Biodiesel

Biodiesel is a renewable alternative fuel created from vegetable oils, animal fats, and greases through a chemical process. The chemical process involves reaction of natural oils with an alcohol, and then refining the mixture to create molecules which can be easily burned in a diesel engine. Biodiesel fuel can be used in any diesel engine in pure form or blended with petroleum diesel at any level. Even a blend of 20% bio- and 80% petroleum diesel will significantly reduce carcinogenic emissions and gases that may contribute to global warming. Glycerin is the byproduct of the biodiesel production process, and can be used in personal care products or a variety of chemical applications. What is Biodiesel Biodiesel is a clean burning renewable fuel made using natural vegetable oils and fats. Biodiesel is made through a chemical process which converts oils and fats of natural origin into fatty acid methyl esters (FAME). Biodiesel IS NOT vegetable oil. Biodiesel is intended to be used as a replacement for petroleum diesel fuel, or can be blended with petroleum diesel fuel in any proportion. Biodiesel does not require modifications to a diesel engine to be used. Biodiesel has reduced exhaust emissions compared to petroleum diesel fuel. Biodiesel has lower toxicity compared to petroleum diesel fuel. Biodiesel is safer to handle compared to petroleum diesel fuel. Biodiesel quality is governed by ASTM D 6751 quality parameters. Biodiesel is biodegradable. What is NOT Biodiesel Look Carefully! Many companies and groups improperly use the word biodiesel to describe diesel fuel replacement products they have developed. This creates significant confusion for consumers looking to purchase and use biodiesel. Some of these alternatives have not been properly tested and could lead to damage to vehicles. Below is some information to help distinguish real biodiesel from imposters.

What biodiesel IS NOT: Biodiesel is not vegetable oil. Biodiesel is not vegetable oil diluted with solvents, i.e. diesel fuel or alcohols. Biodiesel is not vegetable oil with special additives to make it run better. Biodiesel is not vegetable oil refined through a conventional oil refinery process. Biodiesel is not vegetable oil refined through thermal depolymerization (renewable diesel). Biodiesel is not a fuel that requires costly modifications to your diesel engine (straight vegetable oil). Biodiesel is not crude methyl esters which have not been refined or minimally refined. Unlike biodiesel, none of the fluids listed above have undergone renewable fuel certification, emissions or toxicity testing, or long-term reliability testing in engines and vehicles. How to Make Sure You are Getting Biodiesel In order to be called biodiesel and receive certain tax credits specifically intended for biodiesel: Biodiesel must be produced from naturally occurring fats and oils using transesterification. Biodiesel must be composed of fatty acid methyl esters. Biodiesel must be refined to remove all trace impurities. Biodiesel must meet the ASTM standard D6751-07b Specification for Biodiesel (B100). If a fuel product does not meet these requirements it IS NOT biodiesel, and does not qualify for tax credits relating to biodiesel. The most important thing to ask your fuel provider is if the biodiesel is ASTM certified.

Biodiesel Benefits Why Use Biodiesel The smartest technologies deliver benefits to multiple interests, including an improved economy, and a positive impact on the environment and governmental policies.

The role of the biodiesel industry is not to replace petroleum diesel, but to help create a balanced energy policy with the most benefit to the United States. Biodiesel is one of several alternative fuels designed to extend the usefulness of petroleum, and the longevity and cleanliness of diesel engines. The ultimate goal is to contribute to building a stronger, more self-sufficient community by way of a community-based biodiesel production model. A community-based biodiesel distribution program benefits local economies, from the farmers growing the feedstock to local businesses producing and distributing the fuel to the end consumer. The money stays in the community while reducing impact on the local environment and increasing energy security. Learn More The links below provide more in depth information on the benefits of biodiesel. Easy To Use No vehicle modifications or special fueling equipment just pump and go. Power, Performance and Economy Proven performance and economy make biodiesel a renewable winner. Emissions & Greenhouse Gas Reduction With lower exhaust emissions biodiesel is helping to reduce pollution and improve health. Lower CO2 emissions help reduce the impacts of global warming. Energy Balance & Security Biodiesel production and use at home, biodiesel helps reduce the need for foreign oil. Toxicity, Biodegradability, Safety & Recycling Less toxic than table salt, biodiesel has minimal environmental impact. With a high flash point, biodiesel is safer to handle and store than petroleum diesel. When made from used oils and fats, biodiesel helps ensure proper recycling of former waste products.

Economic Development Biodiesel helps communities by keeping energy dollars at home. Easy to Use One of the great advantages of biodiesel is that it can be used in existing engines, vehicles and infrastructure with practically no changes. Biodiesel can be pumped, stored and burned just like petroleum diesel fuel, and can be used pure, or in blends with petroleum diesel fuel in any proportion. Power and fuel economy using biodiesel is practically identical to petroleum diesel fuel, and year round operation can be achieved by blending with diesel fuel. Engine and Vehicles All diesel engines and vehicles can use biodiesel or biodiesel blends. Certain older vehicles built before 1993 may require replacement of fuel lines which contain natural rubber, as biodiesel can cause these lines to swell or crack. Blending and Switching with Diesel Fuel Biodiesel can be used 100% (B100) or in blends with petroleum diesel fuel. Blends are indicated by B##, which correspond to the percentage of biodiesel in the blended fuel. For example, a 20% blend of biodiesel with 80% diesel fuel is called B20. When biodiesel is first used in a vehicle, it may release fuel tank deposits which can lead to fuel filter plugging. After this initial period, a user can switch between biodiesel and petroleum diesel whenever needed or desired, without modification. Availability The presence of biodiesel pumps at fueling stations across the country grows daily. Power, Performance and Economy Many alternative fuels have difficulty gaining acceptance because they do not provide similar performance to their petroleum counterparts. Pure biodiesel and biodiesel blended with petroleum diesel fuel provide very similar horsepower, torque, and fuel mileage compared to petroleum diesel fuel. In its pure form, typical biodiesel will have an energy content 5%-10% lower than typical petroleum diesel. However it should be

noted that petroleum diesel fuel energy content can vary as much as 15% from one supplier to the next. The lower energy content of biodiesel translates into slightly reduced performance when biodiesel is used in 100% form, although users typically report little noticeable change in mileage or performance. When blended with petroleum diesel at B20 levels, there is less than 2% change in fuel energy content, with users typically reporting no noticeable change in mileage or economy. Superior Lubrication for Your Engine The injection system of many diesel engines relies on the fuel to lubricate its parts. The degree to which fuel provides proper lubrication is its lubricity. Low lubricity petroleum diesel fuel can cause premature failure of injection system components and decreased performance. Biodiesel provides excellent lubricity to the fuel injection system. Recently, with the introduction of low sulfur and ultra low sulfur diesel fuel, many of the compounds which previously provided lubricating properties to petrodiesel fuel have been removed. By blending biodiesel in amounts as little as 5%, the lubricity of ultra low sulfur diesel can be dramatically improved, and the life of an engines fuel injection system extended. Biodiesel in Cold Weather Just like petroleum diesel fuel, biodiesel can gel in cold weather. The best way to use biodiesel during the colder months is to blend it with winterized diesel fuel. Emissions & Greenhouse Gas reduction Biodiesel is the only alternative fuel to successfully complete the EPAs rigorous emissions and health effects study under the Clean Air Act. Biodiesel provides significantly reduced emissions of carbon monoxide, particulate matter, unburned hydrocarbons, and sulfates compared to petroleum diesel fuel. Additionally, biodiesel reduces emissions of carcinogenic compounds by as much as 85% compared with petrodiesel. When blended with petroleum diesel fuel, these emissions reductions are generally directly proportional to the amount of biodiesel in the blend. Close Contact Benefits from the French Fry Fuel

The reduced particulate and unburned hydrocarbons emissions that result when using biodiesel are a welcome relief in environments where workers and pedestrians are in close proximity to diesel engines, including public transport, mining, and construction. In addition, when high blends of biodiesel are used, the exhaust from diesel engines is often described as smelling like fried food, which aside from causing increased hunger in those nearby, is a welcome relief from the smell of diesel fuel exhaust. A Clean Alternative Fuel for New and Old Engines Diesel engines have long had a reputation of being dirty engines. However, with the advent of newer diesel engines equipped with exhaust gas recirculation (EGR), particulate filters, and catalytic converters, clean diesel technology provides incredible fuel efficiency with ultra low emissions levels. When coupled with the use of biodiesel, both new and old diesel engines can significantly reduce emissions, including particulate matter (black smoke). A Closer Look at Emissions Reduction Studies on biodiesel emissions have been conducted for almost 20 years. In that time biodiesel has undergone the most rigorous testing of any alternative fuel, having been the first and only fuel to be evaluated by the EPA under the Clean Air Act Section 211(b). This study examined the impact of hundreds of regulated and non-regulated exhaust emissions, as well as the potential health effects of these emissions. Some of these results are summarized below. Average Exhaust Emissions for 100% Biodiesel Compared to Petroleum Diesel Fuel* Regulated Exhaust Emissions B100 Particulate Matter Carbon Monoxide Nitrogen Oxides Sulfates -100% -90% -47% -48% -67% +/-

Total Unburned Hydrocarbons Non Regulated Emissions

Polycyclic Aromatic Hydrocarbons (PAH) -80% Nitrated Polycyclic Aromatic Hydrocarbons (nPAH)

Speciated Hydrocarbons Ozone Forming Potential -50% 4 A Comprehensive Analysis of Biodiesel Impacts on Exhaust Emissions, http://www.epa.gov/otaq/models/analysis/biodsl/p02001.pdf (This document requires Adobe Acrobat Reader, click here to download the latest version. Explanation of Emission Types Particulate Matter (Black Smoke) Emissions of particulate matter have been linked to respiratory diseases and are generally considered to be a human health hazard. Emissions of particulate matter are reduced with biodiesel by 47%. Carbon Monoxide Carbon Monoxide is a poisonous gas. Reduced with biodiesel by 48%. Total Unburned Hydrocarbons Compounds which contribute to localized formation of smog. Reduced with biodiesel by 67%. Nitrogen Oxides Compounds which contribute to localized formation of smog. According to NREL (Biodiesel Handling and Use Guidelines 2009 revision) examination of the NOx testing results shows that the effect of biodiesel can vary with engine design, calibration, and test cycle. At this time, the data are insufficient for users to conclude anything about the average effect of B20 on NOx, other than that it is likely very close to zero. Sulfates Sulfates are major contributors to acid rain. These emissions are practically eliminated when using biodiesel. Polycyclic Aromatic Hydrocarbons (PAH and nPAH) These compounds have been identified as carcinogenic (cancer causing) compounds. Biodiesel reduces emissions of these compounds by up to 85% for PAH compounds and 90% for nPAH compounds. Speciated Hydrocarbons These compounds contribute to the formation of localized smog and ozone. The potential for smog formation from speciated hydrocarbons is reduced by 50% when using biodiesel.

Life Cycle Reduction of CO2 Biodiesel helps reduce the risk of global warming by reducing net carbon emissions to the atmosphere. When biodiesel is burned, it releases carbon dioxide to the atmosphere, but crops which are used to produce biodiesel take up carbon dioxide from the atmosphere in their growth cycle. A joint study conducted by the U.S. Department of Agriculture, and the U.S. Department of Energy determined that biodiesel reduces net carbon dioxide emissions to the atmosphere by 78.5% compared with petroleum diesel fuel. Energy Balance and Security The energy balance of a fuel is a ratio of how much energy is required to produce, refine and distribute the fuel compared to the amount of energy the fuel releases when it is burned. This property is used to determine how renewable a fuel is. A higher ratio indicates a lower environmental impact, as less fossil energy is needed to produce, refine and distribute the fuel. Biodiesel has a very high energy balance compared to other alternative fuels. A joint study found that on average biodiesel releases 3.2 units of energy for every one unit of fossil fuel energy used to produce it*. For comparison, diesel fuel delivers only 0.83 units of energy for every unit of fossil fuel energy used to produce it. Grown, Produced and Distributed Locally Worldwide, energy security is becoming a hot topic in government and society. Nearly every country in the world depends on imports of various forms of fossil fuel energy, including oil, coal and natural gas. Without a steady supply of affordable energy a countrys economy grinds to a halt, with no fuel for transportation, energy to run power plants and factories, or heat homes. Biodiesel can improve energy security wherever it is produced in several ways: Domestic Energy Crops When crops used to produce biodiesel are grown in the country in which the fuel is consumed, each gallon of biodiesel displaces a gallon of imported crude oil, reducing a countrys dependence on foreign oil supplies.

Increased Refining Capacity Biodiesel is produced in dedicated refineries which add to overall domestic refining capacity, eliminating the need to import expensive finished product from other countries.

Difficult Targets When biodiesel is produced, distributed and used locally in a community based model it presents a much more difficult target for a potential terrorist attack than large centralized facilities like oil refineries or pipelines used in the petroleum industry. In the United States, the biodiesel industry is supported by the Energy Policy Act (EPAct) compliance strategy. This legislation allows EPAct-covered fleets (federal, state and public utility fleets) to meet their alternative fuel vehicle purchase requirements simply by buying 450 gallons of pure biodiesel, and burning it in new or existing diesel vehicles in at least a 20% blend with diesel fuel. The Congressional Budget Office and the U.S. Department of Agriculture have confirmed that the biodiesel option is the leastcost alternative fuel option for meeting the Federal governments EPAct compliance requirements. Toxicity, Biodegradability, Safety & Recycling Though it is uncommon for the average person to come into direct contact with fuels, occasional spills do occur, and the impact of the fuel on plants and animals must be considered. Biodiesel has been proven to be much less toxic than diesel fuel, and is readily biodegradable. These attributes make it less likely to harm the environment if an accidental spill occurred, and far less costly to repair damage and clean up. Less Toxic than Table Salt Being derived from vegetable oils, biodiesel is naturally non-toxic. The acute oral LD50 (lethal dose) of biodiesel is more than 17.4 g/Kg. By comparison table salt (NaCl) has an LD50 of 3.0g/Kg. This means that table salt is almost 6 times more toxic than biodiesel.

Aquatic Impacts In an aquatic environment, biodiesel is 15 times less toxic to common species of fish than diesel fuel. Biodegradability In both soil and water, biodiesel degraded at a rate 4 times faster than regular diesel fuel, with nearly 80% of the carbon in the fuel being readily converted by soil and water borne organisms in as little as 28 day. A Safe and Stable Fuel Biodiesel is safer to handle than petroleum fuel because of its low volatility. Due to the high energy content of all liquid fuels, there is a danger of accidental ignition when the fuel is being stored, transported, or transferred. The possibility of having an accidental ignition is related in part to the temperature at which the fuel will create enough vapors to ignite, known as the flash point temperature. The lower the flash point of a fuel is, the lower the temperature at which the fuel can form a combustible mixture. For example, gasoline has a flash point of -40 F, which means that gasoline can form a combustible mixture at temperatures as low as -40 F. Biodiesel on the other hand has a flash point of over 266 F, meaning it cannot form a combustible mixture until it is heated well above the boiling point of water. It is rare that fuel is subjected to these types of conditions, making biodiesel significantly safer to store, handle, and transport than petroleum diesel. In fact, the National Fire Protection Association classifies biodiesel as a non-flammable liquid. Recycling: Recovering Energy Resources Biodiesel can be made from many different oils and fats, including many waste products. Waste cooking oil, normally disposed of or used in animal feed mixtures can be converted to high quality biodiesel using a process employed by companies such as Pacific Biodiesel Technologies. The use of used cooking oils as a biodiesel feedstock has increased their value significantly in recent years, making proper collection and recycling of these oils more cost effective, and lowering the volume of these oils destined for sewers and landfills. Other low value oils and fats which can be made into biodiesel include yellow grease, inedible tallow, and trap grease. In one example of the benefits of how biodiesel production can increase recycling, the Pacific Biodiesel production

facilities in the Hawaiian islands have diverted nearly 190,000 tons of used cooking oil and grease trap waste since they began production. Economic Development Since biodiesel is a fuel which can be created from locally available resources, its production and use can provide a host of economic benefits for local communities. The community-based model of biodiesel production is particularly beneficial. In this model, locally available feedstocks are collected, converted to biodiesel, then distributed and used within the community. This model keeps energy dollars in the community instead of sending them to foreign oil producers and refineries outside the community. The peripheral benefits of this type of model are different for each case, but can include: Increased tax base from biodiesel production operations. Jobs created for feedstock farming and/or collection. Skilled jobs created for biodiesel production and distribution. Income for local feedstock producers and refiners. Sustainable Farming and Value Added Agriculture Biodiesel feedstock can come from a variety of agricultural crops. When these crops are grown in a sustainable manner, using good stewardship practices, there are long term benefits to farmers, farming communities and the land. Many crops which yield oils used for biodiesel production can be a beneficial rotation for other food crops, including soybeans when used in a traditional corn rotation, and canola when used in a wheat rotation. Using crops in rotation can improve soil health and reduce erosion. The overall impacts of growing energy crops are complex, with thousands of variables. However, the added value created for oilseed crops by the production of biodiesel is a tangible benefit for farming communities, and when coupled with sustainable farming practices can provide benefits to farming communities and the environment. Sustainable Biodiesel Production

Since there are multiple feedstocks from which to make biodiesel, plant operators can opt for the least expensive feedstock currently available, if they have a multiple-feedstock system. This flexibility makes producers less subject to price fluctuations. One example of this is noted by the prices of soybean oil. Its price has doubled in recent years, and is predicted to continue to rise according to a 2001 study by the U.S. Department of Agriculture. The study projects a total cash crop increase of $5.2 billion by 2010 an average net increase to farms of $300 million per year with soybean prices increasing 17 cents per bushel annually over that period. Everybody Wins Ultimately this creates multiple beneficiaries of the production of biodiesel. By virtue of a successful market and feedstock flexibility, plant operators and farmers can both continue to operate in a marketplace with increases in revenue projected to bring $24 billion to the U.S. by 2015. Process Technology Designed for Versatility Put our versatile, robust biodiesel technology at the heart of your enterprise to produce consistently high quality fuel at a competitive price. Since 1996 we have provided our customers with efficient and appropriately scaled technology to convert a multitude of fats, oils and greases, virgin and waste, into 100% high quality ASTM specification biodiesel. Our combination of real world production experience and robust process technology have made us a premier provider of biodiesel process systems and equipment to companies seeking to weather the ups and downs of volatile feedstock and fuel markets, while delivering the quality and consistency their customers demand. Get acquainted with the complete set of technology features and benefits only Pacific Bidodiesel offers to ensure success for your biodiesel enterprise.

Proven Experience for a Competitive Edge The greening of America and rising petroleum costs are spurring rapid growth for the biodiesel industry. As your proven partner, Pacific Biodiesel not only assures successful establishment of your operation, but gives you a competitive edge. Our decade of experience building and operating biodiesel plants insures that we will design and build for you the right size plant, with the right equipment, installed and brought on line on time and within budget. Since 1996, Pacific Biodiesel has owned and operated biodiesel plants utilizing multiple feedstocks including used cooking oil, yellow grease, brown grease, soybean oil, cottonseed oil, canola oil, and tallow. From the beginning, we have shared our technology and experience with customers in the United States and abroad. Our participation ranges from providing basic process systems to delivering turn-key biodiesel production facilities complete with management oversight and ongoing operational support. No other technology provider in the industry delivers this range of services, equipment, or support. The competence behind our commitment to plant owners and operators is firmly rooted in our own operational experience. Thats unique and valuable. Water-free Processing for State-of-the-Art Technology Through extensive research, Pacific Biodiesel Technologies has developed a unique biodiesel refining technology that uses no water and provides consistently high fuel quality. Our dry refining process is superior to water wash and ion exchange resin processes in both cost and efficiency at removing a multitude of trace contaminants which can negatively affect oxidative stability and cold weather performance. This process is standard in our biodiesel systems, and can be retrofit to any existing biodiesel plant. Multi-Feedstock Flexibility for Changing Markets To maximize profitability, biodiesel plants must be able to respond to market fluctuations in the price and availability of various feedstocks, with the flexibility to quickly transition from one feedstock to another. We provide a robust and adaptable process technology to meet these goals. Other plant manufacturers claim multi-feedstock capability, but glaze

over the critical details such as specifying which feedstocks are supported, in what proportions, and what are the resulting yields. Some companies will claim that used oils and greases can be used in their process, but they employ inappropriate process chemistry that can result in losses in efficiency that can exceed 30%. Pacific Biodiesels unique reaction technologies allow the use of up to 50% FFA feedstock without loss of yield. Our process is also designed to handle contaminants commonly found in used and unrefined oils and fats, but which competitors fail to mention as diminishing production factors.These include moisture, insoluble and inorganic impurities, excess unsaponifiable matter, and phospholipids. We have been processing used and unrefined oils and fats for more than a decade. No one provides more robust solutions for using multiple feedstocks to adapt to challenging market changes. Superior Fuel Quality for End-user Satisfaction We guarantee that our process plants will meet ASTM standards using a multitude of feedstocks. Pacific Biodiesels robust process chemistry and three-stage product refining produce a fuel with quality that is second to none. Our multi-stage reaction efficiently converts fatty acids and glycerides to methyl esters, while our vacuum distillation and dry refining steps remove trace amounts of water, methanol and minor impurities to yield a fuel with exceptional quality and a long shelf life. Quality Equipment for the Long Haul As producers, we understand the importance of avoiding downtime to make repairs. In biodiesel production, Inferior equipment is the primary cause. Our process equipment is constructed of stainless steel and with specially design elastomers for superior longevity and lower maintenance costs. The quality of our equipment in materials and manufacturing is backed by a blanket one-year warranty, with a five-year warranty on all process vessels. Extended warrantees are also available. One of the biggest mistakes a producer can make is choosing equipment that was not designed or built for a long service life under rigorous conditions. The use of low grade materials, including plastic vessel and pipe, not only falls short of profitable performance, but is unsafe. The use of

lower quality components and wear parts in competitors systems ignore the long-term maintenance and replacement costs. Designed for Safety Careful attention to safe operating practices is pervasive in the design of Pacific Biodiesel Technologies equipment. We apply the principles of intrinsically safe design whenever possible, and closely follow NFPA, ASME, and UL codes for all vessels, piping systems and electrical equipment. Pacific Biodiesel Technologies is committed to designing, engineering, and fabricating systems that enhance the safety and ergonomics of its biodiesel plants. High Yield Efficiency for the Bottom Line By employing precise reaction chemistry and proprietary ester and byproduct refining technologies, our process delivers the highest possible yield from any feedstock used. Many technology providers skirt the issue of yield losses inherent to traditional process chemistry, particularly the lack of proper equipment to treat and recover crude ester and byproduct streams. Our process is designed to recycle every drop of feedstock diverted in the production process and sized to ensure consistent output even through feedstock transitions. Complete Methanol Recovery for Reduced Costs A comprehensive approach to methanol recovery is essential to ensuring a competitive edge. Some technology providers claim to offer methanol recovery technology, but limit the process to recycling methanol from the biodiesel refining step, while the crude byproducts (glycerin) remain untreated. Their process actually results in a loss of methanol and produces a hazardous waste stream. Other biodiesel producers have turned to off the shelf distillation units, or to suppliers of methanol recovery equipment to other industries, often with poor results. Pacific Biodiesel Technologies process equipment recovers all excess methanol, and is specifically designed for the biodiesel production process. Careful attention is paid to specifying equipment and creating conditions that maintain high product quality during evaporation and distillation. The use

of our three-step recovery system keeps methanol consumption to the theoretical minimum while producing high quality co-products. 85% Glycerin Purity for Increased Revenue Pacific Biodiesel Technologies proprietary byproduct refining technology allows the recovery of 85%+ pure glycerin from the crude byproduct stream. The resulting glycerin is suitable for use as animal feed, is upgradeable to USP quality, or can be used in a multitude of other areas. Also, recycling excess methanol and feedstock residues into the process improves yield and lowers operating costs. Reduced Environmental Footprint for Sustainability A small environmental footprint is an essential aspect of a sustainable biodiesel facility. Our processes come standard with vapor recovery to eliminate fugitive emissions. The use of our proprietary dry refining process eliminates the use of water and creates a nonhazardous solid from product impurities. Methanol recovery from all process streams keeps methanol consumption to a minimum. Our facilities may be equipped with stateof-the-art cooling tower and boiler water treatment options to eliminate chemical use in these areas, also. [1] http://www.biodiesel.com/ BIODIESELUL Biodieselul reprezinta un carburant alternativ pentru motoarele de tip diesel al carui principal avantaj il reprezinta faptul ca este un carburant regenerabil, non-toxic si biodegradabil. Deasemenea poate fi utilizat in majoritatea motoarelor de tip diesel fara a fi necesare modificari ample ale acestora. Este obtinut in urma unor reactii chimice dintre lipide (de origine vegatala sau animala) cu un alcool in urma carora se obtin esteri ai acizilor grasi.

Procedeul de transesterificare al uleiurilor vegetale este cunoscut inca din anul 1853, un astfel de experiment fiind condus de catre cercetatorii E. Duffy si J. Patrick, cu multi ani inaintea aparitiei primului motor diesel. Posibilitatea folosirii uleiurilor vegetale pe post de combustibil pentru motorul cu combustie interna a fost studiata in mai multe tari in perioada 1920 1930 si mai tarziu in timpul celui de-al Doilea Razboi Mondial.Din cauza unor dificultati tehnice cum ar fi viscozitatea ridicata, incercarile de a inlocui motorina cu uleiul vegetal au fost in mare masura abandonate. Pe data de 31 august 1937 G. Chavanne in cadrul Universitatii din Bruxelles obtine patentul pentru Procedura de transformare a uleiurilor vegetale pentru folosirea lor drept combustibili, acesta descriind metoda de transesterificare a uleiurilor vegetale folosind etanol in scopul separarii acizilor grasi de glicerol inlocuind glicerolul cu alcooli liniari de catena scurta. Este prima mentionare a obtinerii a ceea ce definim in ziua de azi ca biodiesel. Mult mai recent, in 1977 cercetatorul Expedito Parente inventeaza si prezinta patentul pentru primul proces de obtinere la scara industriala a biodieselului. Pe parcursul anilor 90, uzine de obtinere a biodieselului au fost deschise in multe tari din Uniunea Europeana, incluzand Cehia, Germania si Suedia. Franta lanseaza productia locala de biodiesel din uleiul de rapita, ce intra intr-un amestec de 5% cu motorina in combustibilul pentru masini si intr-un procent mai mare in combustibilul destinat transportului public. Renault, Peugeot si alti producatori de masini au certificat moatoare de camioane ce pot folosi amestecuri de pana la 50%. In 1990 Institutul pentru Biocombustibili din Austria identifica 21 de tari cu proiecte de obtinere a biodieselului in vederea comercializarii acestuia. In prezent biodieselul pur (100%) este distribuit in multe benzinarii din Europa. Proprietati Se analizeaza experimental proprietatile fizico-chimice a diferitelor amestecuri de biodiesel si motorina (densitate, vascozitate, punct de inflamabilitate, punct de tulburare, punct de congelare, compozitie elementara, analiza termica) facandu-se apoi o analiz comparativ cu diferite standarde pentru biodiesel.

Biodieselul are proprietati de lubrificare superioare motorinei si o cifra cetanica mai mare. Aditia biodieselului reduce uzura sistemului de combustie si mareste perioada de functionare a echipamentului de injectie ce se bazeaza pe combustibil pentru lubrificare. Puterea calorica atinge o valoare de 37.27 Mj/kg. Are un punct de fierbere ridicat si o presiune de vaporizare scazuta. Temperatura de aprindere este mai ridicata decat cea a motorinei, de asemenea are o densitate mai mare. Biodieselul nu contine sulf si este folosit drept aditiv pentru lubrificare in motorina. Tehnologii de obtinere a biodieselului Grasimile si uleiurile sunt formate din trigliceride. Fiecare triglicerida este compusa din trei acizi grasi de catena lunga cu un numar de atomi de carbon cuprins intre 8 si 22, care sunt legati de o molecula de glicerol. Biodieselul este format din acizi grasi care sunt legati chimic de o molecula de metanol. In urma procesului de transesterificare, molecula de glicerol este indepartata aproape complet din compozitia biodieselului finit. Tehnologiile de obtinere a biodieselului comercial pot fi clasificate astfel: A. B. C. D. E. F. G. Transesterificarea in cataliza omogena alcalina a uleiurilor rafinate Transesterificarea catalizata bazic a grasimilor vegetale cu un continut scazut de Transesterificarea in cataliza acida Transesterificarea in cataliza eterogena bazica si acida Transesterificarea enzimatica Transesterificarea folosind microunde Transesterificarea folosind ultrasunete Tehnologiile se pot realiza in sistem batch in cazul obtinerii biodieselului la nivel domestic sau continuu in cazul obtinerii acestuia la nivel industrial. Tehnologia de obtinere in sistem batch permite controlul calitativ al produsului de reactie in cazul utilizarii materiilor prime de o calitate medie precum ulei prajit reciclat sau grasimile animale.

acizi grasi liberi si a grasimilor animale

Pentru ca biodieselul sa corespunda in punct de vedere calitativ, trebuie sa ii lipseasca din compozitie alcoolii, catalizatorul, sapunurile, glicerina, trigliceridele care nu au reactionat sau au reactionat partial si acizii grasi liberi. In prezent exista numeroase produse pe baza de metil esteri utilizate in procesele chimice la nivel industrial sau pentru fabricarea lubrifianti industriali. Insa cerintele de procesare a acestor produse nu sunt suficiente pentru obtinerea unui biodiesel corespunzator din punct de vedere calitativ. Cea mai comuna problema o reprezinta prezenta trigliceridelor care nu au reactionat sau au facut-o partial si a glicerinei, care cresc nivelul de vascozitate, temperatura punctului de tulburare si cea a punctului de curgere, acesti factori ducand la posibile avarii ale motorului. A. Transesterificarea in cataliza omogena alcalina a uleiurilor rafinate Transesterificarea catalizata bazic a uleiurilor vegetale rafinate prezinta o eficienta ridicata de pana la 99,9% si produce biodiesel de buna calitate dupa indepartarea excesului de metanol, catalizator bazic si glicerina. Reactia chimica necesita trei molecule de metanol (sau alt alcool) pentru fiecare molecula de triglicerida, care corespunde cu aproximativ 10% greutatea de metanol per masa de ulei procesat. Principalul produs secundar de reactie este glicerina. Mici cantitati de acizi grasi liberi (1,5%) sunt convertite in sapunuri. Aceste sapunuri sunt in mod normal indepartate odata cu glicerina sau odata cu procesul de rafinare al uleiului crud. Drept catalizatori bazici mai pot fi utilizati hidroxidul de sodiu sau metoxidul de sodiu. Catalizatorii pe baza de sodiu nu formeaza fertilizator ca produs de reactie. Acizii sunt utilizati atat pentru a stopa emulsifierea glicerinei in vederea unei procesari partiale ulterioare, cat si pentru a neutraliza catalizatorul bazic.

Obtinerea de biodiesel utilizand cataliza alcalina Exista numeroase variatii ale tehnologiei alcaline de obtinere a bioidieselului. Diferiti catalizatori, inclusiv cei nonbazici, pot fi utilizati. Etanolul anhidric, alcooli izopropilici sau butidici pot substitui metanolul, insa timpul de reactie este prelungit, iar randamentul

de obtinere a biodieselului poate scadea, fiind necesare masuri mai riguroase de control al calitatii precum si procese aditionale. Procesul de transesterificare bazica este realizat la atmosfera standard si la o temperatura de 60oC. Deasemenea exista variatii ale acestei tehnologii in care sunt utilizate temperaturi si presiuni mai inalte. Uneori distilarea este utilizata pentru controlul calitatii. B. Transesterificarea catalizata bazic a grasimilor vegetale cu un continut scazut de acizi grasi liberi si a grasimilor animale Transesterificarea catalizata bazic ce utilizeaza ca materie prima acizi grasi liberi reprezinta o variatie a transesterificarii catalizate omogene alcaline. Astfel, o mica cantitate de catalizator este adaugata la materia prima pentru a reactiona cu acizi grasi liberi si forma sapunuri. Apoi sapunurile sunt indepartate, iar procesul de transesterificare incepe. In cazul producatorilor locali, utilizarea acestei tehnologii prezinta dezavantajul pierderii unei cantitati de ulei pur egal cu cea de sapun, fara posibilitatea valorificarii lui. Insa la nivel industrial, sapunurile pot fi reintroduse in reactie pentru obtinerea de produse utilizabile in agricultura. Aceasta variatie a procesului de transesterificare poate fi utilizata in functie de disponibilitatea pe piata locala agricola a acizilor grasi si a valorii acestor produse (care ar trebui sa fie mai mare decat a biodieselului). C. Transesterificarea in cataliza acida cu utilizarea clorurii de colina *xZn Cl2 pentru obtinerea biodieselului Clorura de colina *xZnCl2 este utilizata drept catalizator acid de tip Lewis pentru transesterificarea uleiului. Obtinerea biodieselului folosind clorura de colina *xZnCl2 este eficienta, prezentand numeroase avantaje precum modalitatea de prepaare usoara, prestul scazut sau randamentul de obtinere al biodieselului similar cu cel obtinut in urma utilizarii altui tip de catalizator. Taria acida Lewis a lichidului ionic creste odata cu augmentarea cantitatii de ZnCl2. Datorit aciditatii scazute a catalizatorului, randamentul de obtinere este mai mare decat al altor lichide ionice. Reactia are loc la un raport molar metanol-ulei vegetal 16:1 la o temperatura de 70oC, transesterificare fiind promovata de speciile acide Lewis:

Zn3Cl7-, Zn2Cl5- si ZnCl3- din catalizatori. Randamentul de obtinere al biodieselului este usor crescut cu cresterea lui x de la 1 la 3. Timpul optim de reactie este de 72 de ore, iar clorura de colin 2ZnCl2 este un catalizator tipic pentru acesta abordare a reactiei de transesterificare, conversia maxima de 54,52% fiind atinsa la 10 % clorura de colina 2ZnCl2. Datorita reversibilitatii reactiei de transesterificare folosita la obtinerea biodieselului producerea unui bun randament poate fi grabita prin introducerea unui exces de metanol pentru a schimba echilibrul. La un raport mai mic de 16, raportul de metanol: ulei are un efect semnificativ asupra activitatii catalitice. La adaugarea unei cantitti mari de metanol, concentratia catalizatorului este diluata la o cantitate fixa de clorur de colina 2ZnCl2 si ulei vegetal, iar depasirea raportului 16 de metanol nu are niciun efect asupra performantei catalizatorului. Mai mult, un raport molar mai mare de metanol: ulei duce la o problema de separare in timpul reciclarii. Astfel, raportul molat optim de metanol : ulei vegetal este de 16:1. Influena temperaturii asupra reactiei de esterificare devine mai mica odata cu cresterea acesteia. Totusi, daca temperatura de reactie ajunge la punctul de fierbere a metanolului de 80 si 90oC, metanolul se va vaporiza rapid i va forma un numar mare de bule care inhiba reactia la interfata dintre cele doua faze. In plus, pentru conservarea energiei, este necesara alegerea unei temperaturi relativ scazute. Astfel, temperatura optima de reactie pentru transesterificarea uleiului la biodiesel este in jurul valorii de 70oC. D. Transesterificarea in cataliza eterogena bazica si acida Acizii grasi liberi reactioneaza cu metanolul (1:1) si cu catalizatorul acid precum acidul sulfuric, pentru a forma metilesteri. Randamentul acestei reactii este in general de 96%, ceea ce inseamna ca un procent de aproximativ 4% de acizi grasi liberi nu reactioneaza, urmand ca acestia sa reactioneze cu catalizatorul bazic in urmatorul pas si formeaza sapunuri. In cazul in care sapunurile nu sunt indepartate inainte de transesterificare, sunt necesare teste de control al calitatii in vederea evidentierii prezentei sapunurilor. Restul procesului este similar cu cel descris mai devreme. Insa acest proces

are un randament ce poate depasi valoarea de 99%, depinzand de cantitatea de acizi grasi din materia prima originala si de varietatea de produse secundare rezultate. E. Transesterificarea enzimatica Poate avea loc n dou sisteme de reacie pentru obinerea de biodiesel pe cale enzimatic i anume: metanoliz n sistem cu agitare continu, respectiv metanoliz n sistem cu deplasare i recirculare. n primul caz reacia are loc folosind un reactor de tip batch n care enzima este supus agitrii mpreun cu amestecul de reacie de la nceputul reaciei pn la finalizarea acesteia, n timp ce, n al doilea caz, reacia are loc prin recircularea amestecului de reacie peste stratul fix de enzim reactor tip coloan cu umplutur. Condiiile de reacie folosite n ambele cazuri sunt cele care s-au dovedit a fi optime pentru metanoliza enzimatic a uleiului de floarea soarelui catalizat de Novozym 435. Reaciile au fost monitorizate timp de 24 h, iar pentru aceasta s-au prelevat probe din amestecul de reacie la intervale regulate de timp i s-au analizat. Analizele efectuate au urmrit determinarea randamentului n esteri metilici i au fost realizate cu ajutorul cromatografiei n faz gazoas. Randamentele sunt net superioare n sistemul cu agitare, cnd nc de la nceputul reaciei enzima se afl n contact cu toat cantitatea de ulei ceea ce duce la o vitez mai mare de reacie. Astfel, dup primele 15 min, randamentul global pentru reacia cu agitare este deja de 23,6% (m/m), Obtinerea de biodiesel folosind cataliza enzimatica F. Transesterificarea asistata de microunde Transesterificarea poate fi efectuata prin reactia catalitica sau necatalitica folosind diferite sisteme de incalzire.

Un sistem de incalzire alternativa - "de incalzire cu microunde", a fost folosit n ultimii ani, mai ales in testarile de laborator si la nivel de pilot. In acest caz reactia de transesterificare este accelerata intr-un timp de reactie scurt. Ca urmare, are loc o reducere importanta a cantitatii de produse secundare si un timp scurt de reactie. Se utilizeaza un sistem de incalzire tip cuptor cu microunde. Intreg sistemul a fost echipat cu un condensator cu reflux, un agitator magnetic i un detector de temperatura, tip noncontact in infrarosu, care permite controlul continuu si constant al temperaturii de lucru. Compozitia de acizi grasi a uleiului i analiza probelor de biomotorina se efectueaza pe cromatograf de gaz 6890N echipat cu detector de ionizare cu flacara. G. Transesterificarea asistata de ultrasunete In prezent, biodieselul este, in principal produs in reactoare lot. Folosirea ultrasunetelor in transesterificarea uleiurilor la biodiesel permite prelucrarea in linie continua, la orice scara. Ultrasonicarea duce la o crestere a randamentului de biodiesel pana la 99%. Reactoarele cu ultrasunete reduc timpul de prelucrare la mai putin de 30 de secunde (prelucrarea conventionale 1 - 4 ora/sarja). Mai important, ultrasonicarea reduce timpul de separare de la 5 - 10 ore (folosind agitatie conventionale) la mai putin de 60 de minute. Transesterificarea cu ultrasunete implica urmatorii pasi: 1. 2. 3. 4. centrifuge; 5. biodiesel convertit este spalat cu apa. uleiul vegetal este amestecat cu metanol (care produc esterii de metil) sau amestecul este nclzit la temperaturi ntre 45 i 65 0C; apoi este trecut prin sonicator timp de 5 la 15 secunde. Sonicarea se glicerina, care se obtine ca produs secundar, este separata folosind etanol (pentru etil esteri), precum si cu catalizatorii;

efectueaza la o presiune ridicate (De la 1 la 3bar, manometru);

Utilizari Biodieselul pur, denumit B100, este de fapt un monoalchilester al acizilor grai derivai din uleiurile vegetale sau animale. Biodieselul este un combustibil alternativ care poate fi utilizat n form pur sau n amestec cu motorin, atunci cnd este ars n motoarele cu ardere intern, sau cu combustibilii pentru cazane atunci cnd este utilizat n scopuri casnice. Strategiile de dezvoltare se direcioneaz pe utilizarea biodieselului spre zonele sensibile din punct de vedere ambiental, ca de exemplu: transportul transportul public local: taxi, autobuze, servicii; vehicule publice: salubrizare strzi, colectare gunoi menajer, ntreinere spaii verzi; vehicule agricole i de transport i n zonele agricole; vehicule ale armatei i cile ferate. Avantaje Biodieselul este un combustibil curat. La utilizarea accestuia se reduc Biodieselul inlocuieste cu succes motorina, petrolul, sau poate fi amestecat cu Utilizarea biodiesel-ului - obtinut prin transesterificarea uleiului de sofranel cu semnificativ emisiile de noxe comparativ cu motorina. acestea In orice proportie. alcooli inferiori (metanol, etanol, etc.) - drept combustibil pentru motoarele diesel moderne nu presupune modificari constructive esentiale ale acestuia . de: - dioxidul de sulf cu 100% - dioxidul de carbon 10-50% - dioxidul de azot 5-10% Biodieselul este mai sigur de manipulat decat motorina. Biodieselul este biodegradabil deoarece se obtine din resurse regenerabile. Calitatea biodieselul este reglementata de ASTM D 6751. Biodieselul are toxicitate mai mica comparativ cu motorina si se reduc emisiile

Dezavantaje Vascozitatea mai mare face ca pomparea sa fie mai dificila. Valorile mai ridicate ale temperaturii de tulburare si a punctului de lichefiere

pot pune probleme la pornirea motorului la temperaturi mai scazute iar consumul de combustibil este mai ridicat. Procentul emisiilor de oxizi de azot (NOx) este mai ridicat. Puterea dezvoltata de motorul este cu 5% mai mica comparativ cu puterea Exista pericolul depunerilor la nivelul injectorului iar gradul de uzura al

dezvoltata la utilizarea diesel-ului clasic. motorului s-a dovedit a fi mai ridicat. [2] http://biofuels.dbioro.eu/biodiesel.php