Abstract Process Economics Program Report 251A ADVANCES IN BIODIESEL AND RENEWABLE DIESEL PRODUCTION (December 2007)

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1 Abstract Process Economics Program Report 251A ADVANCES IN BIODIESEL AND RENEWABLE DIESEL PRODUCTION (December 2007) The use of a renewable fuel such as vegetable oil in Rudolf Diesel s compression ignition engine dates back to These renewable fuels were replaced by the availability of cheap petroleum-based fuels in the 20 th century. There has been resurgence in the 21 st century in the use of renewable fuels for diesel engines. One of the fastest growing petroleum-diesel alternatives is biodiesel. Biodiesel is the mono-alkyl ester of fatty acids (FAME) and is produced by the reaction of an alcohol usually methanol in the presence of a catalyst with feedstocks such as virgin vegetable oil (VO), animal fats (AF) and used cooking oil (UCO). The resulting fatty acid methyl ester (FAME) can be blended with petroleum-based diesel or used as a complete replacement in diesel engines with minimal engine modifications. The global production capacity of biodiesel is growing exponentially with capacity projected to increase from a capacity of 12.6 million t/yr (3.8 billion gal/yr) in 2006 to over 80 million metric tons/yr (24 billion gal/yr) by 2010 (Chemical Economics Handbook, Biodiesel, 2006). An emerging alternative to biodiesel is a renewable diesel. Renewable diesel is a longchain hydrocarbon (C12-C22) produced by the hydrogenation over a catalyst of some of the same feedstocks that are used to produce biodiesel. Several companies had announced plans to construct renewable diesel production facilities. They include Neste Oil, PetroBras, and joint ventures Tyson Foods/ConocoPhillips, Tyson Foods/Syntroleum and UOP/Eni SpA. There are multiple reasons for the use of fuels derived from renewable resources which include: improvement in energy security, reduction in Greenhouse gases (GHG), reduction in particulates (PM), CO, and sulfur emissions, improvement in local economy and the rising costs of petroleum and natural gas. Legislation in the EU, US and Brazil has been enacted to encourage the production and consumption of renewable fuels. In this report, PEP examines the technologies and economics for the production of biodiesel (FAME) from refined soybean oil by a homogeneous alkaline catalyst process and a heterogeneous catalyst process recently commercialized by Axens. We also examine the technologies and economics for the production of renewable diesel via hydrogenation of soybean oil. Both in-house hydrogen manufacture and purchase of hydrogen delivered via pipeline cases are evaluated. This report will be of interest to producers and consumers of diesel fuel, producers of methanol and hydrogen, oleochemical manufacturers, producers of vegetable oils and animal fats and catalyst manufacturers. SRI Consulting PEP Report 251A

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3 SRIC agrees to assign professionally qualified personnel to the preparation of the Process Economics Program s reports and will perform the work in conformance with generally accepted professional standards. No other warranties expressed or implied are made. Because the reports are of an advisory nature, neither SRIC nor its employees will assume any liability for the special or consequential damages arising from the Client s use of the results contained in the reports. The Client agrees to indemnify, defend, and hold SRIC, its officers, and employees harmless from any liability to any third party resulting directly or indirectly from the Client s use of the reports or other deliverables produced by SRIC pursuant to this agreement For detailed marketing data and information, the reader is referred to one of the SRI Consulting programs specializing in marketing research. THE CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS PROGRAM covers major hydrocarbons and their derivatives on a worldwide basis. In addition the SRIC DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Western Europe, Canada, and East Asia, South America and Mexico.

4 CONTENTS 1 BIODIESEL AND RENEABLE DIESEL INTRODUCTION BIODIESEL SUMMARY INTRODUCTION Energy Security Environmental Aspects Renewable Diesel Emissions Improvement in Local Economy BIODIESEL CHEMISTRY RENEWABLE DIESEL CHEMISTRY BIODIESEL TECHNICAL APECTS TECHNICAL ASPECTS OF RENEWABLE DIESEL BIODIESEL FEEDSTOCKS RENEWABLE DIESEL FEEDSTOCKS PROCESS OVERVIEW Biodiesel ALKALINE CATALYZED PROCESS BIODIESEL VIA HETEROGENEOUS CATALYSIS RENEWABLE DIESEL OVERVIEW PROCESS ECONOMICS CAPITAL COSTS Discussion of Capital Costs Biodiesel Renewable Diesel RENEWABLE DIESEL PRODUCTION COSTS Feedstock Costs By-Product Credit SRI Consulting iii PEP Report 251A

5 CONTENTS (Continued) PRODUCTION COSTS REGULATORY ISSUES SUMMARY INDUSTRY STATUS INTRODUCTION ENERGY SECURITY REDUCTION IN GREENHOUSE GASES REDUCTION IN EMISSIONS IMPROVEMENT IN LOCAL ECONOMY REGULATORY STATUS EU Legislation EU Common Agricultural Policy US BIOFUELS POLICY AND LEGISLATION Increase Demand for Biofuels Reduce Cost of Biofuels to Consumer BIODIESEL PRODUCTION Brazil BIODIESEL QUALITY Co-Product Glycerin (Glycerol) Credit DIESEL MANUFACTURERS TECHNOLOGY PROVIDERS RENEWABLE DIESEL OVERVIEW Challenges Blenders Credit Lubricity Summary SRI Consulting iv PEP Report 251A

6 CONTENTS (Continued) 4 BIODIESEL FEEDSTOCKS INTRODUCTION Vegetable Oils Volume PRODUCTIVITY OIL CONTENT Land Requirements Land Requirements in EU Soybean Oil Rapeseed/Canola Oil Palm Oil UNITED STATES BIODIESEL FEEDSTOCKS Animal Fats and Recycled Cooking Oil Yellow Grease Trap Grease Soapstock Microalgae Jatropha Mustard Oil SUMMARY BIODIESEL & RENEWABLE DIESEL PRODUCTION INTRODUCTION CHEMISTRY TECHNOLOGY REVIEW BIODIESEL Transesterification via Alkaline Catalysis Batch Transesterification of Vegetable Oil SRI Consulting v PEP Report 251A

7 CONTENTS (Continued) Continuous Production of Biodiesel Transesterification by Hetergeneous Catalysis Transesterification by Non-alkaline Catalyst Transesterification by Acid Catalysis Feedstock Quality and Pretreatment Esterification of FFA Esterification via Homogeneous Catalysis Esterification via Heterogeneous Acidic Catalyst Esterification using Heterogeneous Non-Acidic Catalyst OTHER TECHNOLOGIES Biocatalysis Microbiodiesel Supercritical Processing Tranesterification with No Catalyst Co-Solvent Processes BIODIESEL QUALITY BQ-9000 Program BIODIESEL PHYSICAL PROPERTIES Freezing Points Cold Flow Properties Cloud Point CFPP Pour Point Cetane Number Flash Point Heat of Combustion Viscosity Fuel Lubricity SRI Consulting vi PEP Report 251A

8 CONTENTS (Continued) Iodine Number and Fuel Oxidative Stability Oxidative Stability Material Compatibility RENEWABLE DIESEL CHEMISTRY Renewable Diesel Technology Review SUMMARY BIODIESEL FROM REFNIED VEGETABLE OIL VIA ALKALINE CATALYSIS INTRODUCTION CHEMISTRY Transesterification PROCESS SUMMARY PROCESS DESCRIPTION Overview Section 100-Transesterification Section 200-Recovery Methanol Recovery Washing Drying Section 300-Glycerin Recovery Glycerin Pretreatment Glycerin Concentration Glycerin Purification PROCESS DISCUSSION Capacity Feedstocks Refined Vegetable Oil Lower Quality Feedstocks SRI Consulting vii PEP Report 251A

9 CONTENTS (Continued) Other Alcohols Transesterification Other Reactor Types BIODIESEL PURIFICATION Biodiesel Bleaching Methanol Recovery By-Product Glycerin Recovery MATERIALS OF CONSTRUCTION PRODUCT QUALITY WASTE STREAMS DISCUSSION CAPITAL AND PRODUCTION COSTS Raw Material Costs By-Product Credit Capacity Related Costs Biodiesel with Crude Glycerin Byproduct CAPITAL AND PRODUCTION COSTS Capital Costs Production Costs DISCUSSION CRUDE GLYCERIN CASE PRODUCTION AND CAPITAL COSTS SUMMARY RENEWABLE DIESEL FROM VEGETABLE OIL VIA HYDROTREATING INTRODUCTION LEGISLATION European Union United States Brazil SRI Consulting viii PEP Report 251A

10 CONTENTS (Continued) OVERVIEW CHEMISTRY Hydrogenation of Unsaturated Bonds Hydrodeoxygenation Decarboxylation Hydroisomerization Process Summary PROCESS OVERVIEW PROCESS DESCRIPTION Section 100-Synthesis Section 200-Recovery Section 300-Hydrogen Production PROCESS DISCUSSION Feedstock Selection Capacity Integrated vs. Stand-Alone Blenders Credit Reactor Design Hydrogen Sources Hydrogen Consumption Hydrogen Purification Distillation Column LPG WASTE STREAMS CAPITAL AND PRODUCTION COST ESTIMATES Merchant Hydrogen Case PRODUCTION COSTS SRI Consulting ix PEP Report 251A

11 CONTENTS (Continued) Raw Material Costs By-Product Credit Capital Related Costs IN-HOUSE HYDROGEN CASE Capital Costs Production Costs SUMMARY BIODIESEL VIA AXENS ESTERFIP-H PROCESS INTRODUCTION CHEMISTRY Transesterification PROCESS OVERVIEW Transesterification via Homogeneous Catalysis Transesterification via Heterogeneous Catalysis PROCESS DESCRIPTION Section Feed Pretreatment Transesterification Second Stage Transesterification Section 200 Purification Product Purification Methanol Dehydration Section 300 Glycerin Recovery PROCESS DISCUSSION Transesterifier Design Reactor Configuration Product Purification SRI Consulting x PEP Report 251A

12 CONTENTS (Concluded) Glycerin Recovery PRODUCT QUALITY WASTE SUMMARY PRODUCTION AND CAPITAL COSTS CAPITAL COSTS PRODUCTION COSTS Net Production Cost Product Value Base Case DISCUSSION OF CAPITAL AND PRODUCTION COSTS Raw Material Costs Capital Related Costs Energy Costs By-Product Credit Biodiesel with Crude Glycerin Byproduct CAPITAL AND PRODUCTION COSTS CRUDE GLYCERIN CASE Capital costs Crude Glycerin Case Production Costs Product Value DISCUSSION CRUDE GLYCERIN CASE PRODUCTION AND CAPITAL COSTS SUMMARY APPENDIX A: PATENT SUMMARY TABLES... A-1 APPENDIX B: DESIGN AND COST BASES... B-1 APPENDIX C: CITED REFERENCES... C-1 APPENDIX D: PATENT REFERENCES BY COMPANY... D-1 APPENDIX E: PROCESS FLOW DIAGRAM... E-1 SRI Consulting xi PEP Report 251A

13 ILLUSTRATIONS 2.1 Biodiesel Process flow Axens heterogeneous Catalysis Process Renewable Diesel Block Flow Diagram Renewable Diesel Simplified Flow Diagram Biodiesel Economics (Cents per Gallon) Biodiesel Economics (Cents per Liter) Renewable Diesel Costs (Cents per Gallon) Renewable Diesel Costs (Cents per Liter) Comparison of Renewable and Biodiesel Economics (Cents per Gallon) Comparison of Renewable and Biodiesel Economics (Cents per Liter) Biodiesel and Renewable Diesel Cost Sensitivities United States Fuel Consumption European Fuel Consumption Petroleum Prices Natural Gas Prices Biodiesel Plant Locations in the United States Productivity of Oilseeds vs. Price US Diesel Consumption Triglyceride Structure Palmitic Acid Stearic Acid Oleic Acid Linoleic Acid Linolenic Acid Eruric Acid Biodiesel Block Flow Connemann_CD Process SRI Consulting xii PEP Report 251A

14 ILLUSTRATIONS (Concluded) 5.10 Lurgi Transesterification Process Esterfip-H Block Flow Diagram Simplified Esterfip-H Flow Diagram Vegetable Oils Processing Routes Renewable Diesel Simplified Flow Diagram Cloud Point vs. Iso/Normal Paraffin Ratio Biodiesel by Alkaline Catalysis... E Triglyceride Structure Biodiesel Process Block Flow Mixer Settler Soybean and Palm Oil Prices Renewable Diesel... E Petrobras H-Bio Block Flow Fixed Bed Reactor Configuration NExBTL Synthesis Reactor Historical Vegetable Oil Prices Product Value vs. Raw Material Costs Biodiesel via Heterogeneous Catalysis... E Triglyceride Structure Biodiesel Production via Homogeneous Catalysis Esterfip-H Block Flow Diagram Esterfip-H Block Simplified Flow Diagram Axens Transesterification Reactor Vegetable Oil Prices SRI Consulting xiii PEP Report 251A

15 TABLES 2.1 Emissions Data for Diesel and Biodiesel Emissions Data for NExBTL Diesel Compared to ECN Comparison of Physical Properties Capital Cost Summary Biodiesel Production Costs Renewable Diesel Economics Typical Feedstock Composition Emissions Data for Diesel and Biodiesel Emissions Data for NExBTL Diesel Compared to ECN EU Renewable Guidelines EU Excise Tax Rates, Top 10 Biodiesel Producers European Biodiesel Production European Biodiesel Production Capacity US Biodiesel Production Capacity, September Comparison of Biodiesel Specifications Biodiesel Technology Providers World Biodiesel Feedstocks Global Production of Vegetable Oils Table Land Use Comparison Yield of Crude Oil from Processing of Oil Bearing Material Projected Land Requirements for Oilseeds Global Soybean Production 2005/06 Crop Year Global Rapeseed/Canola Production Crop Year 2005/ Global Palm Kernel Production Crop Year 2005/ US Supply of Vegetable Oil 2005/ Animal Fat Production SRI Consulting xiv PEP Report 251A

16 TABLES (Continued) 4.11 Typical Feedstock Composition Fatty Acid Profiles Seed Meal Glucosinolate Content Biodiesel Source Compositions Biodiesel Feedstock Compositions Comparison of Biodiesel Specifications Selected Fuel Properties for Diesel and Biodiesel Fuels Physical Properties of Selected Biodiesel Sources Diesel & Biodiesel Fuel Standards Comparison of Physical Properties Fatty Acid Molecular Weights Cloud Point of Pure N-Paraffins Product Distribution of Hydrotreated Vegetable Oils Conoco/Phillips Renewable Diesel from Beef Tallow Low Concentration Renewable Diesel Content Effects Biodiesel Source Compositions Biodiesel Production Design Bases Biodiesel from RVO via Alkaline Catalysis Crude Glycerin Recovery Stream Flows Biodiesel from RVO via Alkaline Catalysis Crude Glycerin Recovery Major Equipment Biodiesel from RVO via Alkaline Catalysis Crude Glycerin Recovery Utilities Summary Comparison of Biodiesel Specifications Waste Summary Biodiesel from RVO via Alkaline Catalysis Crude Glycerin Recovery Total Capital Investment Biodiesel from RVO via Alkaline Catalysis Crude Glycerin Recovery Capital Investment by Section SRI Consulting xv PEP Report 251A

17 TABLES (Continued) 6.10 Biodiesel from RVO via Alkaline Catalysis Crude Glycerin Recovery Production Costs Biodiesel from RVO via Alkaline Catalysis Crude Glycerin Recovery Major Equipment Biodiesel from RVO via Alkaline Catalysis Crude Glycerin Recovery Utilities Summary Biodiesel from RVO via Alkaline Catalysis Crude Glycerin Recovery Total Capital Investment Biodiesel from RVO via Alkaline Catalysis Crude Glycerin Recovery Capital Investment by Section Biodiesel from RVO via Alkaline Catalysis Crude Glycerin Recovery Production Costs Biodiesel Source Compositions Biodiesel Feedstock Compositions Product Distribution of Hydrotreated Vegetable Oils Melting Point of Pure N-Paraffins Low Concentration Renewable Diesel Content Effects Cloud Point vs. Iso/Normal Ratio Comparison of Physical Properties Renewable Diesel Production Design Bases Renewable Diesel from RVO via Hydrogenation Major Equipment Hydrodeoxygenation vs. Decarboxylation Reactions Hydrodeoxygenation vs. Decarboxylation Reactions Fatty Acid Molecular Weights Biodiesel Source Compositions Biodiesel Feedstock Compositions Battery Limits Capital Investment Renewable Diesel from RVO with Merchant Hydrogen Major Equipment SRI Consulting xvi PEP Report 251A

18 TABLES (Continued) 7.17 Renewable Diesel from RVO with Merchant Hydrogen Utilities Summary Renewable Diesel from RVO with Merchant Hydrogen Total Capital Investment Renewable Diesel from RVO with Merchant Hydrogen Capital Investment by Section Renewable Diesel from RVO with Merchant Hydrogen Production Costs Capital Costs BLI Renewable Diesel from RVO with Hydrogen Production Utilities Summary Renewable Diesel from RVO with Hydrogen Production Production Costs Biodiesel Source Compositions Biodiesel Feedstock Compositions Feedstock Specifications Biodiesel Production via Heterogeneous Catalysis Design Bases Biodiesel via Heterogeneous Catalysis Esterfip-H Process Stream Flows Comparison of Biodiesel Specifications Biodiesel by Esterfip-H Process Major Equipment Biodiesel by Esterfip-H Process Utilities Summary Biodiesel by Esterfip-H Process Total Capital Investment Biodiesel by Esterfip-H Process Capital Investment by Section Biodiesel by Esterfip-H Process Production Costs Biodiesel by Esterfip-H Process Crude Glycerin Case Major Equipment SRI Consulting xvii PEP Report 251A

19 TABLES (Concluded) 8.13 Biodiesel by Esterfip-H Process Crude Glycerin Case Utilities Summary Biodiesel by Esterfip-H Process Crude Glycerin Case Total Capital Investment Biodiesel by Esterfip-H Process Crude Glycerin Case Capital Investment by Section Biodiesel by Esterfip-H Process Crude Glycerin Case Production Costs A.1 Advances in Biodiesel Production Patent Summary... A-3 SRI Consulting xviii PEP Report 251A

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