Emulsifier JEB 60 for Biodiesel

Transcription

1 Emulsifier JEB 60 for Biodiesel

2 BIODIESEL 1st Generation Biodiesel is a liquid fuel produced from vegetable oils and animal fats, the most used raw materials for this purpose are rapeseed, sunflower and soybean. The properties of biodiesel are virtually the same as those of diesel fuel in density and cetane number. It presents a higher flashpoint. Therefore, biodiesel can be blended with diesel for use in engines and boilers, and even replace it altogether if they fit properly. ASTM (American Society for Testing and Materials Standard) describes biodiesel as monoalkyl esters of long fatty acids chains derived from renewable lipids such as vegetable oils or animal fats, and which are used in compression ignition engines. However, the most common esters are those of methanol and ethanol (obtained from the transesterification of any type of vegetable oils or animal fats or esterification of fatty acids) because of their low cost and their chemical and physical advantages. As for the use of biodiesel as an automotive fuel, it should be noted that the characteristics of the esters are more similar to those of diesel that unmodified vegetable oil. The viscosity of the ester is greater than twice of the diesel compared to ten times or more that of the crude oil, in addition, cetane value of esters is higher, being suitable for use as fuel. ASTM specified various tests to be performed on fuels to ensure proper operation. Table 1 lists the specifications for biodiesel and corresponding test method. Biodiesel needs to have a specification that lists the properties and ensure product quality. In addition, biodiesel must meet the requirements for automotive fuels and minerals that are contained in the European standard EN-590. Specific requirements and control methods for marketing and distribution of fatty acid methyl esters (Fatty Acid Methyl Ester, FAME) for use in diesel engines with 100% concentration found in the standard EN for determining the specifications of petrol, diesel, fuel oil and liquefied petroleum gases and regulating the use of certain biofuels.

3 Chart 1 Biodiesel Properties Properties Unit Limits Min. Max. Test Method Ester Content % (m/m) 96.5 b EN Density at 15 ºC Kg/m³ EN ISO 3675 Viscosity at 40 ºC mm²/g EN ISO 3104 Flashpoint ºC 120 pren ISO 3679 Sulfur content mg/kg 10.0 pren ISO Carbon residue destilate residue) (in 10% of % (m/m) 0.30 EN ISO 5165 Cetane Index 51.0 EN ISO 5165 Sulfated ash content % (m/m) 0.02 ISO 3987 Water content mg/kg 500 EN ISO Total contamination mg/kg 24 EN Copper strip corrosion (3h at 50ºC) Clasification Class 1 EN ISO 2160 Oxidation stability 110ºC Hours 6.0 EN Acid value mg KOH/g 0.50 EN Iodine value g lodine/100g 120 EN Methyl ester of linoleic acid % (m/m) 12.0 EN Polyunsaturated methyl esters (>= to 4 double bonds) % (m/m) 1 Content of Methanol % (m/m) 0.20 EN Content of Monoglyceride % (m/m) 0.80 EN Content of diglyceride % (m/m) 0.20 EN Content of triglycerides % (m/m) 0.20 EN Free glycerol % (m/m) 0.02 EN Total glycerol % (m/m) 0.25 EN Metals of group I (Na+K) mg/kg 5.0 EN Metals of group II (Ca+Mg) mg/kg 5.0 pren Phosphorus content mg/kg 10.0 EN 14107

4 PROCESSES FOR OBTAINING BIODIESEL Raw Materials The most common raw materials used for the production of biodiesel (EU) are waste cooking oil and sunflower oil (the average content of sunflower oil is 44% so that Spain will be the best option in terms of energy agriculture ). It is also being tested on rapeseed oil and Brassica carinata. Any material containing triglycerides can be used for production of biodiesel (sunflower, rapeseed, soybean, used frying oil, beef tallow,...). Moreover, in EU, the use of oils is still not significant. Below (Table 2), are the main raw materials for the production of biodiesel. Conventional Oils Alternative Oils Other Sources Sunflower Brassica Carinata GM Seed Oil Rape Cynara Curdunculus Animal fats (beef and buffalo tallow) Coconut Camelina Sativa Microalg oils Soy Crambe Abyssinaca Microbial oil production Palm Pogianus Cooking oil Chart 2: Main raw materials for production of Biodiesel Conventional vegetable oils Raw materials conventionally used in the production of biodiesel have been oilseed oils like sunflower and rapeseed (Europe), soybeans (USA) and coconut (Philippines) and oils such as palm oil fruits (Malaysia and Indonesia). For reasons of weather, rapeseed (Brassica Napus) occurs mainly in Northern Europe and sunflower (Helianthus Annuus) in southern Mediterranean countries such as Spain or Italy. The use of these oils to produce biodiesel in Europe has been associated with regulations of compulsory setaside of the Common Agricultural Policy (CAP) which allows the cultivation of oilseeds at reasonable prices. Nevertheless, the dedication of land only for the production of energy commodities poses a risk because these surfaces vary over time, as the scheme depends of food grains supply and demand, which implies that this index is subject to alterations.

5 Alternative vegetable oils In addition to conventional vegetable oils, other species more adapted to the conditions of each country-area and better positioned in the field of energy crops. Include the use as raw materials for the production of biodiesel from oils of Camelina Sativa, Crambe Abyssinica and Jatropha Curcas. There are other crops that are better adapted to the conditions of southern European countries and having higher production yields. Specifically, Cynara Cardunculus and Brassica Carinata. The Brassica Carinata is a real alternative to extensive dry or irrigated lands. The Cynara Cardunculus is a multiannual and permanent crops, about ten years occupation of land, and primarily oriented to the production of biomass, but can also exploit their seeds to obtain oil. Obtained from 2,000 to 3,000 kg of seeds, which oil serves as raw material for biodiesel production. Genetically modified vegetable oil Oils and fats mainly differ in their fatty acid content. Oils with high proportions of unsaturated fatty acids such as sunflower oil or Camelina Sativa, improves biodiesel operability at low temperatures, but reduce their stability to oxidation, resulting in a high iodine value. For this reason, some oils with high content of unsaturated can be considered as raw material to produce biodiesel, which have been genetically modified to reduce this proportion, as high oleic sunflower oil. Waste cooking oil The used cooking oil is one of the alternatives with better prospects in the production of biodiesel, as it is the cheapest raw materials, and its use as fuel avoided waste treatment costs. Spain is a major consumer of vegetable oils, focusing on consumption of olive oil and sunflower. This oils have a low level of reuse, so do not suffer major changes and are well suited for use as biofuel. Also, as an added value, the use of oils means good management and use of the waste, the report on the regulatory framework proposed recycle Cooking oil into biodiesel. Collection of this oil is problematic once blended with residual water. The European Commission proposes that the Ministry of Environment and the municipalities create a fried oil and fats oleins collection system in three stages: industrial, hospitality and domestic, with special attention to its control and traceability due to its nature as waste. Animal Fats In addition to vegetable oils and waste cooking oils, animal fats, and more specifically, the beef tallow can be used as feedstock for biodiesel transesterification. Tallow has varying degrees of quality with regard to their use in food, using the worst in the formulation of animal feeds. The application of animal fats arose from the prohibition of its use in the production of feed, such as output for the same product. However, there is currently no industrial application level. Oils from other sources Moreover, it is noteworthy lipid production of compositions similar to vegetable oils, by microbial processes, from algae, bacteria and fungi as well as from microalgae.

6 Transesterification The chemical reaction as the industrial process used in production of biodiesel, is called transesterification, which consists of three consecutive reversible reactions. The triglyceride is converted consecutively diglyceride, monoglyceride and glycerin. In each reaction, one mole of methyl ester is released. This whole process is carried out in a reactor where the reactions occur in subsequent phases and separation, purification and stabilization. Existing technologies may be combined in different ways by varying the process conditions and the feeding thereof. Technology choice will be a function of the desired production capacity, power, quality, alhohol and catalizator recovery. Generally smaller plants with different supply capacity and quality in the food (simultaneously use refined oils and reused) are using Batch or discontinuous processes. Continuous processes, however, are more suitable for large capacity plants justifying increased staff and require a more uniform feed. CH2 O CO R1 CH O CO R2 CH2 O CO R3 + CH3OH CH3 O CO R3 + CH2 O CO R3 CH O CO R2 CH2 OH Triglyceride Methanol Methyl Ester Diglyceride CH2 O CO R1 CH2 OH CH O CO R2 + CH3OH CH3 O CO R1 + CH O CO R2 CH2 OH CH2 OH Diglyceride Methanol Methyl Ester Monoglyceride CH2 OH CH2 OH CH O CO R2 + CH3OH CH3 O CO R2 + CH OH CH2 OH Monoglyceride CH2 OH Methanol Methyl Ester Glycerin

7 Discontinuous Transesterification Process It is the simplest method for the production of biodiesel that have reported ratios 4:1 (alcohol: triglyceride). These reactors with agitation, where the reactor may be sealed or fitted with a reflux condenser. The most usual operating conditions are at temperature of 65 C, although temperature ranges from 25 C to 85 C have also been published. The most common catalyst is NaOH although KOH is also used in ranges from 0.3% to 1.5% (depending if the catalyst used is KOH or NaOH). Rapid agitation is required for proper mixing of the oil in the reactor, the catalyst and the alcohol. Towards the end of the reaction, the agitation must be smaller to allow the glycerol ester phase separation. Results between 85% and 94% have been published in professional literature. In transesterification, when using acid catalysts, elevated temperatures are required, and long reaction times. Some plants are using two stages operating systems, with elimination of glycerol between them to increase the final yield to percentages higher than 95%. Temperatures higher and higher ratios of alcohol-oil can also increase the reaction yield. The reaction time is usually between 20 minutes and one hour. Figure 1 reproduces a block diagram of a discontinuous process of transesterification. Alcohol Separation Water R-OH + Water Alcohol Catalyst Oil R-OH Washing Separation BIODIESEL REACTOR Separation R-OH + Water Fatty Acids Crude Glycerin Graph 1. Discontinuous transesterification process Conditioning Refinement Salts Glycerin

8 Continuous Process A discontinuous process variation is the use of continuous reactors stirred tank type, called CSTR (Continuous Stirred Tank Reactor). This type of reactor can varied its volume to permit longer residence times and achieve increase reaction results. Thus, after decantation of glycerol in the first separator, the reaction in a second CSTR is much faster, with a percentage of 98% of reaction product. An essential element in the CSTR reactor design is to ensure that the mixture is suitably carried out so that the composition in the reactor is substantially constant. This has the effect of increasing the dispersion of the glycerol in the ester phase. The result is that time required for phase separation increases. There are several processes using intense mixing to promote the esterification reaction. The reactor used in this case is of tubular type. The reaction mixture is moved longitudinally by this type of reactor, with little mixing in the axial direction. Such Plug Flow Reactor, (PFR), behaves like small CSTR reactors in series. The result is a continuous system that requires lower residence times (of the order of 6 to 10 minutes) with the consequent saving, being smaller reactor for conducting the reaction. This type of reactor can operate at elevated temperature and pressure to increase the conversion rate. Graph 2 presents a block diagram of a transesterification process with plug flow reactors. In this process, triglycerides are introduced with the alcohol and the catalyst and subjected to different operations (two reactors are used) to yield the ester and glycerin. Heterogeneous catalysis within the basic catalysts are easily deactivated by the presence of free fatty acids (FFA) and water which promotes the formation thereof. For treating feeds with some degree of acidity is preferred esterification of free fatty acids which superacids that have a high reaction rate of transesterification, which implies that it requires two reactors with an intermediate stage of water removal. Thus, feeds with up to 30% FFA can be esterified with methanol, reducing presence of FFA below 1%. This prior stage of esterification can be carried out with higher alcohols or glycerin that is attractive in biodiesel production as a byproduct of the process. Triglycerides Alcohol Catalyst Mix and Heater Reactor 1 Alcohol Ester Glycerol Separation Reactor 2 Glycerol Alcohol Alcohol Chart 2. Process for obtaining biodiesel by plug flow reactors.

9 The biodiesel glycerin byproduct In the synthesis of biodiesel, are formed between the oil and alcohol, usually methyl esters in a proportion of approximately 90% plus 10% glycerol. Glycerin is a very valuable product that in case to be refined at pharmaceutical grade can cover the operating costs of the manufacturing plant. Glycerin is removed from the process when it comes to washing with water. However, the glycerin in the biodiesel can be due to an inappropriate process, such as an insufficient glycerin separation phase or an insufficient washing with water. The glycerin is used in the manufacture, storage, softening and moisturizing product lot, they may be alkyd resins, cellophane, snuff, explosives (nitroglycerin), drugs and cosmetics, urethane foams, foods and beverages, etc. Thus, glycerin is a byproduct of biodiesel production, at pharmaceutical and industrial qualities. These glycerol have a positive economic value and its marketing is part of the biodiesel profitability. However, the increased supply of glycerin is already causing a decrease in its selling prices with the consequent loss of return-incomes for the biodiesel sector. At the current level of production, the glycerin have enough outlets now, but getting a biodiesel production of the magnitude of the target for 2020 could cause glycerin market saturation, so it is especially important to ensure marketing channels of this product. With the increase in production of biodiesel, glycerine faces research and development challenges to find outlet to its significant increase in the coming years. Therefore, we must find new outlets and end product applications or find new applications in which glycerin acts as a chemical feedstock. Energy balance of biodiesel production The energy balance of biodiesel, considering the difference between the energy that produces 1kg. of biodiesel and the energy required for the production thereof, since agricultural to industrial phase is positive by at least 30%. Therefore it can be considered a sustainable activity. In addition to the favorable conditions, from ecological point of view and energy, worth mentioning the possibility of immediate use in engines. Biodiesel burns perfectly without requiring any modifications to existing engines and boilers, and also can alternatively powered with diesel fuel or mixture of both. This is the major difference, relative to other fuel substitution as bioethanol, which requires irreversible changes in engines. The use of biodiesel increases engine life due to its higher lubricity, while no changes in consumption of fuel, ignition, power and engine torque.

10 BIODIESEL 2º Generation (Renewable Biodiesel) Renewable Diesel is a clean alternative fuel that can be used in pure form, or mixed with traditional diesel, reduces emissions up to 80%. The renewable diesel is produced from renewable & sustainable raw materials as waste from refining and vegetable oil production. An alternative fuel similar to conventional or fossil diesel. Renewable-Biodiesel can be produced from a wide variety of non-food feedstocks as well as waste/residue, used vegetable oil, animal fats or industrial wastes, for energy production used in transport, heating and power generation. and meets the standard requirements in EU, and the U.S. FBC (Renewable Biodiesel Technologies) do not use raw materials from edible oils, unlike most other producers / refineries worldwide. Therefore, renewable FBC diesel refineries are due NO impact on the steady increase in basic food lately also affect the profitability of producers / biodiesel refineries that use products from food chain. RENEWABLE BIODIESEL MARKET: The global market for Renewable Biodiesel is ready for explosive growth over the next ten years. Europe accounts for 85% of global production and consumption of renewable biodiesel. The U.S. are currently in production climbed at a higher rate than the European. Elsewhere in the world the renewable diese / biodiesel recorded a significant increase due to the reaction of governments to reduce energy dependence on oil imports, and is intended to search for alternatives to fossil fuels. The economic and environmental security has led to new government priorities and goals as Brazil, China, India and Europe, encouraged by reducing oil imports and increased consumption and production of alternative and renewable fuels. Market demand renewable diesel: diesel consumption in Europe and the U.S. increased by 4.5% per year since In 2007, the production of biodiesel in Europe and U.S. reached only 1.8% of the total diesel consumption. Biodiesel production in Europe and the U.S. increased on average by 52% per year since 2002.

11 Major influence factors on renewable diesel demand are: Factor Influence Renewable Diesel Demand Demand End-user awareness, diesel is up to 30% more efficient than gasoline. In 1999 demand for diesel fuel exceeded gasoline demand. According to government estimations, in 2015 diesel fuel consumption will exceeds that of gasoline at a ratio of 2 to 1. Governments Incentives Dwindling reserves and rising oil prices. Dependence on oil imports. Kyoto Accords and other directives. Reasons environmental (greenhouse gas / air quality) Europe leads the world with regard to standards ¹ reaching up to 7% mixing ratio in 2010 and 20% by The Government of E.U. Europe and the US leads the world toward credits ($ 1 per gallon in the U.S.), tax exemption, tax reduction related to the production of renewable diesel / biodiesel, for the creation of a stable and viable market for renewable diesel. ¹ Standard Biodiesel refers to a specific requirement of mixture (%) of renewable diesel / biodiesel with conventional diesel. For example: 7% standard reflects the requirement of mixing 7 liters of renewable diesel / biodiesel per 100 liters of diesel

12 2º GENERATION BIODIESEL COMPETITIVENESS: 2nd generation renewable diesel use an exclusive technology that enables use inedible low cost raw materials that reduce total operating cost by 50%. Therefore ensures sustainable production standards according to U.S. biodiesel ASTM / EU at competitive prices and to ensure a return on investment of two digits for investors. More Advantages of FBC Renewable Diesel: FACTS ADVANTAGES of FBC Renewable Diesel Biodiesel Concurrence Oil (raw material) suppose up to 90% of total operation cost of Biodiesel producers. Excess glycerol production has resulted in an excess of glycerin market. Recycled raw materials. Easily capable of processing low cost biodiesel from a non-edible oil with a high% FFA (Free Fatty ACCID) which reduces the overall cost up to 60%. Substantially reduces the production of glycerin as a byproduct of 10-12% to 3-4%, and the increase is proportional to the production of renewable diesel. Up to 70% of the methanol is recovered, refined and reused. Raw materials for products are recovered, treated with methanol catalyzed recycle and then transferred to the raw materials tank. Edible oils used are not limited to soybean oil or canola that are subject to constant price increases ² due to high demand of food and biodiesel industry. Currently producers get low returns or even losses. Byproduct glycerin production 10-12% Methanol recovery is common. Waste recovery is not common and in most cases is restrictive. Low investment and fast ROI. FBC provides advanced technology for small biodiesel plants, modulated according to customer needs in beneficial conditions, with a return on investment much higher than conventional plants. A plant of the same capacity (tons / year) of the competition, with lower diesel technologies can cost approximately 10% more (depending on the technology), excluding the cost of land lease, finance costs, working capital for raw materials, unforeseen...

13 Work Method The Renewable Diesel refineries are flexible in terms of raw materials, especially waste and non-food waste, not limited to liquid waste (waste product of refining vegetable oils with high FFA (Free Fat Accid), yellow grease (used cooking oil) brown grease (food waste), and other DAF sludge. Food Oils Sunflowers; soybean; Palm Cottonseed; Ropeseed, etc. Vegetal Oil Refinery Food Waste Byproduct Waste Byproduct Other non-food waste / residues with high Free Fatty Acids (FFA) content. Soap-stock Used Cooking Oil 2º GENERATION BIODIESEL ASSERTIVE MARKET: Given the decline and / or suspension of the operation of traditional biodiesel market in the EU currently only 15% of production of local capacity available. The rest is imported. Given our high level (lower operating cost / high profit margin, IRR> 50%) we are able to compete in the market easily. Our main objective is the development of new refineries in different biodiesel markets, EU Members States that are required to expand its biodiesel production quota within three years.

14 BIODIESEL EMULSIONS - BASIC TECHNOLOGY Fuelia has concentrated its energies in the creation of a second generation emulsifier for diesels and biodiesels. The results are improved fuels able to fulfil the European standards on environmental policies and rules since the actual fuels available direct from the refinery plants are not quite managing to meet these requirements. Our technology has been applied to diesels and biodiesels (1 st or second generation), in pure form or any mix of them as B-10, B-20, B-50 Emulsion is obtained by mechanical and ultrasound micronization process that results in micro-drops formed by the three basic elements of the product: water in the core, hydrofuel covering the water particles and finally the emulsifier between both previous elements with a membrane that also helps in binding them to other micro-drops. Fuel WATER Emulsifier

15 The nature of the new resulting fuel modifies the traditional combustion sequence. Engine injectors ignite the fuel by compressing hydrofuel in such a way that the explosion overheats the water particles trapped in the core of the micro-drops. This overheating results in water vapour that generates a turbulence inside the engines combustion chamber. This vapour breaks up the hydrofuel molecules resulting in complete burning of the fuel that compensates the loss of energy due to the presence of the water particles added. The vapour also eliminates un-burnt residual particles and helps the cleaning of engine parts and exhaust system Emulsified Fuels Primary Atomization Complete Combustion Corporation Products Emulsion Tecnology Biodiesel Process Emulsion Process Waste Collection Secondary Atomization Reduced Emissions + Water Vapor

16 SOME ADVENTAGES A. Emulsified fuels with Fuelia s additives can be used on all sort of engines and boilers as: cars, industrial vehicles, military machinery, ships, home heating etc... Without having to modify any actual components of the injection / carburettors system or nozzle parts in burners. B. The chemical formula contained in Fuelia s additives makes for a better combustion eliminating most of the usual un-burnt residual particles having a cooling effect on engines and resulting in a smoother and more silent running. Similar effects are noticed in boilers tested with our fuel. Boiler parts become fouling free and therefore show considerable efficiency improvements. C. When using emulsified fuels with Fuelia s additives, distance and engine performance equals that of engine running with traditional fuel. Though we have observed that large truck engines running to extreme speed and fully loaded with 38 tons lose around 4% of power which can be taken as an irrelevant data, this loss of performance will rarely take place in normal driving conditions. D. The final price of the emulsified fuel with Fuelia s additive is defined by the water % added to the final fuel (varies from 10 % up to 30 % according to the target user) and the fixed emulsifier percentage ( %). The sum resulting by adding the cost of fuel, emulsifier, water and the costs of running the blending plant (including business benefits) will always be inferior to the final price offered by the actual distributors. BIODIESEL (1 st or second generation) - BLENDING PROPORTIONS For engines (trucks, buses, boats, trains, generators ) For Boilers (Industrial burners, boilers ) Water (%) Diesel (%) JEB 40 (%)

17 Additive ENGINES % BOILERS Additive % Water 12-15% Water 18-20% Transport Diesel % Industrial Diesel Heating diesel % INDUSTRIAL BLENDING FACILITIES

18 Control Board FUEL Additives WATER END PRODUCT Scheme Description Figure 1 represents the basic device for making emulsified fuel according to our invention. The devise comprises: Fuel tank 1, adapted to contain the fuel to emulsify. The reservoir is connected via pipe 2 to a variable displacement hydraulic pump 3 through the check valve 4, and a volumetric meter 5, 6 connected to the first mixer and the control panel 7. The additive flows from the additive tank 8, and feed pipe 9 that connected to the first hydraulic variable displacement pump 10, through the check valve 11, and a volumetric meter 12, connected to the first mixer 6 and control panel 7. The pipe 13 mixer output 6 is connected to the second mixer 14, static, through the flow sensor 15 which, in turn, is electrically connected to the control panel 7. The water supply is obtained from the water tank 16 through pipe 17, the hydraulic variable displacement pump 18, the check valve 19, and a volumetric meter 20, connected to second mixer 14 and the control box 7. The final product (emulsion) exits the secondary mixer 14 via pipe 21 through flow sensor 22 which is also electrically connected to the control panel 7 to the storage area (not shown) for the end emulsified product. When preparing the emulsified fuel according to the invention, it is preferable to mix the additive package with the fuel prior to adding water. If the order of preparation is reversed, the product obtained would risk being unstable. Furthermore, it is found that the mixer should be constructed and used so that internal pressure reaches ar least 10 bars/cm².

19 All ingredients, except the propellant, are used at room temperature. The fuel (diesel) generally remains liquid at room temperature of 18ºC 20ºC, although during the process in the fuel is heated slightly to improve its ability to mix. It is advisable to heat the fuel to temperatures between 30ºC 60ºC (Buncker 5-6), depending on fuel use, preferably 40ºC. It s equally necessary to use treated water free of bacteria in order to improve the stability of the final product. The average particle size of the final product (emulsion) must be least then 0.01 mm for optimal results. BLEND IT BY YOURSELF In case of small quantities you can make an emulsion blending with simple means like small industrial mixer: STEP ONE: Prepare the quantities of each component (fuel; water; additive) Additive Water Fuel

20 STEP TWO: Blend the fuel with the additive until mix will be perfectly homogeneous. 1. FUEL 2. Additive STEP THREE: Blend the first mix (fuel-additive) with the water until mix will be perfectly homogeneous. Water Blend (fuel-additive)

21 PRODUCT SUPPLY Our products are provided in different types of containers, according to each customer needs: Capacity 25 L 50 L 100 L Capacity 200 L Capacity L