Water and Sediment
Water can be present in two forms, either as dissolved water or as suspended water droplets. while biodiesel is generally considered to be insoluble in water, it actually takes up considerably more water than diesel fuel. Biodiesel can contain as much as 1500 ppm of dissolved water while diesel fuel usually only takes up about 50 ppm . The standards for diesel fuel (ASTM D 975) and biodiesel (ASTM D 6751) both limit the amount of water to 500 ppm. For petroleum-based diesel fuel, this actually allows a small amount of suspended water. However, biodiesel must be kept dry. This is a challenge because many diesel storage tanks have water on the bottom due to condensation.
Suspended water is a problem in fuel injection equipment because it contributes to the corrosion of the closely fitting parts in the fuel injection system. Water and sediment contamination is basically housekeeping issues for biodiesel. Water can also contribute to microbial growth in the fuel. This problem can occur in both biodiesel and conventional diesel fuel and can result in acidic fuel and sludge that will plug fuel filters. Sediment may consist of suspended rust and dirt particles or it may originate from the fuel as insoluble compounds formed during fuel oxidation.
Some biodiesel users have noted that switching from petroleum-based diesel fuel to biodiesel causes an increase in sediment that comes from deposits on the walls of fuel tanks that had previously contained diesel fuel. Because its solvent properties are different from diesel fuel, biodiesel may loosen these sediments and cause fuel filter plugging during the transition period.
Storage stability refers to the ability of the fuel to resist chemical changes during long term storage. These changes usually consist of oxidation due to contact with oxygen from the Air. The fatty acid composition of the biodiesel fuel is an important factor in determining Stability towards air. Generally, the polyunsaturated fatty acids (C18:2, linolenic acid; C18:3 linolenic acid) are most susceptible to oxidation.
The changes can be catalysed by the presence of certain metals (including those making up the storage container) and light. If water is present hydrolysis can also occur. The chemical changes in the fuel associated with oxidation usually produce hydroperoxides that can, in turn, produce short chain fatty acids, aldehydes, and ketones, under the right conditions, the hydroperoxides can also polymerize. Therefore, oxidation is usually denoted by an increase in the acid value and viscosity of the fuel. Often these changes are accompanied by a darkening of the biodiesel colour from yellow to brown and the development of a “paint” smell. When water is present, the esters can hydrolyze to long chain free fatty acids which also cause the acid value to increase.
There is currently no generally accepted method for measuring the stability of biodiesel. The techniques generally used for petroleum-based fuels, such as ASTM D 2274, have been shown to be incompatible with biodiesel. Other procedures, such as the Oil Stability Index or the rancimat apparatus, which are widely used in the fats and oils industry, seem to be more appropriate for use with biodiesel. However, the engine industry has no experience with these tests and acceptable values are not known. Also, the validity of accelerated testing methods has not been established or correlated to actual engine problems. If biodiesel’s acid number, viscosity, or sediment content increase to the point where they exceed biodiesel’s ASTM limits, the fuel should not be used as a transportation fuel.
Additives such as BHT and TBHQ (t-butylhydroquinone) are common in the food industry and have been found to enhance the storage stability of biodiesel. Biodiesel produced from soybean oil naturally contain some antioxidants (tocopherols, i.e., vitamin E), providing some protection against oxidation (some tocopherol is lost during refining of the oil prior to biodiesel production). Any fuel that will be stored for more than 6 months whether it is diesel fuel or biodiesel should be treated with an antioxidant additive. The oxidation reactions affect the fuel quality of biodiesel, primarily during extended storage. The oxidation stability study was conducted for a period of 30 months. Biodiesel kept in an argon atmosphere could increase its stability.
All biodiesel production facilities should be equipped with a laboratory so that the quality of the final biodiesel product can be monitored. It is also important to monitor the quality of the feed stocks. One strategy used by many producers is to draw a sample of the oil (or alcohol) from each delivery and use that sample to produce biodiesel in the laboratory. This test can be fairly rapid (1 or 2 hours) and can indicate whether serious problems are likely in the plant. Measuring feedstock quality can usually be limited to acid value and water content.
These are not too expensive ($500 for the acid value equipment and $5,000 for the water measurement equipment) and can be operated by less experienced technicians. To monitor the completeness of the reaction according to the total glycerol level specified In ASTM D 6751 requires the use of a gas chromatograph and a skilled operator. Large producers will find that having this equipment on-site is necessary. Commercial laboratories (i.e. Magellan Midstream Partners) are available that can analyze the samples but the cost is $80-$ 150/test and the time required may be several days. Smaller producers will need to use a more robust production process involving extra methanol and probably multiple reaction steps. Then the product quality can be monitored through periodic testing by an outside laboratory.
Other possibilities for monitoring the trans-esterification reaction and assessing fuel quality are methods based on spectroscopy (such as near- infrared spectroscopy) or physical properties (such as viscometer). These methods although they are not (yet?) ASTM methods are usually faster and easier to use than gas chromatography. However, some of them require extensive calibration. They also cannot accurately quantify glycerol at the low levels called for in the ASTM standard. To circumvent this, comparison to a reaction and product known to meet ASTM standards is needed.
Influence of Temperature
The temperature influence is statistically significant in the range studied. This effect has a positive influence on the response. As the temperature increases, the solubility of methanol in the oil increases and so does the speed of reaction. As a matter of fact, at low temperatures, methanol is not soluble at all in the oil; when the stirring is started an emulsion appears. The reaction takes place at the interface of the droplets of alcohol in the oil and then as soon as the first FAMEs are formed, the alcohol solubilises progressively because the esters are mutual solvents for the alcohol and the oil.
Biodiesel is an important new alternative transportation fuel. It can be produced from many vegetable oil or animal fat feed stocks. Conventional processing involves an alkali catalysed process but this is unsatisfactory for lower cost high free fatty acid feed stocks due to soap formation. Pre-treatment processes using strong acid catalysts have been shown to provide good conversion yields and high quality final products. These techniques have even been extended to allow biodiesel production from feed stocks like soap stock that are often considered to be waste. Adherence to a quality standard is essential for proper performance of the fuel in the engine and will be necessary for widespread use of biodiesel. Biodiesel is alternative resources which are economic, sufficient and readily available are to be identified and appropriate type of technology which can produce biodiesel of acceptable quality is to be developed.