 1,3-Butadiene Production by an Indirect Route via 1,3-BDO... 50 Figure 4.5: Production of Mitochondrion Acetyl-CoA... 52 Figure 4.6: Production of Cytosolic Acetyl-CoA from Mitochondrial Acetyl-CoA Using Citrate and Oxaloacetate Transporters... 52 Figure 4.7: Production of Cytosolic Acetyl-CoA from Mitochondrial Acetyl-CoA Using Citrate and Malate Transporters... 53 Figure 4.8: Production of Cytosolic Acetyl-CoA from Mitochondrial and Peroxisomal Acetyl-CoA Via Acetylcarnitine... 53 Figure 4.9: Production of Cytosolic Acetyl-CoA from Cytosolic Pyruvate... 54 Figure 4.10: Production of Cytosolic Acetyl-CoA from Phosphoenolpyruvate (PEP)... 54 Figure 4.11: Production of 1,3-Butanediol from Acetyl-CoA... 55 Figure 4.12: 1,3-BDO to Butadiene Reaction Scheme... 56 Figure 4.13: Simplified Flow Diagram: Bio-based 1,3-Butadiene Production by a Direct Route... 58 Figure 4.14: Direct Production of Butadiene via Crotyl Alcohol... 60 Figure 4.15: Direct Production of Butadiene via Erythrose-4-phosphate... 61 Figure 4.16: Direct Production of Butadiene via Acetyl-CoA and Malonyl-CoA... 62 Figure 5.1: Block Flow Diagram for Cobalt Process... 65 Figure 5.2: Process Flow Scheme for Dehydration of Butanol... 71 Figure 5.4: United States Corn Price... 88 Figure 5.5: Estimated United States Glucose Price... 89 December 2014 ix 2014 IHS
Figure 5.6: Sensitivity of Bio-based 1,3-butadiene Production Cost to Glucose Feedstock Cost... 90 Figure 5.7: Sensitivity of Bio-Based 1,3-Butadiene Product Value Including 15% Pretax ROI To Glucose Feedstock Cost... 91 Figure 6.1: Simplified Flow Diagram: Bio-based 1,3-Butadiene Production by an Indirect Route via 1,3-BDO... 92 Figure 6.2: Production of Mitochondrion Acetyl-CoA... 94 Figure 6.3: Production of Cytosolic Acetyl-CoA from Mitochondrial Acetyl-CoA Using Citrate and Oxaloacetate Transporters... 94 Figure 6.4: Production of Cytosolic Acetyl-CoA from Mitochondrial Acetyl-CoA Using Citrate and Malate Transporters... 95 Figure 6.5: Production of Cytosolic Acetyl-CoA from Mitochondrial and Peroxisomal Acetyl-CoA Via Acetylcarnitine... 95 Figure 6.6: Production of Cytosolic Acetyl-CoA from Cytosolic Pyruvate... 96 Figure 6.7: Production of Cytosolic Acetyl-CoA from Phosphoenolpyruvate (PEP)... 96 Figure 6.8: Production of 1,3-Butanediol from Acetyl-CoA... 97 Figure 6.9: 1,3-BDO to Butadiene Reaction Scheme... 99 Figure 6.11: United States Corn Price... 115 Figure 6.12: Estimated United States Glucose Price... 116 Figure 6.13: Sensitivity of 1,3-Butadiene Production Cost to Glucose Feedstock Cost... 116 Figure 6.14: Sensitivity of 1,3-Butadiene Product Value Including 15% Pretax ROI to Glucose Feedstock Cost... 117 Figure 7.1: Simplified Flow Diagram: Bio-based 1,3-Butadiene Production by a Direct Route... 118 Figure 7.2: Direct Production of Butadiene via Crotyl Alcohol... 120 Figure 7.3: Direct Production of Butadiene via Erythrose-4-phosphate... 121 Figure 7.4: Direct Production of Butadiene via Acetyl-CoA and Malonyl-CoA... 121 Figure 7.6: United States Corn Price... 139 Figure 7.7: Estimated United States Glucose Price... 140 Figure 7.8: Sensitivity of 1,3-Butadiene Production Cost to Glucose Feedstock Cost... 141 Figure 7.9: Sensitivity of 1,3-Butadiene Product Value Including 15% Pretax ROI to Glucose Feedstock Cost... 142 December 2014 x 2014 IHS