Biodiesel

Biodiesel refers to a vegetable oil- or animal fat-based diesel fuel consisting of long-chain alkyl (methyl, propyl or ethyl) esters. Biodiesel is typically made by chemically reacting lipids (e.g., vegetable oil, animal fat (tallow^[1][2])) with an alcohol producing fatty acid esters.
Biodiesel is meant to be used in standard diesel engines and is thus distinct from the vegetable and waste oils used to fuel converted diesel engines. Biodiesel can be used alone, or blended with petrodiesel. Biodiesel can also be used as a low carbon alternative to heating oil.

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.^{[citation needed]} 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 10 August 1893 running on nothing but peanut oil. In remembrance of this event, 10 August has been declared "International Biodiesel Day".^{[citation needed]}

·         It is often reported that Diesel designed his engine to run on peanut oil, but this is not the case. Diesel stated in his published papers, "at the Paris Exhibition in 1900 (Exposition Universelle) there was shown by the Otto Company a small Diesel engine, which, at the request of the French government ran on arachide (earth-nut or pea-nut) oil (see biodiesel), and worked so smoothly that only a few people were aware of it. The engine was constructed for using mineral oil, and was then worked on vegetable oil without any alterations being made. The French Government at the time thought of testing the applicability to power production of the Arachide, or earth-nut, which grows in considerable quantities in their African colonies, and can easily be cultivated there." Diesel himself later conducted related tests and appeared supportive of the idea.^[28] 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."

·         Despite the widespread use of petroleum-derived diesel fuels, interest in vegetable oils as fuels for internal combustion engines was reported in several countries during the 1920s and 1930s and later during World War II. Belgium, France, Italy, the United Kingdom, Portugal, Germany, Brazil, Argentina, Japan and China were 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 results 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 31 August 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.^[29]

·         More recently, in 1977, Brazilian scientist Expedito Parente invented and submitted for patent, the first industrial process for the production of biodiesel.^[30] 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."^[31] As of 2010, Parente's company Tecbio is working with Boeing and NASA to certify bioquerosene (bio-kerosene), another product produced and patented by the Brazilian scientist.^[32]

·         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.^[33] 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.

Applications

Biodiesel can be used in pure form (B100) or may be blended with petroleum diesel at any concentration in most injection pump diesel engines. New extreme high-pressure (29,000 psi) common rail engines have strict factory limits of B5 or B20, depending on manufacturer.^{[citation needed]} Biodiesel has different solvent properties than petrodiesel, and will degrade natural rubber gaskets and hoses in vehicles (mostly 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.^[8] 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.^[9

Vehicular use and manufacturer acceptance

In 2005, Chrysler (then part of DaimlerChrysler) released the 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.^[11] In 2007, DaimlerChrysler indicated its intention to increase warranty coverage to 20% biodiesel blends if biofuel quality in the United States can be standardized.^[12]
The Volkswagen Group has released a statement indicating that several of its vehicles are compatible with B5 and B100 made from rape seed oil and compatible with the EN 14214 standard. The use of the specified biodiesel type in its cars will not void any warranty.^[13]
Mercedes Benz does not allow diesel fuels containing greater than 5% biodiesel (B5) due to concerns about "production shortcomings".^[14] Any damages caused by the use of such non-approved fuels will not be covered by the Mercedes-Benz Limited Warranty.
Starting in 2004, the city of Halifax, Nova Scotia decided to update its bus system to allow the fleet of city buses to run entirely on a fish-oil based biodiesel. This caused the city some initial mechanical issues, but after several years of refining, the entire fleet had successfully been converted.^[15][16]
In 2007, McDonalds of UK announced it would start producing biodiesel from the waste oil byproduct of its restaurants. This fuel would be used to run its fleet.^[17]

Railway usage

British train operating company Virgin Trains claimed to have run the UK's first "biodiesel train", which was converted to run on 80% petrodiesel and 20% biodiesel.^[18]
The Royal Train on 15 September 2007 completed its first ever journey run on 100% biodiesel fuel supplied by Green Fuels Ltd. His Royal Highness, The Prince of Wales, and Green Fuels managing director, James Hygate, were the first passengers on a train fueled entirely by biodiesel fuel. Since 2007, the Royal Train has operated successfully on B100 (100% biodiesel).^[19]
Similarly, a state-owned short-line railroad in eastern Washington ran a test of a 25% biodiesel / 75% petrodiesel blend during the summer of 2008, purchasing fuel from a biodiesel producer sited along the railroad tracks.^[20] The train will be powered by biodiesel made in part from canola grown in agricultural regions through which the short line runs.
Also in 2007, Disneyland began running the park trains on B98 (98% biodiesel). The program was discontinued in 2008 due to storage issues, but in January 2009, it was announced that the park would then be running all trains on biodiesel manufactured from its own used cooking oils. This is a change from running the trains on soy-based biodiesel.^[21]

Aircraft use

A test flight has been performed by a Czech jet aircraft completely powered on biodiesel.^[22] Other recent jet flights using biofuel, however, have been using other types of renewable fuels.
On November 7, 2011 United Airlines flew the world's first commercial aviation flight on a microbially derived biofuel using Solajet™, Solazyme's algae-derived renewable jet fuel. The Eco-skies Boeing 737-800 plane was fueled with 40 percent Solajet and 60 percent petroleum-derived jet fuel. The commercial Eco-skies flight 1403 departed from Houston's IAH airport at 10:30 and landed at Chicago's ORD airport at 13:03.^[23]

As a heating oil

Main article: Bioliquids

Biodiesel can also be used as a heating fuel in domestic and commercial boilers, a mix of heating oil and biofuel which is standardized and taxed slightly differently than diesel fuel used for transportation. It is sometimes known as "bioheat" (which is a registered trademark of the National Biodiesel Board [NBB] and the National Oilheat Research Alliance [NORA] in the U.S., and Columbia Fuels in Canada).^[24] Heating biodiesel is available in various blends. ASTM 396 recognizes blends of up to 5 percent biodiesel as equivalent to pure petroleum heating oil. Blends of higher levels of up to 20% biofuel are used by many consumers. Research is underway to determine whether such blends affect performance.
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, 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 a 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.^[25] A technical research paper^[26] 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 B20 biodiesel could reduce UK household CO₂ emissions by 1.5 million tons per year.
A law passed under Massachusetts Governor Deval Patrick requires all home heating diesel in that state to be 2% biofuel by July 1, 2010, and 5% biofuel by 2013.^[27] New York City has passed a similar law.

Production methods

Supercritical process

An alternative, catalyst-free method for transesterification uses supercritical methanol at high temperatures and pressures in a continuous process. In the supercritical state, the oil and methanol are in a single phase, and reaction occurs spontaneously and rapidly.^[4] The process can tolerate water in the feedstock, free fatty acids are converted to methyl esters instead of soap, so a wide variety of feedstocks can be used. Also the catalyst removal step is eliminated.^[5] High temperatures and pressures are required, but energy costs of production are similar or less than catalytic production routes.^[6]

Ultra- and high-shear in-line and batch reactors

Ultra- and High Shear in-line or batch reactors allow production of biodiesel continuously, semi- continuously, and in batch-mode. This drastically reduces production time and increases production volume.^{[citation needed]}
The reaction takes place in the high-energetic shear zone of the Ultra- and High Shear mixer by reducing the droplet size of the immiscible liquids such as oil or fats and methanol. Therefore, the smaller the droplet size the larger the surface area the faster the catalyst can react.

Ultrasonic reactor method

In the ultrasonic reactor method, the ultrasonic waves cause the reaction mixture to produce and collapse bubbles constantly. This cavitation provides simultaneously the mixing and heating required to carry out the transesterification process. Thus using an ultrasonic reactor for biodiesel production drastically reduces the reaction time, reaction temperatures, and energy input. Hence the process of transesterification can run inline rather than using the time consuming batch processing. Industrial scale ultrasonic devices allow for the industrial scale processing of several thousand barrels per day.^[7]

Lipase-catalyzed method

Large amounts of research have focused recently on the use of enzymes as a catalyst for the transesterification. Researchers have found that very good yields could be obtained from crude and used oils using lipases. The use of lipases makes the reaction less sensitive to high FFA content, which is a problem with the standard biodiesel process. One problem with the lipase reaction is that methanol cannot be used because it inactivates the lipase catalyst after one batch. However, if methyl acetate is used instead of methanol, the lipase is not in-activated and can be used for several batches, making the lipase system much more cost effective.^[8]