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Produced by Arie van der Winden
Table of Contents
Preamble 7 Chapter 1: Introduction 8 Should You Make Your Own Biodiesel? 8 Chapter 2: Biodiesel 9 What is Biodiesel? 9 Advantages of Biodiesel 10 Disadvantages Biodiesel 11 Speciﬁcations 13 Quality 14 Chapter 3: WVO Collection 19 Negotiating for WVO: 20 What to be aware of: 21 Chapter 4: WVO Preparation 22 Heating 22 Filtration 23
Testing for Water 24 Chapter 5: Chemicals 27 Iso Propyl Alcohol 27 Methanol 28 Sodium Hydroxide (NaOH) 29 Sodium Methoxide 30 Chapter 6: Environment, Health and Safety 31 Environment 31 Health 32 Safety 33 Chapter 7: Storage 40 Biodiesel Containers 40 Chapter 8: Equipment-41 Chapter 9: How I make Biodiesel 42 Introduction 42 Making Sodium Methoxide 43 Heating & Straining the WVO 44
Chapter 9: Biodiesel Batch Information 49 Appendix 1: Frequently Asked Questions 53 Can I use Biodiesel in my old Diesel Engine? 53 Will it affect the Fuel Lines? 54 What is Methanol? 55 Is Methanol hazardous or dangerous? 56 What can I do to reduce my exposure to Methanol? 57 What do I do if I breathe in Methanol or spill some on myself? 58 What do I do if I spill Methanol? 59 What do I do in case of a Methanol ﬁre? 60 How should I store Methanol? 61 How should I dispose of Methanol? 62 How can I buy Methanol? 63 Where can I ﬁnd more information? 64 Appendix 2: Glossary of Terms 65
I have been researching Biodiesel for several years and had so much information available that it became difﬁcult to keep it organised. I decided to put some of this information in a book, which will be easy to access. My aim is to keep this up to date and make it available on the Internet as an eBook. The book is divided into the following chapters: • • • • • • • • • • • Chapter 1 : Introduction Chapter 2 : Biodiesel Chapter 3 : Waste Vegetable Oil Collection Chapter 4 : Waste Vegetable Oil Preparation Chapter 5 : Chemicals Chapter 6 : Environment, Health & Safety Chapter 7 : Storage Chapter 8 : Processing Equipment Chapter 9 : How I make Biodiesel Appendix 1 : Frequently Asked Questions Appendix 2 : Glossary of Terms
Chapter 1: Introduction
Should You Make Your Own Biodiesel? You can make your own. The question is, should you? Yes, why not? You will help the environment and safe money. I hope to share my experience to make the operation safer, should you decide to go ahead and make your own. Here are a few points to consider: • In no way should you be making your own Biodiesel unless you receive proper training and instruction from a professional on how to handle the chemicals and any other components used in the making of Biodiesel. Before you purchase anything, make sure you have a reliable supply of feedstock and chemicals. Can you assure that the quality of the Biodiesel meets speciﬁcations? Many Biodiesel producers have in-house labs or take other measures to ensure that the quality of the Biodiesel they produce meets ASTM standards for optimal performance of diesel engines and vehicles. How much Biodiesel will you actually use? If you use a small amount of Biodiesel, it may be more cost-effective to simply purchase your Biodiesel from a reputable producer or retail distributor. How will you store the Biodiesel? Storage is another quality-related issue as Biodiesel should not be stored for more than six months as it will degrade. Check with your local Council about their fuel storage regulations. At what percentage will you use the Biodiesel? Most engine and vehicle manufacturers warrant their vehicles for use of up to 5% of Biodiesel in Petrodiesel (B5). The use of highlevel blends (B20+) and pure Biodiesel (B100), should probably be avoided. It’s up to you as you will loose your warranty of any fuel related problems.
• • •
Chapter 2: Biodiesel
What is Biodiesel? Fatty Acid Methyl Esters (FAME) are receiving increasing attention as a non-toxic, biodegradable, and renewable alternative diesel fuel. These esters have become known as Biodiesel. Many studies have shown that the properties of Biodiesel are very close to Petrodiesel. Therefore, Biodiesel can be used in diesel engines with few or no modiﬁcations. Biodiesel has a higher Cetane Number than Petrodiesel, no aromatics, and contains 10 to 11% oxygen by weight. These characteristics of Biodiesel reduce the emissions of Carbon Monoxide (CO), Hydrocarbon (HC), and particulate matter (PM) in the exhaust gas compared with Petrodiesel. Biodiesel is a mixture of Methyl Esters of long chain Fatty Acids. It is produced by the Transesteriﬁcation of Vegetable Oils and Animal Fats – all of which belong to a group of organic Esters called Triglycerides. Typical examples are Rape Seed Oil, Canola Oil, Soya Bean Oil, Sunﬂower Oil, Palm Oil, Cotton Seed Oil, etc. from vegetable sources, beef and sheep tallow and poultry oil from animal sources and also from used cooking oil. The chemistry is basically the same irrespective of the feedstock. Biodiesel is an environmentally friendly replacement for, or additive to, Petrodiesel. Biodiesel can be easily mixed with Petrodiesel to create a Biodiesel blend. Biodiesel requires no special storage or fuel dispensing facilities.
Advantages of Biodiesel One of the key advantages of Biodiesel is that it is renewable fuel. Fossil fuels (like petrol & diesel) are non-renewable. Renewable fuels like Biodiesel are sustainable source of fuel because, as long as they are produced in a ecologically sustainable way, they will not run out. Biodiesel has also been shown to greatly reduce net CO2 greenhouse gas emissions. This is because CO2, which is released when the fuel is burnt, is captured by growing plants, the oil of which, is processed into another batch of Biodiesel. Using Biodiesel also has the potential to greatly reducing our reliance on expensive imported oil, leading to the creation of local jobs and the improvement of our balance of payments situation. Biodiesel performs very much like Petrodiesel as it has similar power, torque and fuel economy. The big advantage in using Biodiesel is that harmful exhaust emissions are substantially reduced compared to Petrodiesel. Emissions such as unburned hydrocarbons, Carbon Monoxide, Sulphur, aromatics and particulates are reduced when using Biodiesel. Biodiesel provides better engine lubrication than Low Sulphur Petrodiesel. Biodiesel is also safer to handle due to its excellent biodegradability characteristics, low toxicity and high ﬂashpoint. The great thing about Biodiesel is that it can be made from waste vegetable oil. This means that not only do vehicles running on Biodiesel produce less harmful air pollution, they are also beneﬁting the environment by reusing oil that would normally go into landﬁll or be used for feedstock.
Disadvantages Biodiesel Biodiesel experiences difﬁculties in cold weather, my ﬁrst batch, made of Cotton Seed WVO, had a Cloud Point of + 5C. This could cause some problems in the winter as temperatures drop to -5 C were we live.
Drivability I have used a mix of 30 % Biodiesel up to now and have noticed no difference in performance. It’s a great feeling you have driven past the Service Station on your own home made fuel.
Speciﬁcations Biodiesel speciﬁcations have been implemented in several countries around the world. Two sets of standards may be used, they are: • ASTM D 6751
This is a test used in the USA and several other countries. ASTM stands for: American Society of Testing and Materials. • EN 14214
This is a test used in the Europe. This test is a standard of the European Committee for Standardisation (CEN).
Quality Modern Diesel engines require quality fuel. Making your own Biodiesel is taking a risk as you may end up with three potentially fuel pump, injector and engine damaging substances, they are: • • • • Free Glycerine Poorly Converted WVO. Sodium Hydroxide Sodium Methoxide
Free Glycerine Free Glycerine and mono-, di- and triglycerides (poor ester conversion) will form gum-like deposits around injector tips and valve heads. For Glycerine analysis get a test kit for determining Ethylene Glycol in motor oil. This test is simple and it generates a purple colour if substantial free glycerol is present.
Poorly Converted WVO WVO, which has not been converted, will substantially increase cold starting problems and ﬁlter plugging. The Biodiesel will have a high Pour Point and may solidify in your fuel tank. I test each batch by refrigerating 100 ml of the Biodiesel overnight. Our fridge operates at + 5 C and if I see any cloudiness I will not use it.
Sodium Hydroxide Sodium Hydroxide can damage the injector pump. The key to good Biodiesel is: • • • Use pure chemicals, and measure them accurately. Follow the instructions carefully. Proper washing will remove Glycerine, Sodium Methoxide and Sodium Hydroxide.
Sodium Methoxide Sodium Methoxide is highly toxic and corrosive can damage your health and your vehicle’s: • • • Fuel Pump Filters Injectors
As mentioned above, proper washing will remove Sodium Methoxide.
Chapter 3: WVO Collection
Animal fat or vegetable oil can be used to make Biodiesel; some are more preferred then others. Because of their high levels of Free Fatty Acids, Animal Fats should be lowest on your list. Virgin vegetable oil will be the best to use. Unfortunately, virgin oil is the most expensive to obtain. In the middle is the Waste Vegetable Oil (WVO). WVO in this book refers to oil collected from Fish & Chips shops and restaurants. A wide variety of Vegetable Oils can be used, including: • • • • • • Canola Oil Soybean Oil Sunﬂower Oil Corn Oil Peanut Oil Cotton Seed Oil
Of these oils, the soybean, sunﬂower and canola are best, followed by the corn and peanut oil. On the bottom of the list are coconut, palm and hydrogenated oils due to their tendency to be solid at room temperatures. These may be used, but, might require preheating to liquefy. The ﬁrst step in setting up to make your own Biodiesel is to secure a regular supply of WVO. It took me some time to establish a regular supply within a reasonable travelling distance from home. Unfortunately all of my supplies are solid at room temperature. Once you have a regular supply, make sure you follow up and take the WVO away as soon as it is available. I provide my suppliers with clean empty 20 litre steel containers.
Negotiating for WVO: If a restaurant owner or manager is offered a way to reduce their operation cost, most are willing to help you. They are looking for a person that they can depend on and will collect the WVO as agreed. Be sure to be courteous and clean when collecting from your source. Always clean up after yourself. Do buy their take away from time to time or dine at the restaurant.
What to be aware of: Often, restaurants will just give you their WVO, but they don't put much effort into proper storage. The most important thing to be aware of is WATER contamination. If your source of WVO has been contaminated with water, you will need to get the water out before processing. Water in the WVO will cause the batch to have foam on the top of the Biodiesel. If the water contamination is heavy, the batch can form chunks of soap. Try to avoid these sources all together. If your unsure, always pre-test before you process with it.
Chapter 4: WVO Preparation
The next step is preparing the WVO for use in the Biodiesel processor. The WVO will contain crumbs and other solids. It may also contain water. To clean the oil I carry out the following steps: • • • • Heating My supply of WVO is solid at room temperature and needs to be heated before I can use it. I heat the WVO, to about 60°C, with a gas burner under a 20 litre steel drum. It takes about half an hour to completely melt the WVO in the pail. Safety Do this step slowly! Water, settled in the bottom of the drum, can suddenly boil and blow the oil out of the drum. Have the burner on the lowest setting until the oil is all ﬂuid. The oil is then ﬂuid enough for the “Filtration” step. Heating Filtration Testing for Water Dewatering
Filtration WVO often contains foreign matter such as crumbs and it always wise to filter the WVO before processing. The more you can remove before processing, the better. Many people choose to make their own screen filter while others choose to purchase pre-fabricated filters. I use a kitchen strainer with cheese cloth. There are two main types of filters you can buy, they are: • • Bag Filters Bag filters are simply screened bags the WVO is poured through to filter the oil. To ﬁlter the solids, from the WVO, I use a steel kitchen strainer followed by ﬁne cloth, similar to cheese cloth. This takes out most of the solids. Cartridge Filters Cartridge filters work by pumping the oil through a spin on filter or in-line element filter. Coffee Filters Coffee filters are paper filters. I use them as a final filter. They are cheap at A$ 1.85 for 40 filters. I use one filter for each 10 litres of finished Biodiesel. Bag Filters Cartridge Filters
Testing for Water I test a small batch for water, before I do anything else. WVO must be dry for the conversion process. I put about 100 ml of WVO in an old frying pan an heat it, on my barbeque plate, to about 70°C. If any water is present it will “bubble”. This means I will have to heat the whole batch! If any water is present remove it by the following methods: • Settling the water
This method saves energy. Heat the oil to 60°C, maintain the temperature for 15 minutes and let it settle for at least 24 hours. Drain the water in a slop bucket. Any WVO drained this way will solidify (in my case) and I skim this off for reuse. • Boiling the water off
Less-preferred method as it uses more energy, and helps to form more FFA in the oil. Heat the oil slowly and stir frequently if possible. I heat the oil to 120°C. Picture on the next page.
Chapter 5: Chemicals
Chemicals described in the book are the ingredients used in titration and the WVO conversion process. The chemicals I use are: • • • • Iso Propyl Alcohol Iso Propyl Alcohol is used for titration. Iso Propyl Alcohol Methanol Sodium Hydroxide (NaOH) Sodium Methoxide
Methanol Methanol is used to make Sodium Methoxide. Safety Methanol is a toxic chemical. It can enter the body through breathing in the vapour, direct skin contact or by accidental swallowing. It can cause nausea, dizziness and visual disturbances that can result in blindness. Swallowing small quantities could pose a signiﬁcant health threat to the central nervous system and could also affect other vital organs. It is a cumulative poison and repeated exposure to relatively low concentrations could cause harm in the longer term.
Sodium Hydroxide (NaOH) Sodium Hydroxide (NaOH) is used to make Sodium Methoxide. Safety Sodium Hydroxide
Sodium Methoxide Sodium Methoxide is the catalyst used in the conversion of WVO to Biodiesel. Safety Sodium Methoxide
Chapter 6: Environment, Health and Safety
Section 6 of this book gives a description of the following: • • • • Environment Health Safety Housekeeping
Space has been provided on many pages to assist in future updates. Environment Biodiesel is nearly carbon-neutral, meaning it contributes almost zero emissions to global warming! Biodiesel has the following environmental advantages over “Petroleum Diesel”: • • • • • • • • Reduction of net carbon dioxide (CO2) emissions. Reduction of sulphur dioxide (SO2) emission. Reduction or increase of nitrous oxide (NOx) emissions, depending on the age of the vehicle and the tuning of the engine. Reduction of soot emissions. Reduction of carbon monoxide (CO) emissions. Reduction of hydrocarbon (HC) emissions. Reduction of all Polycyclic Aromatic Hydrocarbons (PAH). Biodiesel replaces the exhaust odour typical of petroleum diesel with the pleasant smell of fried chips.
Health Your health is the most important thing in life. When we are young health is not a topic we dwell on frequently but as you get older and health problems occur, it becomes foremost in our minds. This book often mentions the dangers of the chemicals used in making Biodiesel and I suggest you take heed.
Safety I worked for 46 years in the Petroleum & Chemical Industry as an Operator, Production Superintendent and Production Planner and I am very concerned about the safety and health of people making Biodiesel at home. Safety is a vital part of all work carried out in the Biodiesel Processing Shed. Protection of people and equipment must at all times be the number one priority. To assist in this I use the following safety equipment: • • • • • • Triton Powered Respirator Plastic Gloves Rubber Safety Boots Safety Shower Eye Wash Fire Protection
Triton Powered Respirator I purchased a Triton Powered Respirator last year to give me protection when working in dusty conditions. This unit is useful for splash protection and when handling Sodium Hydroxide powder. The cartridges supplied are not suitable for handling Methanol or Sodium Methoxide. INSERT PICTURE HERE
Plastic Gloves I use Plastic Gloves when handling WVO and the chemicals used in Biodiesel processing. Rubber Safety Boots When I work in the shed I use steel capped rubber safety boots. The steel caps are needed when handling heavy drums of oil and chemicals.
Safety Shower I have installed a Safety Shower just outside the shed in case I get splashed with chemicals. It is a simple shower head with a quick action valve operated by a a chain and handle. See picture. below: INSERT PICTURE HERE
Eye Wash I purchased an Eye Wash Bottle from a safety equipment supplier and keep it nearby in the Biodiesel Processing Shed. INSERT PICTURE HERE
Fire Protection There is a serious risk of ﬁre and explosion because Methanol is highly ﬂammable and there are many potential sources of ignition in most homes such as: • • Normal electrical equipment, for example kitchen appliances, plugs and switches. Open ﬂames, for example gas burners.
It is also possible that a violent chemical reaction could occur by: • • Making a mistake with the recipe, for example getting the quantities wrong or adding the chemicals in the wrong order. Poor mixing; or making too much at once.
Any of these could result in the mixture splashing or boiling over, causing serious burns. My Biodiesel Processing Shed is equipped with the following Fire Protection: • • A Dry Powder Fire Extinguisher. A CO2 Fire Extinguisher.
I also have a Fire Water Pump and a 30 m Hose Reel set up about 10 m from the shed. The Fire Pump draws water from a 20,000 litre Fish Pond. I test the pump before I start processing each batch of WVO.
Housekeeping Housekeeping is an important part of the overall operation. Oil spills are slippery and could result in falls and injury. Chemical spills are a health and ﬁre danger. • Clean all spills immediately.
After processing your Biodiesel, carry out the following: • • • • • • Safely dispose of all paper ﬁlters and rags in the rubbish bin. Wash your plastic gloves. Clean your breathing apparatus and store it in a clean bag or case. Hot water wash all your titration and testing equipment. Place your slop bucket in a locked, well ventilated area. Put your clothes in the washing.
Note: Please make sure the person who cleans your clothes is not exposed to any dangerous chemicals. Cleaning personnel is often forgotten in safety discussions.
Chapter 7: Storage
Storage is important as you are using ﬂammable materials. Store all chemicals out of reach of children, preferably in a locked cabinet. If you use an open ﬂame when heating your WVO, keep the Methanol and Sodium Methoxide away from the area. Biodiesel Containers Look for the triangular shape with the "2" inside, usually on the bottom. This is HDPE (High Density Poly Ethylene), which is what you are looking for. Any container designed to hold fuel will safely hold Biodiesel.
This chapter describes the equipment I use and will show pictures of my setup. To make Biodiesel, as per the process in this book, you need the following equipment: • • • • • • • • • • • • • Plastic Gloves. Chemical Goggles. Respirator with ﬁlters suitable for Methanol vapour. Scales that weigh 0 to 50 gram with 0.1 gram accuracy. pH meter. Aquarium air pump, hose and a “T” piece. Air stones (2), wooden type, not blue ones. Glass measuring cylinder ( 20 ml ). Glass measuring cylinder ( 1000 ml ). 2 Litre Clear Glass Container (Flagon). 20 litre Pails for WVO collection. Gas Burner to WVO. Biodiesel Processing Vessel.
With steel containers you can use LPG heaters to heat the WVO, then switch to an immersion heater before adding the Methanol.
How I make Biodiesel
Introduction To make Biodiesel efﬁciently, from WVO, we have to avoid one major problem: • Soap Formation
Soap is formed, during base-catalysed Transesteriﬁcation, when Sodium ions combine with Free Fatty Acids, present in WVO. Soap reduces the yield because it bonds the Methyl Esters to water. The bonded Methyl Esters get washed out at the washing stage but make water separation more difﬁcult and increase water consumption. This process takes care of the free Fatty Acids. I use Sodium Hydroxide, because it is easy to obtain. I buy it from supermarkets, in 500 gram containers, for A$ 3.95.
Making Sodium Methoxide 1. Mixing Sodium Hydroxide (NaOH) with Methanol is an exothermic reaction, generating heat. It's nasty stuff and it's not easy to mix. It must be thoroughly mixed before you use it, with all the Sodium Hydroxide (NaOH) dissolved. Safety Take FULL SAFETY PRECAUTIONS when working with Methanol, Sodium Hydroxide (NaOH) and Sodium Methoxide! Use a tough, thick, container made of HDPE (High Density Polyethylene) usually marked "HDPE" on the bottom, with the international code "2", with a tight stopper and a screw on cap. I make enough Sodium Methoxide to process 10 litres of WVO. 1. Measure 2 litres of Methanol into the container. 2. Add the amount of Sodium Hydroxide obtained from the titration result. 3. Tightly ﬁt the cap and swirl the mixture vigourously for a minute. 4. Slowly release the cap the let any vapour escape. 5. Do this four or ﬁve times and check the results. Safety Sodium Methoxide and Methanol are DANGEROUS CHEMICALS. Take full safety precautions, wear Breathing Apparatus, safety goggles, plastic gloves and clothing, have running water nearby. Do not breathe the fumes.
Heating & Straining the WVO The following is the procedure I use to make a batch of 10 litres of Biodiesel: • • • Melt all WVO, then strain through a metal kitchen strainer and a ﬁne cloth. Pour 10 litres of WVO into your Biodiesel Processor. Heat the WVO in your Biodiesel Processor to 55°C.
Titration Now you should be ready for titration (testing). • • • • • Add 10 ml of Iso Propyl Alcohol into your titration container. I use a spice container. Add enough drops of Turmeric Mixture until the solution turns yellow. Add 1 ml of the WVO to the titration container. Add enough of the 1 % Sodium Hydroxide Solution until the liquid in the titration container turns pink. If the solution changes back to yellow add some more until the pink colour stays for 5 minutes.
Making Sodium Methoxide When the Titration is successfully completed, make enough Sodium Methoxide for the quantity of WVO you are going to process. I suggest you start with 10 litres of WVO initially until you are conﬁdent enough to make larger batches. Safety: Remember, put the Sodium Hydroxide (NaOH) into the Methanol. The mixture will become warm and may produce some vapour.
Adding the Sodium Methoxide to the WVO • • • Add the 2 litres of Sodium Methoxide to the 10 litres of WVO in the Biodiesel Processor. Keeping the solution at 55 °C, turn on the agitator and mix for 50 - 60 minutes. After 24 hrs. drain the Glycerine from the Biodiesel Processor, noticing the dark colour (near black). When the colour begins to lighten (honey colour), switch receptacles as this is your raw Biodiesel. This must now be washed.
Safety: Take care, the Glycerine is quite hot and caustic!. Dispose of the Glycerine into a slop container and store in a safe, well ventilated area.
Washing the Biodiesel Some people do not wash their Biodiesel but I do not want any soap or Sodium Methoxide in my vehicle fuel tank. To wash the Biodiesel I use a 20 litre HDPE drum with a drain valve and a screw on cap. Below is the procedure I use, which has been quit successful. • • • • • • • • • Add 3 litres of hot water to the container and shake gently. Leave to settle for one hour. Drain most of the cloudy water. Add 3 litres of hot water to the container and shake vigourously. Leave to settle for one hour. Drain most of the cloudy water. Do this ﬁve times. Let the washed Biodiesel settle for 24 hours. Drain any remaining water.
Chapter 9: Biodiesel Batch Information
In this chapter I will give details of the batches of Biodiesel I made. Batch 1 Batch 1 was made from Cotton Seed WVO. This WVO is a liquid at room temperature. Quantities used: WVO: 10 Litres Methanol: 2 Litres Sodium Hydroxide: 65 Grams Biodiesel Yield: 9 Litres. I lost some during the washes because I didn’t let it settle long enough. Picture of Batch 1 Biodiesel below.
Batch 2 Batch 2 was made from unknown WVO. This WVO was a solid at room temperature. Quantities used: WVO: 10 Litres Methanol: 2 Litres Sodium Hydroxide: 65 Grams Biodiesel Yield: 10 Litres. The Biodiesel was waxy and needs to be processed again. I probably didn’t use enough Sodium Hydroxide as my titration was difﬁcult to do. Picture of Batch 2 Biodiesel below.
Appendix 1: Frequently Asked Questions
Can I use Biodiesel in my old Diesel Engine? Biodiesel will clean your injectors and fuel lines. If you have an old diesel vehicle, there's a chance that your ﬁrst tank or two of Biodiesel could free up all the accumulated Petrodiesel deposits and clog your fuel ﬁlter. Buy a new ﬁlter before using Biodiesel and be prepared to change ﬁlters soon.
Will it affect the Fuel Lines? Old vehicles (older than mid-90s) might require upgrades of fuel lines as Biodiesel may swell certain types of rubber. Almost all new vehicles should have no problem with Biodiesel, but check with the vehicle manufacturer.
What is Methanol? Methanol, also known as wood alcohol or methyl alcohol, is made primarily from natural gas or coal, and can also be produced from renewable resources such as landﬁll gas and digester gas. Methanol is actually present within the human body in small quantities from eating fruits and vegetables, and drinking diet soda containing artificial sweeteners. According to the FDA, as much as 500 milligrams per day of Methanol is safe in an adult’s diet. In the body, Methanol is metabolised in the liver, converted first to formaldehyde, and then to formate. As a building block for many biological molecules, formate is essential for survival. Methanol is a chemical used to make hundreds of products that touch our daily lives, from plastics and paints, to construction materials and clothing.
Is Methanol hazardous or dangerous? Yes, Methanol is a hazardous chemical that is highly ﬂammable and toxic. Methanol must be properly stored, transported and used by people that have been properly trained in its handling. Methanol is extremely toxic to humans if ingested or if vapours are inhaled. Direct exposure to Methanol should be avoided, as Methanol can be harmful if swallowed, absorbed through the skin, or inhaled. Ingestion of as little as one to four ounces can cause irreversible injury to the nervous system, blindness or even death. Methanol can cause poisoning, systemic acidosis, optic nerve damage and central nervous system (CNS) effects. Methanol can also degrease the skin, which may cause dermatitis. Symptoms of acute Methanol exposure may include headache, weakness, drowsiness, nausea, difﬁcult breathing, drunkenness, eye irritation, blurred vision, loss of consciousness, and possibly death. Patients may improve and then get worse again up to 30 hours later.
What can I do to reduce my exposure to Methanol? First, make sure that you receive proper training and guidance on handling Methanol. Be aware of the hazardous properties of Methanol, and exercise caution to avoid contact with it. Avoid breathing of Methanol vapour. Proper ventilation is required to ensure safe working conditions. The type of ventilation will depend upon such factors as dead air spaces, temperature, convection currents and wind direction and must be considered when determining equipment location, type and capacity. If mechanical ventilation is used, spark-proof fans should be implemented. At a minimum, wear side-shielded safety spectacles and plastic gloves.
What do I do if I breathe in Methanol or spill some on myself? In case of Methanol contact with skin, remove contaminated clothing, wash with soap and water for 15 minutes, and seek medical attention if irritation occurs. If Methanol comes in direct contact with eyes, immediately ﬂush eyes with copious amounts of tepid water for at least 15 minutes. The patient should be taken to a health care facility, and referral to an ophthalmologist considered. In case of inhalation of Methanol vapour, remove the individual to fresh air. Asphyxiation from vapour may require artiﬁcial respiration. Ingestion of Methanol is life threatening. Onset of symptoms may be delayed for 18 to 24 hours after ingestion. Due to the risks of aspiration into the lungs, do NOT induce vomiting. The decision to induce vomiting should be left to a medical professional attending the victim. Transport immediately to a health care facility where standard Methanol ingestion treatment can be administered. Immediate medical attention is critical!
What do I do if I spill Methanol? If a Methanol spill occurs, stop or reduce discharge of material if this can be done without risk. Call your local ﬁre department for immediate assistance. Isolate the spill or leak area immediately for at least 100 metres in all directions. Eliminate all sources of ignition, and stay upwind. Do not touch or walk through the spilled material. Prevent Methanol from entering into waterways, sewers, basements or conﬁned areas. A vapour suppressing foam may be used to reduce vapours. For small spills (up to 200 litres) absorb with earth, sand or other non-combustible material and transfer to containers for later disposal. For large spills, dike far ahead of liquid spill for later disposal, and follow local emergency protocol for handling. Spills into large natural bodies of water, such as rivers and oceans, cannot be contained. For releases into soil, surface water or groundwater, Methanol has a half-life of just one to seven days, and given its high rate of biodegradation, Methanol spills are not likely to persist. Methanol is used extensively in the nation’s wastewater treatment facilities to reverse the damaging effects of nitrate build-up in sensitive aquifers and waterways by accelerating biodegradation. As a ﬂammable and toxic chemical, caution must be exercised to avoid contact with Methanol.
What do I do in case of a Methanol ﬁre? Accumulations of Methanol vapours in conﬁned spaces may explode if ignited, and containers ﬁlled with Methanol may rupture violently if exposed to ﬁre or excessive heat for a prolonged duration. Methanol ﬂames are almost invisible in bright sunlight conditions, but they may be detected by the heat generated or the burning of other materials. Large amounts of water will remove heat and can be effective in diluting Methanol to the point where most ﬁres can be readily extinguished. To prevent ﬁres keep open ﬂames, sparks and oxidants away from Methanol. Dry chemical powder, carbon dioxide and alcohol-resistant foam extinguish Methanol ﬁres by oxygen deprivation. Fire-ﬁghters should use full-face, self-contained breathing apparatus, and wear impervious clothing, gloves and boots. For larger ﬁres involving a tank, rail car or tank truck, isolate for 1/2 mile in all directions, also consider evacuation for 1/2 mile in all directions. Keep any Methanol containers cool by spraying with water.
How should I store Methanol? Methanol should always be kept within closed systems or approved containers and never left open to the atmosphere. Containers should be labelled in accordance with local regulations and site requirements. You should have comprehensive product handling procedures and systems in place at all storage and transfer points. Materials and methods of construction must be compatible with Methanol service. Methanol is non-corrosive to most metals at ambient temperatures; exceptions include lead, magnesium and platinum. Mild steel is usually selected as the construction material. Tanks built with copper alloys, zinc (including galvanised steel), aluminium or plastics are not suitable for Methanol-water solutions. While plastics can be used for short-term storage, they are generally not recommended for longterm storage due to deterioration effects and the subsequent risk of contamination. Furthermore, coatings of copper (or copper alloys), zinc (including galvanised steel) or aluminium are attacked slowly.
How should I dispose of Methanol? Large quantities of waste Methanol can either be disposed of at a licensed waste solvent company or reclaimed by ﬁltration and distillation. Waste Methanol, or water contaminated with Methanol, must never be discharged directly into sewers or surface waters. Do not pour Methanol down the drain, on the ground or into any body of water. Methanol is a hazardous material and must be disposed of properly. Check with local environmental ofﬁcials for instructions on how to safely dispose of Methanol in your community.
How can I buy Methanol? The Methanol Institute serves as the trade association for the global Methanol industry, and members supply most of the world’s Methanol. Biodiesel facility operators and engineering ﬁrms interested in obtaining Methanol for Biodiesel production should visit their web site at: http://www.methanol.org Click on the “Biodiesel” page, and go to: “Want to Purchase Methanol: Fill out our Methanol Source Request.” Simply complete and submit this on-line form, letting them know what your Methanol needs are, and they will forward this form to major Methanol suppliers and encourage them to contact you.
Where can I ﬁnd more information? Visit the “Biodiesel” section of: http://www.methanol.org and click on the report “A Biodiesel Primer: Market & Public Policy Developments, Quality, Standards and Handling.” You can also visit the web site of the National Biodiesel Board at: http://www.biodiesel.org.
Appendix 2: Glossary of Terms
The following is a glossary of the most common terms used in this book: Acid A classiﬁcation of substances that liberate hydrogen ions in water, and are normally sour and corrosive, with a pH lower than 7. A compound or atom that donates protons. AFFF Aqueous Film Forming Foam. Used to ﬁght alcohol ﬁres. Alcohol A large classiﬁcation of organic compounds containing one or more hydroxyl groups attached to carbon atoms. Aliphatic Any non-aromatic organic compound having an open chain structure. Alkali A classiﬁcation of substances that liberate hydroxide ions in water, to form caustic and corrosive solutions which turn litmus paper blue, with a pH higher than 7, for example Sodium Hydroxide. A compound that reacts with or neutralises hydrogen ions. Aniline Point A laboratory test, indirectly measuring the aromatics content of oil by its reaction with aniline. The Aniline Point is the temperature at which the aniline-oil mixture changes colour. Lower aniline points indicate higher aromatic levels.
Anhydrous Without water, dry. Liquids and solids (powders) are sold as "anhydrous" when they have been processed to remove water from the end product. Transesteriﬁcation of Biodiesel must be an anhydrous process or funny things happen. Water in the vegetable oil causes either no reaction or cloudy Biodiesel, and water in Sodium Hydroxide (NaOH) or Methanol renders it less useful or even useless, depending on how much water is present. Either let your vegetable oil settle for 2-3 days before using and drain the water off the bottom, or heat the oil and boil off the water. Store Sodium Hydroxide (NaOH) and Methanol in (separate) air-tight containers. Aromatics A class of hydrocarbons of which Benzene is the parent. They are called ”Aromatics” because many of their derivatives have sweet or aromatic odours. These hydrocarbons are of relatively high speciﬁc gravity and possess good solvent properties. Aromatics, especially those with two or more benzene rings, have poor oxidation stability and a low VI. ASTM American Society for Testing and Materials - an international voluntary standards organisation that develops and produces technical standards for materials, products, systems and services. Base A classiﬁcation of substances which when combined with an acid will form a salt plus water, usually producing hydroxide ions when dissolved.
Bubble Wash A method of ﬁnal washing of Biodiesel through air agitation. Biodiesel ﬂoats above a quantity of water. Bubbles from an aquarium air pump and air stone are injected into the water causing the bubbles to rise. At the Water / Biodiesel interface, the air bubbles carry water up through the Biodiesel by surface tension. Simple diffusion causes water-soluble impurities in the Biodiesel to be extracted into the water. As the bubble reaches the surface and breaks, the water is freed and percolates back down through the Biodiesel again. Carbon chain The atomic structure of hydrocarbons in which a series of carbon atoms, saturated by hydrogen atoms, form a chain. Volatile oils have shorter chains. Fats have longer chain lengths, and waxes have extremely long chains. Carboxyl Carboxylic - the univalent acid radical (-COOH), present in most organic acids, this making them biodegradable. Catalyst A substance which without itself undergoing any permanent chemical change, facilitates or enables a reaction between other substances. Cetane Number Measure of fuel ignition characteristics. Like the octane number used for gasoline, the higher the value, the better the fuel performance. A higher cetane number correlates with improved combustion, improved cold starting, reduced noise, white smoke, HC, CO and particulate emissions particularly during early warm-up phase. The EPA uses this parameter as a measure of aromatic content in fuel. Typical Cetane numbers around the world are as follows: Europe: 43 - 57, average 50 U.S. lower, minimum 40, average 43.
Cloud Point The Cloud Point is the temperature at which, under test conditions similar to those of the Pour Point test, the sample ﬁrst exhibits a haziness or cloud due to the separation of minute wax crystals. Colloid A stable system of small particles dispersed in something else. A multi-phase system in which one dimension of a dispersed phase is of colloidal size. Colloids are the liquid and solid forms of aerosols, foams, emulsions, and suspensions within the colloidal size class. Milk and smoke are both colloids. Colloidal size is typically 001 micron to 1 micron in any dimension. Dispersions where the particle size is in this range are referred to as colloidal aerosols, colloidal emulsions, colloidal foams, or colloidal suspensions. Emulsion A usually unstable dispersion of two liquids which do not normally mix (they are immiscible). Emulsions can be formed either by mechanical agitation, or by chemical processes. Unstable emulsions will separate over time or temperature, stable emulsions will not separate. Ester A classiﬁcation of organic compounds occurring naturally as oils and fats, produced by replacing the hydrogen of an acid by an alkyl, aryl, radical. A compound of an organic acid bonded via an ester bond to an alcohol. Any of a large group of organic compounds formed when an acid and alcohol is mixed. CH3COOCH3 (Methyl Acetate) is the simplest ester. Biodiesel is often described as a Fatty Acid Methyl Ester (FAME). Ethanol C2H6O or CH3-CH2-OH - An organic alcohol also called ethyl alcohol, formed when fermenting sugars or glycerine. Ethanol is also a great solvent.
Lower Explosivity Limit The lower explosive limit (LEL) of a ﬂammable liquid is deﬁned as the minimum concentration of the vapour in air for which a ﬂame can propagate. The Methanol LEL is 6% by volume. FAME Fatty Acid Methyl Ester, a commonly used chemical term for Biodiesel. Fat A classiﬁcation of natural Esters of glycerol, and fatty acids existing as solids at room temperature. Fatty Acid A carboxylic acid (or organic acid), often with a long aliphatic tail (long chains), either saturated or unsaturated. Flash Point The lowest temperature at which it can form an ignitable mix with air. Free Fatty Acids Fatty acid hydrocarbon chains detached from other molecules, like glycerol. Hydrocarbon A compound of hydrogen and carbon, often occurring as long atomic chains in which each carbon atom is attached to two hydrogen atoms forming a long chain. They store a great deal of energy.
Hydrogenation A chemical reaction in which unsaturated bonds between carbon atoms are reduced by attachment of a hydrogen atom to each carbon. When the process is carried to completion it converts unsaturated fatty acids to saturated ones. Changing the degree of saturation of the fat changes important physical properties such as melting point, which is why the liquids become semisolid. Since partially hydrogenated Vegetable Oils are much less expensive than most other fats with similar characteristics, and because they have other desirable characteristics leading to longer shelf life, they are the predominant fat used in most commercial baked goods. Hygroscopic The tendency of something to absorb water (usually from humidity in the air). Biodiesel absorbs water to about 1200 parts per million (PPM). Methanol and KOH are also hygroscopic. Keep containers closed. Indicator A substance which changes colour at a given stage as a result of a chemical reaction. Phenolphthalein is commonly used in titration measuring the acidity of WVO. Iodine Number Standard natural oil assay to measure the degree of unsaturation (or the number of double bonds present) in Vegetable Oils and fats. Life-cycle analysis A total valuation of a process, in which all the inputs and outcomes of a reaction are fully considered.
Lipid A classiﬁcation of organic compounds, including fatty acids, oils, waxes and steroids, that are insoluble in water but soluble in organic solvents. They consist of a polar head with one to three non polar tails. A triglyceride is a type of lipid, the glycerine being the head and the ester chains being the tails. Methanol CH3OH - A volatile colourless alcohol, derived originally as wood alcohol, used as a racing fuel and as a solvent. Also called methyl alcohol. Lethal if consumed. Used to make Methoxide in Biodiesel production. Methanol absorbs water from the air, so keep the container closed tightly, and purchase Methanol which is known to be dry (anhydrous) or is 99.9% pure. Oxidation Burning in oxygen, normally highly exothermic (heat releasing), but also any increase in oxidisation state, (i.e. loss of electrons). Results in the formation of an oxide, rusting or corroding. Various materials, such as copper and brass, may oxidise in the presence of vegetable oil or Biodiesel. pH A measure of acidity and alkalinity of a solution on a scale with 7 representing neutrality. Lower numbers indicate increasing acidity, and higher numbers increasing alkalinity. Each unit of change represents a tenfold change in acidity or alkalinity. pH is mathematically found by taking the negative logarithm of the effective hydrogen-ion concentration or hydrogen-ion activity. The units are gram equivalents per litre of the solution.
Pour Point The low temperature ﬂow characteristics of lubricating oil are measured by a Pour Point test. The Pour Point refers to the lowest temperature at which the oil will ﬂow under speciﬁed conditions. The test is carried out by putting a small quantity of oil into a tube of standard size, which is then placed in a refrigerated bath. A thermometer is placed in the oil and the tube is tilted at regular intervals. The lowest temperature at which the oil continues to ﬂow is called the “Pour Point”. Rape Seed Oil A vegetable oil produced from rape seed. Used mainly in Europe to make Biodiesel. Saponiﬁcation The reaction of an ester with a metallic base and water. The making of soap. This happens sometimes when you use too much Sodium Hydroxide (NaOH) in a Biodiesel reaction... No worries - you can re-react the resulting top layer of unreacted liquid, and if you wish you can turn the semi-solid bottom layer into soap by adding more Sodium Hydroxide (NaOH) (make sure you know how much to add...). Saturated A fat or fatty acid in which there are no double bonds between the carbon atoms of the fatty acid chain. Saturated fats tend to be solid at room temperature. Sodium Hydroxide Sodium Hydroxide (NaOH). Strongly alkaline and extremely corrosive. Mixing with ﬂuids usually causes heat, and can create enough heat to ignite ﬂammables (such as Methanol), so add slowly. For Biodiesel, this is one of the main reactants. Make sure you are purchasing "anhydrous Sodium Hydroxide." Anhydrous means it's dry, and water turns Biodiesel into soap. Store this product in an airtight container to prevent KOH from absorbing water and CO2 from the air. Store separately.
Sodium Methoxide An organic salt, in pure form a white powder. In Biodiesel production, "Sodium Methoxide" is a product of mixing Methanol and Sodium Hydroxide , yielding a solution of Sodium Methoxide. Sodium Methoxide is a liquid that kills nerve cells before you can feel the pain. Rinse with water and seek medical attention immediately. Also highly explosive. Making Sodium Methoxide is the most dangerous step when making Biodiesel. Carefully consider the safety of the design of your equipment and workspace before producing, and wear protective clothing and a respirator when handling. Use immediately as Sodium Methoxide loses reactive properties with time. Suspension A dispersion of a solid in a gas, liquid, or solid Tallow One of the harder organic fats derived from animal carcasses, made by rendering the internal body fat found within the abdominal cavity under the backbone and surrounding the kidneys. This material was greatly used in manufacture of soap and candle wax. Transesteriﬁcation The process of making Biodiesel by the separation of the three hydrocarbon chains from a lipid triglyceride to form glycerol, and Biodiesel. It is the process of exchanging the alkyl group of an ester by another alcohol. These reactions are often catalysed by the addition of an acid or base. Acids can catalyse the reaction by donating an electron to the alkyl group, thus making it more reactive, while bases can catalyse the reaction by removing an electron from the alcohol, thus making it more reactive. Triglyceride Natural fats and oils, composed of glycerine and three fatty acid chains.
ULSD Ultra Low Sulphur Diesel. A type of diesel fuel promoted in recent years in an attempt to reduce atmospheric pollution but at the expense of engine wear. Unsaturated A fat or fatty acid containing double or occasionally triple bonds. Many Vegetable Oils contain Fatty Acids with one of more double bonds in them. Fat molecules are monounsaturated if each contains one double bond, and polyunsaturated if each contain more than one. Viscosity The viscosity of a ﬂuid is a measure of the resistance to ﬂow. Viscosity Index Viscosity Index (VI) is a measure of the change in viscosity of an oil with temperature. Higher VI indicates a smaller decrease in viscosity as the temperature is increased. VI is calculated from the kinematic viscosity of oil at 40 and 100°C. WVO Waste Vegetable Oil. The oil we collect from restaurants and Fish & Chips shops.
Test batches Whenever you're trying a new method, it's always a good idea to make small test batches of a litre or less ﬁrst to familiarise yourself with the process before moving on to bigger batches. Most people use kitchen blenders for this -- but don't use it for food again afterwards!
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