Bio Voyager

Biodiesel refers to a non-petroleum-based diesel fuel consisting of short chain alkyl (methyl or ethyl) esters, made by transesterification of vegetable oils or animal fats, which can be used (alone, or blended with conventional petrodiesel) in unmodified diesel-engine vehicles. Biodiesel is distinguished from the straight vegetable oil (SVO) (aka "waste vegetable oil", "WVO", "unwashed biodiesel", "pure plant oil", "PPO") used (alone, or blended) as fuels in some converted diesel vehicles. "Biodiesel" is standardized as mono-alkyl ester and other kinds of diesel-grade fuels of biological origin are not included.

Bus run by biodiesel 

Blends

Blends of biodiesel and conventional hydrocarbon-based diesel are products most commonly distributed for use in the retail diesel fuel marketplace. Much of the world uses a system known as the "B" factor to state the amount of biodiesel in any fuel mix: fuel containing 20% biodiesel is labeled B20, while pure biodiesel is referred to as B100. It is common to see B99, since 1% petrodiesel is sufficiently toxic to retard mold. Blends of 20 percent biodiesel with 80 percent petroleum diesel (B20) can generally be used in unmodified diesel engines. Biodiesel can also be used in its pure form (B100), but may require certain engine modifications to avoid maintenance and performance problems. Blending B100 with petro diesel may be accomplished by:

• Mixing in tanks at manufacturing point prior to delivery to tanker truck
• Splash mixing in the tanker truck (adding specific percentages of Biodiesel and Petro Diesel)
• In-line mixing, two components arrive at tanker truck simultaneously.

Origin

On August 31, 1937, G. Chavanne of the University of Brussels (Belgium) was granted a patent for a 'Procedure for the transformation of vegetable oils for their uses as fuels' (fr. 'Procédé de Transformation d’Huiles Végétales en Vue de Leur Utilisation comme Carburants') Belgian Patent 422,877. This patent described the alcoholysis (often referred to as transesterification) of vegetable oils using ethanol (and mentions methanol) in order to separate the fatty acids from the glycerol by replacing the glycerol with short linear alcohols. This appears to be the first account of the production of what is known as 'biodiesel' today.^[2]

Applications

Biodiesel can be used in pure form (B100) or may be blended with petroleum diesel at any concentration in most modern diesel engines. Biodiesel has different solvent properties than petrodiesel, and will degrade natural rubber gaskets and hoses in vehicles (mostly found in vehicles manufactured before 1992), although these tend to wear out naturally and most likely will have already been replaced with FKM, which is nonreactive to biodiesel. Biodiesel has been known to break down deposits of residue in the fuel lines where petrodiesel has been used.^[3] As a result, fuel filters may become clogged with particulates if a quick transition to pure biodiesel is made. Therefore, it is recommended to change the fuel filters on engines and heaters shortly after first switching to a biodiesel blend.^{[citation needed]}

Distribution

Biodiesel use and production are increasing rapidly. Fueling stations make biodiesel readily available to consumers across Europe, and increasingly in the USA and Canada. A growing number of transport fleets use it as an additive in their fuel. Biodiesel is often more expensive to purchase than petroleum diesel but this is expected to diminish due to economies of scale and agricultural subsidies versus the rising cost of petroleum as reserves are depleted.

Vehicular use and manufacturer acceptance

In 2005, DaimlerChrysler released Jeep Liberty CRD diesels from the factory into the American market with 5% biodiesel blends, indicating at least partial acceptance of biodiesel as an acceptable diesel fuel additive.^[4] In 2007, DiamlerChrysler indicated intention to increase warranty coverage to 20% biodiesel blends if biofuel quality in the United States can be standardized.^[5]

Railroad use

The British businessman Richard Branson's Virgin Voyager train, number 220007 Thames Voyager ^[6], billed as the world's first "biodiesel train" was converted to run on 80% petrodiesel and only 20% biodiesel, and it is claimed it will save 14% on direct emissions.

Aircraft use

Aircraft manufacturers are understandably even more cautious, but a test flight has been performed by an ex Soviet Aircraft (completely powered on biofuel);^[7] testing has been announced by Rolls Royce plc, Air New Zealand and Boeing (one engine out of four on a Boeing 747);^[8] and commercial passenger jet testing has also been announced^[9] by Virgin Atlantic's Richard Branson.

The world's first biofuel-powered commercial aircraft took off from London's Heathrow Airport on February 24, 2008 and touched down in Amsterdam on a demonstration flight hailed as a first step towards "cleaner" flying. The "BioJet" fuel for this flight was produced by Seattle based Imperium Renewables, Inc.^[10]

As a heating oil

Biodiesel can also be used as a heating fuel in domestic and commercial boilers, sometimes known as bioheat. Older furnaces may contain rubber parts that would be affected by biodiesel's solvent properties, but can otherwise burn biodiesel without any conversion required. Care must be taken at first, however, given that varnishes left behind by petrodiesel will be released and can clog pipes- fuel filtering and prompt filter replacement is required. Another approach is to start using biodiesel as blend, and decreasing the petroleum proportion over time can allow the varnishes to come off more gradually and be less likely to clog. Thanks to its strong solvent properties, however, the furnace is cleaned out and generally becomes more efficient. A technical research paper ^[11] describes laboratory research and field trials project using pure biodiesel and biodiesel blends as a heating fuel in oil fired boilers. During the Biodiesel Expo 2006 in the UK, Andrew J. Robertson presented his biodiesel heating oil research from his technical paper and suggested that B20 biodiesel could reduce UK household CO₂ emissions by 1.5 million tonnes per year

Historical background

Transesterification of a vegetable oil was conducted as early as 1853 by scientists E. Duffy and J. Patrick, many years before the first diesel engine became functional. Rudolf Diesel's prime model, a single 10 ft (3 m) iron cylinder with a flywheel at its base, ran on its own power for the first time in Augsburg, Germany, on August 10, 1893. In remembrance of this event, August 10 has been declared "International Biodiesel Day".

Rudolf Diesel demonstrated a Diesel engine running on peanut oil (at the request of the French government) built by the French Otto Company at the World Fair in Paris, France in 1900, where it received the Grand Prix (highest prize). ^[12]

This engine stood as an example of Diesel's vision because it was powered by peanut oil — a biofuel, though not biodiesel, since it was not transesterified. He believed that the utilization of biomass fuel was the real future of his engine. In a 1912 speech Diesel said, "the use of vegetable oils for engine fuels may seem insignificant today but such oils may become, in the course of time, as important as petroleum and the coal-tar products of the present time."

During the 1920's, diesel engine manufacturers altered their engines to utilize the lower viscosity of petrodiesel (a fossil fuel), rather than vegetable oil (a biomass fuel). The petroleum industries were able to make inroads in fuel markets because their fuel was much cheaper to produce than the biomass alternatives. The result, for many years, was a near elimination of the biomass fuel production infrastructure. Only recently, have environmental impact concerns and a decreasing price differential made biomass fuels such as biodiesel a growing alternative.

Despite the widespread use of fossil petroleum-derived diesel fuels, interest in vegetable oils as fuels in internal combustion engines is reported in several countries during the 1920's and 1930's and later during World War II. Belgium, France, Italy, the United Kingdom, Portugal, Germany, Brazil, Argentina, Japan and China have been reported to have tested and used vegetable oils as diesel fuels during this time. Some operational problems were reported due to the high viscosity of vegetable oils compared to petroleum diesel fuel, which result in poor atomization of the fuel in the fuel spray and often leads to deposits and coking of the injectors, combustion chamber and valves. Attempts to overcome these problems included heating of the vegetable oil, blending it with petroleum-derived diesel fuel or ethanol, pyrolysis and cracking of the oils.

On August 31, 1937, G. Chavanne of the University of Brussels (Belgium) was granted a patent for a "Procedure for the transformation of vegetable oils for their uses as fuels" (fr. 'Procédé de Transformation d’Huiles Végétales en Vue de Leur Utilisation comme Carburants') Belgian Patent 422,877. This patent described the alcoholysis (often referred to as transesterification) of vegetable oils using methanol and ethanol in order to separate the fatty acids from the glycerol by replacing the glycerol by short linear alcohols. This appears to be the first account of the production of what is known as "biodiesel" today.

More recently, in 1977, Brazilian scientist Expedito Parente produced biodiesel using transesterification with ethanol, and again filed a patent for the same process. This process is classified as biodiesel by international norms, conferring a "standardized identity and quality. No other proposed biofuel has been validated by the motor industry."^[13] Currently, Parente's company Tecbio is working with Boeing and NASA to certify bioquerosene (bio-kerosene), another product produced and patented by the Brazilian scientist.^[14]

Research into the use of transesterified sunflower oil, and refining it to diesel fuel standards, was initiated in South Africa in 1979. By 1983, the process for producing fuel-quality, engine-tested biodiesel was completed and published internationally.^[15] An Austrian company, Gaskoks, obtained the technology from the South African Agricultural Engineers; the company erected the first biodiesel pilot plant in November 1987, and the first industrial-scale plant in April 1989 (with a capacity of 30,000 tons of rapeseed per annum).

Throughout the 1990s, plants were opened in many European countries, including the Czech Republic, Germany and Sweden. France launched local production of biodiesel fuel (referred to as diester) from rapeseed oil, which is mixed into regular diesel fuel at a level of 5%, and into the diesel fuel used by some captive fleets (e.g. public transportation) at a level of 30%. Renault, Peugeot and other manufacturers have certified truck engines for use with up to that level of partial biodiesel; experiments with 50% biodiesel are underway. During the same period, nations in other parts of the world also saw local production of biodiesel starting up: by 1998, the Austrian Biofuels Institute had identified 21 countries with commercial biodiesel projects. 100% Biodiesel is now available at many normal service stations across Europe.

In September 2005 Minnesota became the first U.S. state to mandate that all diesel fuel sold in the state contain part biodiesel, requiring a content of at least 2% biodiesel.^[16]

 Properties

Biodiesel has better lubricity than that of today's diesel fuels. During the manufacture of these, to comply with low SO₂ engine emission limits set in modern standards, severe hydrotreatment is included. Biodiesel addition reduces wear^[17] increasing the life of the fuel injection equipment that relies on the fuel for its lubrication, such as high pressure injection pumps, pump injectors (also called unit injectors) and fuel injectors.

Older diesel Mercedes are popular for running on biodiesel.

The volumetric energy density of biodiesel is about 33 MJ/L. This is 9 % lower than regular Number 2 petrodiesel. Variations in biodiesel energy density is more dependent on the feedstock used than the production process. Still these variations are less than for petrodiesel.^[18] It has been claimed biodiesel gives better lubricity and more complete combustion thus increasing the engine energy output and partially compensating for the higher energy density of petrodiesel.^[19]

Biodiesel is a liquid which varies in color — between golden and dark brown — depending on the production feedstock. It is immiscible with water, has a high boiling point and low vapor pressure. *The flash point of biodiesel (>130 °C, >266 °F)^[20] is significantly higher than that of petroleum diesel (64 °C, 147 °F) or gasoline (−45 °C, -52 °F). Biodiesel has a density of ~ 0.88 g/cm³, less than that of water.

Biodiesel has a viscosity similar to petrodiesel, the current industry term for diesel produced from petroleum. Biodiesel has high lubricity and virtually no sulfur content, and it is often used as an additive to Ultra-Low Sulfur Diesel (ULSD) fuel.

Technical standards

Biodiesel sample

The European standard for biodiesel is EN 14214, which is translated into the respective national standards for each country that forms the CEN (European Committee for Standardization) area e.g., for the United Kingdom, BS EN 14214 and for Germany DIN EN 14214. It may be used outside the CEN area as well.

There are other national specifications. ASTM D6751 is the most common standard referenced in the United States and Canada.
There are also DIN standards for three different varieties of biodiesel, which are made of different oils:

• RME (rapeseed methyl ester, according to DIN E 51606)
• PME (vegetable methyl ester, purely vegetable products, according to DIN E 51606)
• FME (fat methyl ester, vegetable and animal products, according to DIN V 51606)

The standards ensure that the following important factors in the fuel production process are satisfied:

• Acid value
• Complete reaction.
• Removal of glycerin.
• Removal of catalyst.
• Removal of alcohol.
• Absence of free fatty acids.
• Low sulfur content.
• Cold Filter Plugging point
• Cloud Point

Basic industrial tests to determine whether the products conform to the standards typically include gas chromatography, a test that verifies only the more important of the variables above. Tests that are more complete are more expensive. Fuel meeting the quality standards is very non-toxic, with a toxicity rating (LD₅₀) of greater than 50 mL/kg.

 Gelling

The cloud point, or temperature at which pure (B100) biodiesel starts to gel, varies significantly and depends upon the mix of esters and therefore the feedstock oil used to produce the biodiesel. For example, biodiesel produced from low erucic acid varieties of canola seed (RME) starts to gel at approximately −10 °C (14 °F). Biodiesel produced from tallow tends to gel at around +16 °C (61 °F). As of 2006, there are a very limited number of products that will significantly lower the gel point of straight biodiesel. A study carried out by Assiniboine Community College in Manitoba Canada managed to produce B100 biodiesel that was a clear flowing liquid at -38° by using a commercially available additive, Wintron XC30, in addition to low temperature filtration.^{[citation needed]} A number of studies have shown that winter operation is possible with biodiesel blended with other fuel oils including #2 low sulfur diesel fuel and #1 diesel / kerosene. The exact blend depends on the operating environment: successful operations have run using a 65% LS #2, 30% K #1, and 5% bio blend. Other areas have run a 70% Low Sulfur #2, 20% Kerosene #1, and 10% bio blend or an 80% K#1, and 20% biodiesel blend. According to the National Biodiesel Board (NBB), B20 (20% biodiesel, 80% petrodiesel) does not need any treatment in addition to what is already taken with petrodiesel.

To permit the use of biodiesel without mixing and without the possibility of gelling at low temperatures, some people modify their vehicles with a second fuel tank for biodiesel in addition to the standard fuel tank. Alternately, a vehicle with two tanks is chosen. The second fuel tank is insulated and a heating coil using engine coolant is run through the tank. When a temperature sensor indicates that the fuel is warm enough to burn, the driver switches from the petrodiesel tank to the biodiesel tank. This is similar to the method used for running straight vegetable oil.

Contamination by water

Biodiesel may contain small but problematic quantities of water. Although it is hydrophobic (non-miscible with water molecules), it is said to be, at the same time, hygroscopic to the point of attracting water molecules from atmospheric moisture^[21]; one of the reasons biodiesel can absorb water is the persistence of mono and diglycerides left over from an incomplete reaction. These molecules can act as an emulsifier, allowing water to mix with the biodiesel.^{[citation needed]} In addition, there may be water that is residual to processing or resulting from storage tank condensation. The presence of water is a problem because:

• Water reduces the heat of combustion of the bulk fuel. This means more smoke, harder starting, less power.
• Water causes corrosion of vital fuel system components: fuel pumps, injector pumps, fuel lines, etc.
• Water & microbes cause the paper element filters in the system to fail ( rot), which in turn results in premature failure of the fuel pump due to ingestion of large particles.
• Water freezes to form ice crystals near 0 °C (32 °F). These crystals provide sites for nucleation and accelerate the gelling of the residual fuel.
• Water accelerates the growth of microbe colonies, which can plug up a fuel system. Biodiesel users who have heated fuel tanks therefore face a year-round microbe problem.
• Additionally, water can cause pitting in the pistons on a diesel engine.

Previously, the amount of water contaminating biodiesel has been difficult to measure by taking samples, since water and oil separate. However, it is now possible to measure the water content using water-in-oil sensors.

Availability and prices

In some countries biodiesel is less expensive than conventional diesel.

Global biodiesel production reached 3.8 million tons in 2005. Approximately 85% of biodiesel production came from the European Union.

In the United States, average retail (at the pump) prices, including Federal and state motor taxes, of B2/B5 are lower than petroleum diesel by about 12 cents, and B20 blends are the same as petrodiesel.^[22] B99 and B100 generally cost more than petrodiesel except where local governments provide a subsidy.

Production

Biodiesel is commonly produced by the transesterification of the vegetable oil or animal fat feedstock. There are several methods for carrying out this transesterification reaction including the common batch process, supercritical processes, ultrasonic methods, and even microwave methods.

Chemically, transesterified biodiesel comprises a mix of mono-alkyl esters of long chain fatty acids. The most common form uses methanol (converted to sodium methoxide) to produce methyl esters as it is the cheapest alcohol available, though ethanol can be used to produce an ethyl ester biodiesel and higher alcohols such as isopropanol and butanol have also been used. Using alcohols of higher molecular weights improves the cold flow properties of the resulting ester, at the cost of a less efficient transesterification reaction. A lipid transesterification production process is used to convert the base oil to the desired esters. Any Free fatty acids (FFAs) in the base oil are either converted to soap and removed from the process, or they are esterified (yielding more biodiesel) using an acidic catalyst. After this processing, unlike straight vegetable oil, biodiesel has combustion properties very similar to those of petroleum diesel, and can replace it in most current uses.

A byproduct of the transesterification process is the production of glycerol. For every 1 tonne of biodiesel that is manufactured, 100 kg of glycerol are produced. Originally, there was a valuable market for the glycerol, which assisted the economics of the process as a whole. However, with the increase in global biodiesel production, the market price for this crude glycerol (containing 20% water and catalyst residues) has crashed. Research is being conducted globally to use this glycerol as a chemical building block. One initiative in the UK is The Glycerol Challenge.

Usually this crude glycerol has to be purified, typically by performing vacuum distillation. This is rather energy intensive. The refined glycerol (98%+ purity) can then be utilised directly, or converted into other products. The following announcements were made in 2007: A joint venture of Ashland Inc. and Cargill announced plans to make propylene glycol in Europe from glycerol^[23] and Dow Chemical announced similar plans for North America.^[24] Dow also plans to build a plant in China to make epichlorhydrin from