Abstract Process Economics Program Report 251 BIODIESEL PRODUCTION (November 2004) Biodiesel is an ester of fatty acids produced from renewable resources such as virgin vegetable oil, animal fats and used cooking oil. It can be used as the sole fuel source (B100) in compression ignition (diesel) engines as a replacement for petroleum based diesel or blended at levels of 2-20% (B2-B20) with minimal engine modifications. Consumption of biodiesel in Europe has reached almost 2.1 million tons /yr (630 million gal/yr) in 2003. It is available at more than 1500 locations in Germany and used in more than 400 fleets in the United States. EU Directive 2003/30/EC sets a target of 5.75% renewable fuels content by 2010. If the target is achieved the estimated production in Europe could reach over 7 million tons/yr (2.1 billion gallons/yr) of biodiesel. Recently passed tax incentives should encourage commercialization in the United States. Biodiesel consumption in the US could reach 1 to 2 billion gallons/yr (3-7million tons/yr) over the next decade. Rationale for the growth of consumption of fuels from renewable resources includes: Improvement in energy security Reduction in Greenhouse gases (GHG) Reduction in particulates (PM), CO and sulfur emissions Improvement in local economy Rising costs of petroleum and natural gas In this report, PEP examines the technologies and economics of two commercial processes for biodiesel production from refined vegetable oil (RVO). We review one of the first commercial continuous patented processes for the production of biodiesel, the Connemann_CD process. This process technology is based on Connemann_CD process patent, US 5,354,878, currently licensed to Westfalia Food Tec. We also review PEP s concept for the production of biodiesel by continuous alkaline-transesterification process modeled after the Lurgi PSI continuous transesterification and glycerin recovery process schemes as described in the open literature. It will be of interest to producers and consumers of diesel fuel. This report will also be of interest to producers of oleochemicals as one part of glycerin is produced as a by-product for every 10 parts of biodiesel. Widespread production of biodiesel has the potential to flood the market with natural glycerin. PEP 04 RGB
CONTENTS 1 BIODIESEL INTRODUCTION... 1-1 2 BIODIESEL SUMMARY... 2-1 INTRODUCTION... 2-1 BACKGROUND... 2-1 ENERGY SECURITY... 2-2 ENVIRONMENTAL ASPECTS... 2-2 CHEMISTRY... 2-3 TECHNICAL ASPECTS... 2-4 BIODIESEL FROM REFINED VEGETABLE OIL... 2-4 PROCESS OVERVIEW... 2-5 Connemann_CD Process... 2-6 Alkaline Catalyzed Process... 2-6 BIODIESEL ECONOMICS... 2-6 Feedstock Costs... 2-7 By-Product Credit... 2-8 Capital Costs... 2-9 Production Costs... 2-9 REGULATORY ISSUES... 2-10 SUMMARY... 2-10 3 BIODIESEL INDUSTRY STATUS... 3-1 INTRODUCTION... 3-1 ENERGY SECURITY... 3-1 REDUCTION IN GREENHOUSE GASES... 3-2 REDUCTION IN EMISSIONS... 3-3 IMPROVEMENT IN LOCAL ECONOMY... 3-4 iii
CONTENTS (Continued) REGULATORY STATUS... 3-4 EU Legislation... 3-4 Germany... 3-6 France... 3-6 EU Common Agricultural Policy... 3-7 US BIOFUELS POLICY AND LEGISLATION... 3-7 Increase Demand for Biofuels... 3-7 US Energy Policy Act (EPACT 1992)... 3-7 Reduce Cost of Biofuels to Consumer... 3-8 Reduce Cost of Biofuel Production... 3-8 BIODIESEL PRODUCTION... 3-10 Canada... 3-16 Brazil... 3-16 Others... 3-16 BIODIESEL QUALITY... 3-17 CO-PRODUCT GLYCERIN (GLYCEROL) CREDIT... 3-17 DIESEL MANUFACTURERS... 3-18 TECHNOLOGY PROVIDERS... 3-18 SUMMARY... 3-20 4 BIODIESEL FEEDSTOCKS... 4-1 INTRODUCTION... 4-1 VEGETABLE OILS... 4-2 Volume... 4-2 Location... 4-3 Oil Content... 4-3 Soybean Oil... 4-4 iv
CONTENTS (Continued) Canola/Rapeseed Oil... 4-5 Land Requirements in EU... 4-6 UNITED STATES BIODIESEL FEEDSTOCKS... 4-6 Animal Fats and Recycled Cooking Oil... 4-8 Yellow Grease... 4-9 Trap Grease... 4-9 Soapstock... 4-10 Microalgae... 4-10 Non-edible oils... 4-10 Mustard Oil... 4-10 SUMMARY... 4-11 5 BIODIESEL PRODUCTION... 5-1 INTRODUCTION... 5-1 CHEMISTRY... 5-1 TECHNOLOGY REVIEW... 5-5 Transesterification via Alkaline Catalysis... 5-5 Batch Transesterification of Vegetable Oil... 5-6 Continuous Production of Biodiesel... 5-7 Transesterification by Heterogeneous Catalysis... 5-10 Transesterification by Non-alkaline Catalyst... 5-12 Transesterification by Acid Catalysis... 5-12 Feedstock Quality and Pretreatment... 5-12 Esterification of FFA... 5-13 Esterification via Homogeneous Catalysis... 5-13 Esterification via Heterogeneous Acidic Catalyst... 5-15 Esterification using Heterogeneous Non-Acidic Catalyst... 5-15 v
CONTENTS (Continued) OTHER TECHNOLOGIES... 5-16 Biocatalysis... 5-16 Supercritical Processing... 5-16 Co-solvent Processes... 5-17 BIODIESEL QUALITY... 5-17 BIODIESEL PHYSICAL PROPERTIES... 5-18 Freezing Points... 5-18 Cold Flow Properties... 5-19 Cloud point... 5-19 CFPP... 5-19 Pour point... 5-19 Cetane Number... 5-19 Flash Point... 5-19 Heat of Combustion... 5-19 Viscosity... 5-20 Fuel Lubricity... 5-20 Iodine Number and Fuel Oxidative stability... 5-20 Oxidative Stability... 5-20 Material Compatibility... 5-20 SUMMARY... 5-25 6 BIODIESEL VIA CONNEMANN CONTINUOUS DEGLYCEROLIZATION (CD) PROCESS... 6-1 INTRODUCTION... 6-1 CHEMISTRY... 6-1 Transesterification... 6-3 PROCESS SUMMARY... 6-3 PROCESS DESCRIPTION... 6-4 Section 100--Biodiesel Synthesis... 6-4 vi
CONTENTS (Continued) Section 200--Biodiesel Purification... 6-5 Methanol Recovery... 6-5 Washing... 6-5 Drying... 6-6 Purification... 6-6 Section 300-Glycerin Recovery... 6-6 Glycerin Pretreatment... 6-6 Methanol Recovery... 6-6 PROCESS DISCUSSION... 6-22 Capacity... 6-22 Process Selection... 6-22 Feedstock... 6-23 Reactor Design... 6-23 Biodiesel Purification... 6-24 Product Bleaching... 6-24 Glycerin Distillation... 6-24 WASTE STREAMS... 6-25 CAPITAL AND PRODUCTION COSTS... 6-31 DISCUSSION CAPITAL AND PRODUCTION COSTS... 6-31 Raw Material Costs... 6-31 By-Product Credit... 6-32 Capital Costs Discussion... 6-32 SUMMARY... 6-32 7 BIODIESEL FROM REFINED VEGETABLE OIL VIA ALKALINE CATALYSIS INTRODUCTION... 7-1 INTRODUCTION... 7-1 CHEMISTRY... 7-1 vii
CONTENTS (Continued) Transesterification... 7-3 PROCESS SUMMARY... 7-3 PROCESS DESCRIPTION... 7-3 Overview... 7-3 Section 100 Transesterification... 7-5 Section 200 Recovery... 7-5 Methanol Recovery... 7-5 Washing... 7-5 Drying... 7-6 Biodiesel Bleaching... 7-6 Section 300--Glycerin Recovery... 7-6 Glycerin Pretreatment... 7-6 Glycerin Concentration... 7-6 Glycerin Purification... 7-7 PROCESS DISCUSSION... 7-19 Capacity... 7-19 Feedstocks... 7-19 Refined Vegetable Oil... 7-19 Lower Quality Feedstocks... 7-20 Transesterification... 7-20 Catalyst selection... 7-20 Reactor design... 7-21 Other Reactor types... 7-22 Biodiesel Purification... 7-22 Biodiesel Bleaching... 7-22 Methanol Recovery... 7-23 By-product Glycerin Recovery... 7-23 MATERIALS OF CONSTRUCTION... 7-24 viii
CONTENTS (Concluded) PRODUCT QUALITY... 7-24 WASTE STREAMS... 7-25 CAPITAL AND PRODUCTION COSTS... 7-26 DISCUSSION CAPITAL AND PRODUCTION COSTS... 7-26 Raw Material Costs... 7-27 By-Product Credit... 7-27 Capital Related Costs... 7-28 SUMMARY... 7-33 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 DIAGRAMS... E-1 ix
ILLUSTRATIONS 2.1 Biodiesel Process Flow... 2-5 3.1 Oil and Natural Gas Prices... 3-2 5.1 Triglyceride Structure... 5-1 5.2 Palmitic Acid... 5-1 5.3 Stearic Acid...5-2 5.4 Oleic Acid... 5-2 5.5 Linoleic Acid...5-2 5.6 Linolenic Acid...5-3 5.7 Eruric Acid... 5-3 5.8 Continuous Transesterification Process... 5-8 5.9 Connemann_CD Process... 5-9 5.10 Lurgi Transesterification Process...5-10 5.11 Esterfip Block Flow Diagram...5-11 6.1 Biodiesel by CD-Process Process Flow Diagram... E-3 6.2 Triglyceride Structure... 6-2 6.3 Connemann_CD Process Block Flow...6-4 6.4 Continuous Venturi Reactor... 6-23 6.5 Soybean Oil Prices... 6-32 7.1 Biodiesel by Alkaline Catalysis Process Flow Diagram... E-9 7.2 Triglyceride Structure... 7-2 7.3 Biodiesel Process Block Flow... 7-4 7.4 Mixer Settler...7-21 7.5 SBO Prices...7-27 x
TABLES 2.1 Emissions Data For Diesel And Biodiesel... 2-3 2.2 Biodiesel Production Costs... 2-7 2.3 Typical Feedstock Composition And Pricing... 2-8 2.4 Capital Costs Biodiesel From RVO... 2-9 2.5 US Diesel vs Biodiesel Blend Costs...2-11 3.1 Emissions Data For Diesel And Biodiesel... 3-3 3.2 EU Renewable Guidelines...3-5 3.3 EU Excise Tax Rates, 2003...3-6 3.4 Biodiesel Demand Scenarios In Millions of Gallons... 3-8 3.5 2003 DOE/USDA Wards... 3-10 3.6 European Biodiesel Production Capacity... 3-11 3.7 European Biodiesel Production Plants, 2003...3-11 3.8 US Biodiesel Production... 3-15 3.9 US Oleochemical Producers... 3-16 3.10 Comparison Of Biodiesel Specifications... 3-17 3.11 Biodiesel Technology Providers...3-19 4.1 Biodiesel Feedstocks... 4-2 4.2 Global Production Of Vegetable Oils...4-2 4.3 Major End-Use Markets For Fats And Oils-2000 (Percent)... 4-3 4.4 Yield Of Crude Oil From Processing of Oil Bearing Material... 4-4 4.5 Global Soybean Production 2003/04 Crop Year...4-5 4.6 Global Rapeseed Production Crop Year 2003/04...4-6 4.7 Typical Feedstock Composition And Pricing... 4-7 4.8 US Supply Of Vegetable Oil 2003/2004...4-7 4.9 Animal Fat Production 2001...4-8 4.10 Fatty Acid Profiles... 4-11 4.11 Seed Meal Glucosinolate Content...4-11 xi
TABLES (Continued) 5.1 Biodiesel Source Compositions...5-4 5.2 Biodiesel Feedstock Compositions...5-4 5.3 Comparison Of Biodiesel Specifications... 5-18 5.4 Selected Fuel Properties For Diesel And Biodiesel Fuels... 5-21 5.5 Physical Properties Of Selected Biodiesel Sources... 5-22 5.6 Diesel & Biodiesel Fuel Standards... 5-23 6.1 Biodiesel Source Compositions...6-2 6.2 Biodiesel Production... 6-8 6.3 Biodiesel From Refined Vegetable Oil Via CD Process Stream Flows...6-10 6.4 Biodiesel From Refined Vegetable Oil Via CD Process Major Equipment...6-17 6.5 Biodiesel From Refined Vegetable Oil Via CD Process Utilities Summary...6-21 6.6 Biodiesel Production Facilities... 6-22 6.7 Waste Summary...6-26 6.8 Biodiesel From Refined Vegetable Oil Via CD Process Total Capital Investment... 6-27 6.9 Biodiesel From Refined Vegetable Oil Via CD Process Capital Investment By Section... 6-28 6.10 Biodiesel From Refined Vegetable Oil Via CD Process Production Costs... 6-29 6.11 Petroleum vs Biodiesel Blend Costs...6-33 7.1 Biodiesel Source Compositions...7-2 7.2 Biodiesel Production Design Bases... 7-8 7.3 Biodiesel From Refined Vegetable Oil Via Alkaline Catalysis Stream Flows...7-10 7.4 Biodiesel From Refined Vegetable Oil Via Alkaline Catalysis Major Equipment...7-15 xii
TABLES (Concluded) 7.5 Biodiesel From Refined Vegetable Oil Via Alkaline Catalysis Utilities Summary...7-18 7.6 Lurgi Psi Designed Transesterification Processes... 7-19 7.7 ASTM Versus DIN vs Lurgi Process...7-25 7.8 Waste Summary...7-26 7.9 Biodiesel From Refined Vegetable Oil Via Alkaline Catalysis Total Capital Investment... 7-29 7.10 Biodiesel From Refined Vegetable Oil Via Alkaline Catalysis Capital Investment By Section... 7-30 7.11 Biodiesel From Refined Vegetable Oil Via Alkaline Catalysis Production Costs... 7-31 7.12 Petroleum vs Biodiesel Blend Costs...7-33 xiii