Safety and Waste Disposal Considerations

Dr. Christie-Joy (C.J.) Brodrick Assistant Professor, JMU Lisa Schweitzer Assistant Professor, VT April 3, 2006

Safety Highlights at JMU

Please note that safety would be an entire day course in itself.

The following presentation is by no means comprehensive or intended to be used by others as a complete safety plan. We are not experts in safety.
What we present here are highlights of how JMU approaches safe production of biodiesel. We touch on what we have found to be key areas with the intention of giving other users a starting point for developing their own safety plans. Safety plans are highly dependent on reactor design, setup, and location, and thus must be developed separately for each operation. We strongly encourage everyone to take the time to write their own plan.
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Handling of Commercial Biodiesel

Chapter 11: Safety and Environmental Regulation
Composition Information: Biodiesel contains no hazardous materials. Biodiesel contains a variety of fatty acid methyl esters with carbon chain lengths varying between 12 and 22, where 18 carbon chains are the most common. Small quantities (less than 1%) of other materials may be present and should not exceed fuel quality standards.

Handling and Storage: Store in clean, dry, approved diesel equipment between 50 F and 120F. Keep away from oxidizing agents, excessive heat, and ignition sources. Store and use in well-ventilated areas. Do not store or use near heat, spark, or flame. Store out of the sun. Do not puncture, drag, or slide drums or totes. Drum and totes are not pressure vessels; never use pressure to empty.
Inhalation: Negligible danger unless heated to produce vapors. www.nrel.gov/vehiclesandfuels/npbf/pdfs/tp36182.pdf
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Safety Data Sheets

To thoroughly understand the hazards involved with working with specific chemicals substances, the biodiesel small-scale unit operator should be familiar with the Material Safety Data Sheets (MSDS).
MSDS contain information on product identification, ingredients and hazardous classification, physical/chemical characteristics, fire and explosion hazard data, fire fighting measures, accidental release measures, health hazard data, first aid measures, toxicology, reactivity (and stability) data, precautions for safe handling, storage and use, control measures, transportation, disposal, regulatory information, additional information.

MSDS LINKS
Vegetable Oil http://sargentwelch.com/pdf/msds/sch94733.pdf Methanol http://www.biodieselgear.com/documentation/methanol.htm Glycerol http://www.biodieselgear.com/documentation/MSDS_Glycerol.pdf KOH http://www.biodieselgear.com/documentation/KOH.htm NaOH http://www.biodieselgear.com/documentation/NaOH.htm Methoxide http://www.sciencestuff.com/msds/C2658.html Glycerol http://www.biodieselgear.com/documentation/MSDS_Glycerol.pdf Biodiesel http://www.biodieselgear.com/documentation/MSDS_BD.pdf
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Sample MSDS Health Info

Data Description

Vegetable Oil

MeOH

KOH

NAOH

Methoxide

Glycerol

Biodiesel

Health
Skin

1
Causes moderate skin irritation. May be absorbed through the skin in harmful amounts. Prolonged and/or repeated contact may cause defatting of the skin and dermatitis.

3
Causes skin burns. May cause deep, penetrating ulcers of the skin.

3
Causes skin burns. May cause deep, penetrating ulcers of the skin. May cause skin rash (in milder cases), and cold and clammy skin with cyanosis or pale color.

3
Avoid contact with eyes, skin, and clothes

0
May cause irritation N/A

Inhalation

Harmful if inhaled. May cause adverse central nervous system effects including headache, convulsions, and possible death. May cause visual impairment and permanent blindness. Causes irritation of the mucous membrane.

Harmful if inhaled. Irritation may lead to chemical pneumonitis and pulmonary edema. Causes severe irritation of upper respiratory tract with coughing, burns, breathing difficulty, and possible coma.

Irritation may lead to chemical pneumonitis and pulmonary edema. Causes severe irritation of upper respiratory tract with coughing, burns, breathing difficulty, and possible coma. Causes chemical burns to the respiratory tract.

Avoid breathing vapors. Use with adequate ventilation

Due to low vapor pressure, inhalation of the vapors at room temperature is unlikely.

Sample MSDS Health Info, cont

Data Description Vegetable Oil MeOH KOH NAOH Methoxide Glycerol Biodiesel

HEALTH
Eyes

1
Produces irritation, characterized by a burning sensation, redness, tearing, inflammation, and possible corneal injury. May cause painful sensitization to light.

3
Causes severe eye burns. May cause irreversible eye injury. Contact may cause ulceration of the conjunctiva and cornea. Eye damage may be delayed. Harmful if swallowed. May cause circulatory system failure. May cause perforation of the digestive tract. Causes severe digestive tract burns with abdominal pain, vomiting, and possible death.

3
Causes eye burns. May cause chemical conjunctivitis and corneal damage.

3
Avoid contact with eyes, skin, and clothes

0
May cause irritiation N/A

Ingestion

May be fatal or cause blindness if swallowed. May cause gastrointestinal irritation with nausea, vomiting and diarrhea. May cause systemic toxicity with acidosis. May cause central nervous system depression, characterized by excitement, followed by headache, dizziness, drowsiness, and nausea. Advanced stages may cause collapse, unconsciousness, coma and possible death due to respiratory failure. May cause cardiopulmonary system effects.

May cause severe and permanent damage to the digestive tract. Causes gastrointestinal tract burns. May cause perforation of the digestive tract. Causes severe pain, nausea, vomiting, diarrhea, and shock. May cause corrosion and permanent tissue destruction of the esophagus and digestive tract. May cause systemic effects.

Harmful if swallowed.

Low toxicity

N/A

JMUs General Safety Gear

goggles gloves clothing aprons

Location, Location, Location

The following is a list of considerations we had when installing our processor units:

Area must well ventilated No open flames (water heater, clothes dryer, or other device nearby) Adequate lighting Clearances for operation Limited access to the area to other adults, children, and pets Eyewash station Fire extinguisher Chemical reaction work area Fume hood (or some other forced draft system that vents to the outside)

Hazards are dependent on system design and operation...

We looked at four processors

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Sample Reactor Documentation

YOU ARE RESPONSIBLE FOR KNOWING AND COMPLYING WITH ALL APPLICABLE LAWS IN YOUR AREA REGARDING THE PRODUCTION, SALE DISTRIBUTION, TRANSPORTATION, STORAGE AND HANDLING OF OILS, ALCOHOLS (METHANOL), CAUSTICS (LYE) AND FUELS (SUCH AS BIODIESEL).

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Examples of Common Hazards

Basic small-scale biodiesel processing steps for a generic reactor: 1. Transfer oil to the processing tank 2. Heat oil to 120F - 130F 3. Check titration level 4. Prepare methoxide - mix methanol and catalyst 5. Combine oil and methoxide 6. Mix (circulation and/or agitation) for fixed time 7. Wait for glycerin to separate from biodiesel 8. Remove gylcerine from processor tank 9. Wash biodiesel 10. Wait for water and biodiesel to separate 11. Remove water from processor tank 12. Transfer biodiesel to storage tank List of common hazards we identified involved with this process: Personnel exposure (to hazardous vapors, liquids, or solids) Fire or explosion Thermal exposure to hot surfaces Slick surfaces (oil)

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Operation Steps 1 and 2: Transfer and Heat Oil

What if oil overheats? Hazard: The oil is usually heated to 110-130F. If the temp gets above 150F, the methanol (when combined with the oil) will boil and overpressure the vessel. The plastic cone-bottom processor tanks could have a vessel failure. Vessel failure could lead to personnel exposure to fumes and/or explosion hazard. Safeguards: Temperature indication (preferably one that is permanently installed in the system). Only the Appleseed reactor has a temperature indication for the operator and it has a vessel overpressure/temperature relief valve that would open to vent the tank (to the outside). JMU Approach: Install an easily viewable thermometer in the system for monitoring temperature while heating. Alternative to this is to use a DVM with a Thermocouple input or other type of portable temperature indication.
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Operation Steps 1 and 2: Transfer and Heat Oil

What if oil spills from the supply drum or while transferring? Hazard: A large spill of oil will cause slick surfaces. It could possible cause irritation to skin if the oil temperature is too hot.

JMU Approach: Install simple secondary containment or at the minimum have materials available for quick cleanup in case of a large spill.

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Operation Steps 1 and 2: Transfer and Heat Oil

What if heating device (element) overheats? Hazard: Very high surface temperatures. This could lead to an operator being burned, or ignition of materials or vapors. Some systems have thermostatically controlled in-tank heating systems so this is unlikely. Others must be monitored closely. JMU Approach: Install a thermostat and internal heater.

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Operation Step 3: Check Titration Level

What if operator is exposed to MeOH fumes or liquid touches the skin/clothing during titration?
Hazard: Exposure to small amounts of Methanol fumes can lead to blindness or death. JMU Approach: Immediately wash if on skin and seek emergency medical treatment.

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Operation Step 4: Prepare Methoxide

What if the methanol leaks from the methanol barrel or methoxide tank? Hazard: This would be a fire hazard. If a leak develops in the Fuelmeister Methanol storage tank, this is a major hazard because of the potential volume of methanol involved (up to a maximum of 55 gallons). The most likely occurrence of a catastrophic barrel leak would be mishandling the barrel during delivery or transport to the processor location. JMU Approach: Leave area immediately. Vent. Use a purchased methanol cleanup kit. Hazard: Operator is or will be exposed to methanol or methoxide fumes. JMU Approach: Remove any exposed clothing and wash skin. Seek emergency treatment.

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Operation Step 4: Prepare Methoxide

What if the operator is exposed to catalyst? Hazard: Base catalyst (KOH and NaOH) are very corrosive Safeguards: Wear proper protective equipment.

JMU Approach: Seek medical attention.

**Note: An alternative to making your own Methoxide would be purchasing it premixed.

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Summary of Key Considerations

Storing and handling of methanol Consider the type, size, and location of methanol storage container(s) Determine safest way to transfer methanol from storage containers into the the system (to limit exposure) Use spill containment and have an emergency plan Methanol catalyst mixing and addition Design of the methoxide system is critical and all safety aspects should be considered/modified. Methoxide addition to the processor should only be done using a closed system. A carboy Methoxide injection system similar to the Biodieselgear or the Appleseed processor could be added to this system.
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Summary of Key Considerations

Heating Method In-tank heating (Appleseed and Biodiesel Gear) is the safest and most effective heating method. Avoid external wrap-heaters. Also, integral tank insulation (standard water heater tank) is preferred. Use a temperature indicator such as a digital volt meter with a thermocouple input or other type of temperature indication so that the operator can easily see the fluid temperatures in the system. Processor Tank Design /Material Compatibility Be aware of materials of construction and weak points in the systems that could be vulnerable to high temperature or pressure. Glycerol and Wastewater Disposal Glycerol has residual methanol in it. If you dont remove the methanol, consider this hazardous waste. Have a plan!
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