1. Overview of Process Safety Biodiesel Process Safety Management for Biofuels 1. Overview of Process Safety Biodiesel This training on process safety is brought to you by the Center for Chemical Process Safety (CCPS), which is a Technology Alliance of the American Institute of Chemical Engineers. The CCPS currently has about 120 member companies worldwide. This material was produced under grant SH-19479-09-60-F-36 from the Occupational Safety and Health Administration, U.S. Department of Labor. It does not necessarily reflect the views or policies of the U.S. Department of Labor, nor does mention of trade names, commercial products, or organizations imply endorsement by the U.S. Government.

PSM DEFINITION “a management system” “prevention of” “preparedness for” “mitigation of” “response to” “restoration from“ Process Safety Management is defined as “a management system that is focused on prevention of, preparedness for, mitigation of, response to, and restoration from……

catastrophic releases of PSM DEFINITION catastrophic releases of chemicals or energy Process Safety Management is defined as “a management system that is focused on prevention of, preparedness for, mitigation of, response to, and restoration …….. from catastrophic releases of chemicals or energy from a process associated with a facility.”

Here is an example of a catastrophic release of energy Here is an example of a catastrophic release of energy. This explosion occurred on October 29, 2007 at the Barton Solvents chemical distribution facility in Des Moines, Iowa, . The initial fire started in the packaging area while a 300-gallon portable stainless steel tank was being filled with a flammable solvent. The Chemical Safety Board (CSB) investigation found that the nozzle and hose used for the solvent transfer were not intended for use in transferring flammable liquids. Furthermore, the steel parts of the plastic fill nozzle and hose assembly were not bonded and grounded. Static electricity accumulated on these parts and sparked to the stainless steel tote body, igniting the vapor that accumulated around the opening of the tote during filling." The entire warehouse at Barton Solvent was destroyed during the fire and Barton's business was significantly interrupted.

The packaging area - where the fire started - had no automatic sprinkler system and was adjoined to the flammable storage warehouse. The CSB investigation found the wall separating the two areas was not fire-rated. As a result, the warehouse was rapidly consumed, and although this area had an automatic sprinkler system, it was incapable of extinguishing the large blaze. The CSB investigation determined that if Barton had implemented a comprehensive static electricity and flammable liquid safety program, in compliance with current regulatory standards and good practice guidelines, the fire likely would have been prevented. These guidelines include OSHA's Flammable and Combustible Liquids standard and codes and recommended practices of the National Fire Protection Association.

Release of Toxic Chemicals The worse industrial accident in history was the release of toxic chemicals at Bhopal, India on December 3, 1984. The deadly chemical, methyl isocyanate (also referred to as MIC) was released at the Union Carbide plant in Bhopal. The official immediate death toll was 2,259. Thousands more died during the months following the release. The total death toll is estimated at about 10,000 people.

Fires in the biodiesel industry Date Location Description Oct., 2009 Savannah, GA “Significant damage”; one worker hospitalized with a broken leg. Sept., 2009 Osceola County, FL Facility completely destroyed July, 2009 Burbank, WA Facility had to be demolished May, 2009 Brewster, MN “Substantial loss” to the plant Now that we have an overview of what process safety is, let’s look specifically at process safety issues within the biodiesel industry. This slide and the next lists fires that occurred at biodiesel faciiities with significant damage to the facility or loss of life. Notice on this slide ,where four fires are listed, that two facilities were destroyed and two suffered “substantial loss”. A fire at your biodiesel facility could mean the loss of your job, if you are lucky. Worse case, it could mean the loss of your life.

Fires in the biodiesel industry Date Location Description July 7, 2006 New Plymouth, Idaho Blue Sky Biodiesel – Son of owner was killed after welding torch caused tank to explode Feb., 2006 Bakersfield, CA American Biofuels' plant was demolished after a methanol tote fell off a forklift. The July , 2006 biodiesel fire listed above in Idaho was particularly tragic because the owner of the facility lost his son in the fire. Personnel at Blue Sky Biodiesel in Idaho had been retrofitting a former fruit-packing plant over the past few months and were just beginning full-scale production of biodiesel. The plant would have produced 1 million gallons per year of biodiesel from multiple feedstocks. Reports indicate that Blaise Black, 25, was welding on top of a storage tank when an explosion ignited a blaze that would destroy part of the plant and take his life. According to the local fire department, a minor evacuation of local residents occurred when officials became concerned that the thick black smoke generated by the fire might be toxic. The Associated Press wire service reported that Rob Black, father of the victim and managing partner of Blue Sky Biodiesel, was on-site and tried in vain to rescue his son, meanwhile sustaining second degree burns and suffering from smoke inhalation. The storage tank where Blaise Black was welding contained an unknown quantity of fuel, and the explosion set off another blast of flames that rapidly enveloped the building, causing tanks containing glycerin, among other flammables, to explode. The fire chief stated that the tank room and boiler rooms of the plant were destroyed, “Most of the main fire [happened] when the glycerin tank exploded, causing the roof of the plant to be set on fire. The ceiling was about a foot thick with foam and different kinds of insulation and burned vigorously. Twelve area volunteer departments, consisting of 75 to 90 firemen, responded to the fire. The fire chief also stated , “It was so hot, we would have to take [one] crew out, put them in rehab and put a new crew in,

Bakersfield, CA Methanol Fire Methanol is one of the most dangerous chemicals handled at a biodiesel facility. It is very flammable with a flashpoint of 52 ‘F. It is also necessary since it transforms fats or oils into the fuel and liberates triglycerides as a marketable coproduct. A one gallon spill of methanol led to the Bakersfield fire. Just weeks after announcing plans to increase production capacity of its existing facility and expand operations to the East Coast, the American Biofuels biodiesel plant in Bakersfield, Calif., was completely destroyed in February, 2006 by a fire caused by a one gallon spill of methanol. The President of Green Star Products, a majority stakeholder in American Biofuels , reported that the fire did not originate in the plant, He stated “ The fire had nothing to do with the plant whatsoever. We have methanol detectors that are state-of-the-art and can detect even a quarter of a percent of methanol in the air. The fires started outside the manufacturing facility. “ Reports on the fire from a variety of sources have blamed static electricity as the cause of the blaze. However, Green Star did not agree with this assessment. Joe LaStella, the president Of Green Star, said a methanol-transporting tote, weighing nearly 2000 lbs, slipped from A forklift and lead to the outbreak of the fire. Quoting Mr. LaStells, “[A tote] has aluminum bars on it, and one of these bars was dragging along, hitting the concrete . it could have easily caused a spark and ignited less than a gallon of the methanol that had spilled and created a fireball that went back to the tote and set the entire 250 gallons on fire,” “This happened outside the plant and then spread into the plant.” The entire plant, which was in full operation at the time of the fire, was destroyed as a result of the fire. The Bakersfield plant was negotiating several marketing opportunities expected later in 2006. The plant is expected to be rebuilt, which normally takes about 16 months .

Methanol Toxicity Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is highly toxic. Drinking 10 ml (1/3 fluid ounce) can cause blindness, and as little as 100 ml (3-1/2 fluid ounces) can cause death. Emergency Overview -------------------------- POISON! DANGER! VAPOR HARMFUL. MAY BE FATAL OR CAUSE BLINDNESS IF SWALLOWED. HARMFUL IF INHALED OR ABSORBED THROUGH SKIN. CANNOT BE MADE NONPOISONOUS. CAUSES IRRITATION TO SKIN, EYES AND RESPIRATORY TRACT. AFFECTS CENTRAL NERVOUS SYSTEM AND LIVER. ------------------------------------------------------------------------------------------------ NFPA Health Rating: 3 - Severe (Poison) NFPA Flammability Rating: 3 - Severe (Flammable) NFPA Reactivity Rating: 1 - Slight NFPA Contact Rating: 3 - Severe (Life) When handling in the lab, use : GOGGLES & SHIELD; LAB COAT & APRON; VENT HOOD; PROPER GLOVES; CLASS B EXTINGUISHER .

Methanol Toxicity Methanol exposures can cause blindness or even death. These severe effects can be caused by ingestion, inhalation, and also through skin absorption. Know the health effects of methanol and the precautions to take! READ THE Material Safety Data Sheet! Potential Health Effects ---------------------------------- Inhalation: A slight irritant to the mucous membranes. Toxic effects exerted upon nervous system, particularly the optic nerve. Once absorbed into the body, it is very slowly eliminated. Symptoms of overexposure may include headache, drowsiness, nausea, vomiting, blurred vision, blindness, coma, and even death. A person may get better but then worse again up to 30 hours later. Ingestion: Toxic. Can intoxicate and cause blindness or death. Usual fatal dose: 100-125 milliliters. (around 3 fluid ounces) Skin Contact: Methyl alcohol is a defatting agent and may cause skin to become dry and cracked. Skin absorption can cause blindness or death. Eye Contact: Irritant. Continued exposure may cause eye lesions. Marked impairment of vision has been reported with repeated exposures.. Aggravation of Pre-existing Conditions: Persons with pre-existing skin disorders or eye problems or impaired liver or kidney function may be more susceptible to the effects of methanol Be sure to read the MSDS provided by your supplier and know what first aid measures to take. (SPEAKER NOTES CONTINUE ON NEXT PAGE)

Methanol Toxicity Methanol exposures can cause blindness or even death. These severe effects can be caused by ingestion, inhalation, and also through skin absorption. Know the health effects of methanol and the precautions to take! READ THE Material Safety Data Sheet! (Do not repeat slide – these are speaker notes continued from previous page) Fire: Flash point: 12C (54F) Flammable limits in air % by volume: lel: 6.0; uel: 36 Flammable Liquid and Vapor! Explosion: Above flash point, vapor-air mixtures are explosive within flammable limits noted above. Moderate explosion hazard and dangerous fire hazard when exposed to heat, sparks or flames. It can be ignited by static electricity spark. Fire Extinguishing Media: Use alcohol foam, dry chemical or carbon dioxide. (Water may be ineffective.) Adsorbent is recommended for spills of this product. 7. Handling and Storage Protect against physical damage. Store in a cool, dry well-ventilated location, away from any area where the fire hazard may be acute. Outside or detached storage is preferred. Separate from incompatibles. Containers should be bonded and grounded for transfers to avoid static sparks. Storage and use areas should be No Smoking areas. Use non-sparking type tools and equipment, including explosion proof ventilation. Containers of this material may be hazardous when empty since they retain product residues (vapors, liquid); observe all warnings and precautions listed for the product. Do Not attempt to clean empty containers since residue is difficult to remove. Do not pressurize, cut, weld, braze, solder, drill, grind or expose such containers to heat, sparks, flame, static electricity or other sources of ignition: they may explode and cause injury or death.

Sodium hydroxide Sodium hydroxide, also called caustic soda and lye, can be fatal if swallowed. It is HARMFUL IF INHALED. It can CAUSE BURNS TO ANY AREA OF CONTACT. It CAN CAUSE BLINDNESS. It REACTS WITH WATER, ACIDS AND OTHER MATERIALS. Emergency Overview of sodium hydroxide -------------------------- On a scale of 1-4 , NaOH has a Health Rating: 4 - Extreme (Poison) Reactivity Rating: 2 - Moderate Contact Rating: 4 - Extreme (Corrosive) Lab Protective Equip: GOGGLES & SHIELD; LAB COAT & APRON; VENT HOOD; PROPER GLOVES Storage : Should be store separately from other chemicals. ----------------------------------------------------------------------------------------------------------- Inhalation: Can cause Severe irritant. Effects from inhalation of mist vary from mild irritation to serious damage of the upper respiratory tract, depending on severity of exposure. Symptoms may include sneezing, sore throat or runny nose. Severe pneumonitis may occur. Ingestion: Corrosive! Swallowing may cause severe burns of mouth, throat, and stomach. Severe scarring of tissue and death may result. Symptoms may include bleeding, vomiting, diarrhea, fall in blood pressure. Damage may appear days after exposure. Skin Contact: Corrosive! Contact with skin can cause irritation or severe burns and scarring with greater exposures. Eye Contact: Corrosive! Causes irritation of eyes, and with greater exposures it can cause burns that may result in permanent impairment of vision, even blindness.

Remaining Course Material Process Hazard Analysis Compliance with fire prevention standards. Standard Operating Procedures Safe work Procedures Mechanical Integrity Management of Change Auditing Process Safety systems Emergency response procedures We have just completed an overview of Process Safety for the biodiesel industry. This overview is one of the nine training modules contained in this course. The screen shows the other eight modules that are planned for this course. The goal of these modules are to prevent injuries and fatalities at your biodiesel facility.