METHANOL SAFE HANDLING MANUAL 4TH EDITION TABLE OF CONTENTS 1 Introduction to the Manual 2 1.1 Purpose of the Manual 2 1.2 The Methanol Value Chain 3 1.3 Methanol Institute Product Stewardship Policy 4 1.4 Methanol Institute Contact Information 5 1.5 About the Authors 5 1.6 Disclaimer 7 2 Methanol General Information 8 2.1 What is Methanol? 8 2.2 The Methanol Life Cycle (Value Chain) 12 2.2.1 Methanol Manufacture 12 2.2.2 Sustainable Production 14 2.2.2.1 Recycling 15 2.2.2.3 Waste Management 16 2.3 The Uses of Methanol 16 2.3.1 Chemical Intermediates 17 2.3.2 Fuel Applications 18 2.3.3 Biodiesel Fuel Production 22 2.4 Emerging Uses of Methanol 25 2.4.1 Wastewater Denitrification 25 2.4.2 Direct Methanol Fuel Cells 28 2.4.3 Turbine Engines 32 2.4.4 Offshore Platforms 35 METHANOL SAFE HANDLING MANUAL: 4TH EDITION II 2.4.5 Marine Fuel 37 2.4.6 Methanol Specifications 39 3 Transportation and Storage of Methanol 40 3.1 Methanol Transportation 40 3.1.1 Ocean-going Transport 40 3.1.2 Rail Transport 41 3.1.3 Tanker Truck Transport 42 3.2 Methanol Storage 42 3.2.1 Docks and Marine Terminals 42 3.2.2 Tank Farms 43 3.2.3 Portable Containers 43 3.2.4 Electrical Classification 46 3.2.5 Grounding and Bonding 46 4 Health and Safety 51 4.1 Exposure to Methanol 51 4.1.1 Routine Sources of Exposure 51 4.1.2 Accidental Sources of Exposure 53 4.1.3 Routes of Exposure 54 4.1.4 Methanol Metabolism 54 4.1.5 Effects of Exposure 54 4.1.5.1 General Symptoms 55 4.1.5.2 Acute Effects 55 4.1.5.3 Chronic Effects 56 4.2 Exposure Control 57 METHANOL SAFE HANDLING MANUAL: 4TH EDITION III 4.2.1 Engineering Controls 57 4.2.1.1 Ventilation 57 4.2.2 Exposure Monitoring 58 4.2.3 Personal Protective Equipment 59 4.2.4 Respiratory Protection 60 4.2.5 Chemical-resistant Clothing/Materials 60 4.3 Safety Precautions 61 4.3.1 Routine Operations 61 4.3.2 Special or High Hazard Operations 63 4.3.2.1 Confined Space Entry 63 4.3.2.2 Hot Work 64 4.4 First Aid Measures 65 4.4.1 Inhalation 65 4.4.2 Skin Contact 66 4.4.3 Eye Contact 66 4.4.4 Accidental Ingestion 66 4.4.5 MI Reference Materials 66 5 Managing Methanol Safely: Process Safety 67 5.1 Definitions 70 5.2 Introduction to Process Safety Management 70 5.3 Comparison - CCPS Risk-based Process Safety VS OSHA Regulations 72 5.4 PSM Elements - Descriptions and Application to Methanol Safe Handling 74 5.4.1 Process Safety Culture 74 5.4.2 Compliance with Standards 75 METHANOL SAFE HANDLING MANUAL: 4TH EDITION IV 5.4.3 Process Safety Competency 79 5.4.4 Work Force Involvement 82 5.4.5 Stakeholder Outreach 88 5.4.6 Process Knowledge Management 93 5.4.7 Hazard Identification and Risk Analysis 95 5.4.8 Operating Procedures 96 5.4.9 Safe Work Practices 98 5.4.10 Asset Integrity and Reliability 99 5.4.11 Contractor Management 100 5.4.12 Training and Performance Assurance 103 5.4.13 Management of Change 104 5.4.14 Operational Readiness 109 5.4.15 Conduct of Operations 112 5.4.16 Emergency Management 113 5.4.17 Incident Investigation 116 5.4.18 Measurement and Metrics 120 5.4.19 Auditing 123 5.4.20 Management Review and Continuous Improvement 125 5.5 Implementing Process Safety 127 5.5.1 What is a "Hazard"? 128 5.5.2 What is a "Risk"? 128 5.5.3 Hazard Identification and Risk Assessment Methods 129 5.5.4 Process Hazard Assessment Documentation 130 METHANOL SAFE HANDLING MANUAL: 4TH EDITION V 6 Fire Safety 131 6.1 Methanol Fire Characteristics 132 6.1.1 Flammability 132 6.1.2 Burning Behavior 134 6.2 Fire Prevention 136 6.2.1 Vapor Control 136 6.2.1.1 Storage Safety Features 136 6.2.1.2 Pressure Relief System 137 6.2.1.3 Gas Detection 138 6.2.2 Removal of Ignition Sources 138 6.3 Fire or Explosion 139 6.4 Fire Detection 140 6.4.1 Automatic Fire Detection 140 6.4.1.1 Smoke Detection 140 6.4.1.2 Heat Detection 140 6.4.1.3 Flame Detection 141 6.4.1.4 Other Means for Detection 141 6.4.2 Manual Fire Detection 142 6.5 Fire Control 142 6.5.1 Fixed Fire Extinguishment 143 6.5.1.1 Gas Fire-extinguishment 144 6.5.1.2 Water Fire-extinguishment 145 6.5.1.3 Foam Fire-extinguishment 147 6.5.2 Manual Response 147 METHANOL SAFE HANDLING MANUAL: 4TH EDITION VI 6.6 Fire Ground Safety 148 6.6.1 personal protection equipment 148 6.6.2 localization and assessment of fire 149 6.6.3 Use of Water 149 6.6.4 Outside Responders 150 6.7 Methanol-gasoline Blended fuels Fire Safety 151 6.7.1 Properties of Methanol-gasoline Blended Fuels 152 6.7.2 Methanol-gasoline Blended-fuel Fires 153 6.7.3 Response to Methanol-gasoline Blended-fuel Fires 154 7 Emergency Response 155 7.1 Spill Prevention 155 7.2 Spill Response 157 7.3 Release Containment 158 7.3.1 Site Control Zones 160 7.4 Spill Cleanup and Remediation 161 7.5 Spill Notification and Reporting 162 7.6 Incident Investigation and Recordkeeping 162 7.7 Incident Command Structure 162 7.7.1 Communications 163 8 Methanol Incidents and Safeguards 164 8.1 Overview of Methanol Incidents 164 8.1.1 Common Causes of Incidents 166 8.1.2 Routine Operations and Maintenance 166 8.1.3 Transportation Activities 167 METHANOL SAFE HANDLING MANUAL: 4TH EDITION VII 8.1.4 Pipeline Incidents 167 8.2 Key Findings 168 8.3 Conclusions 169 8.4 Safeguards 170 8.4.1 Process Safety Management 170 8.4.2 Corrosion Prevention 171 8.4.3 Hot Work Permit Program 171 8.4.4 Fire Prevention and Response 171 8.4.5 Employee Training 172 9 Environmental Protection 173 9.1 Environmental Fate and Transport 174 9.2 Air Emissions 175 9.3 Groundwater Effects 176 9.4 Impacts to Drinking Water 176 9.5 Biological Effects 177 9.6 Climate Effects 178 9.7 Waste Treatment and Disposal 179 10 Product Stewardship and Sustainability 180 10.1 Product Stewardship and Responsible Care 180 10.2 Product Stewardship Management System 181 10.3 Product Stewardship Practices 182 10.3.1 PSP #1: Leadership and Accountability 182 10.3.2 PSP #2: Environmental, Health, and Safety Information 183 METHANOL SAFE HANDLING MANUAL: 4TH EDITION VIII 10.3.3 PSP #3: Selling 183 10.3.4 PSP #4: Public Concerns and Issues 183 10.3.5 PSP #5: Performance Indicators 184 10.4 Sustainability 184 10.4.1 A Primer on Sustainability 184 10.4.2 Alternative Energy 185 11 Risk Communication 188 11.1 What is Risk Communication? 188 11.2 Why is Risk Communication Important? 189 11.3 Risk Communication Basics 190 11.4 Communicating Complex Technical and Scientific Information 191 11.5 Understanding the Public's Perception of Risk 192 11.6 Earning Trust and Building Credibility 193 11.7 Looking for Opportunities to Get Your Message Out 193 12 Glossary 195 12.1 Terms, Abbreviations, and Acronyms 195 13 References 223 Appendix A - Process Safety Information 232 A.1 Chemical Hazards 232 A.2 Process Technology 232 A.3 Process Equipment 233 A.4 Additional Information Required 234 METHANOL SAFE HANDLING MANUAL: 4TH EDITION IX Appendix B - Properties of Methanol/Methyl Alcohol 236 B.1 Physical Properties 236 B.1.1 Solid 236 B.1.2 Liquid 236 B.1.3 Vapor 238 B.2 Chemical Properties 238 B.2.1 Reactivity 239 B.2.2 Decomposition 239 B.2.3 Incompatibilities 239 B.3 Corrosivity to Metals, Alloys, Gaskets, and Plastic 240 B.4 Structure and Properties 243 B.5 Combustion and Ignition Properties 243 B.5.1 Fire Extinguishing Media 244 B.6 Thermodynamic Properties 244 Appendix C - Regulatory, Health, and Safety Information for Methanol 246 C.1 U.S. Regulations and Codes 246 C.2 International Regulations, Standards, and Guidelines 249 C.3 Hazardous Material and Health & Safety Information 253 METHANOL SAFE HANDLING MANUAL: 4TH EDITION X METHANOL SAFE HANDLING MANUAL: 4TH EDITION XI 1 INTRODUCTION TO THE MANUAL This chapter explains the purpose of the manual and provides an introduction to the methanol value chain. The Methanol Institute’s Product Stewardship policy and contact information are also included. 1.1 PURPOSE OF THE MANUAL We at the Methanol Institute intend this manual to serve as a guidance document for methanol distributors and users like you. The purpose of the manual is to promote the safe handling of methanol in order to protect your health and that of your co-workers, your workplace, the environment, and your community. You may be a wastewater treatment plant operator in India, a biodiesel plant manager in Canada, a Health and Safety Coordinator at a formaldehyde plant in Mexico, a tanker truck driver at a chemical distribution warehouse in Algeria, a research engineer developing a fuel cell in New Zealand, an antifreeze production supervisor in East Siberia, or a shipping terminal manager in China.