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Formic Acid -- Is this an issue for injecting water?

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Old Aug 10, 2007 | 07:05 AM
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Formic Acid -- Is this an issue for injecting water?

I pulled this off of wikipedia. No idea if it's true, but I've heard others talk about the risk of formic acid damage when using E85 contaminated with extra water. Does this have any relevance to water injection or injecting a mix of alky/meth and water? Just wondering if there is a risk that I didn't know about.

Thanks.

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Water contamination

In addition to corrosion, there is also a risk of increased engine wear for non-FFV engines that are not specifically designed for operation on high levels (i.e., for greater than 10%) of ethanol. The risk primarily comes in the rare event that the E85 fuel ever becomes contaminated with water. For water levels below approximately 0.5% to 1.0% contained in the ethanol, no phase separation of gasoline and ethanol occurs. For contamination with 1% or more water in the ethanol, phase separation occurs, and the ethanol-water mixture will separate from the gasoline. This can be observed by pouring a mixture of suspected water-contaminated E85 fuel in a clear glass tube, waiting roughly 30 minutes, and then inspecting the sample. If there is water contamination of above 1% water in the ethanol, a clear separation of ethanol-water from gasoline will be clearly visible, with the colored gasoline floating above the clear ethanol-water mixture.

For ethanol contaminated with larger amounts of water (i.e., approximately 11%water, 89% ethanol, equivalent to 178 proof ethanol), considerable engine wear will occur, especially during times while the engine is heating up to normal operating temperatures. For example, just after starting the engine, low temperature partial combustion of the water-contaminated ethanol mixture takes place and causes engine wear. This wear, caused by water-contaminated E85, is the result of the combustion process of ethanol, water, and gasoline producing considerable amounts of formic acid (HCOOH, also known as methanoic acid and sometimes written as CH2O2). In addition to the production of formic acid occurring for water-contaminated E85, smaller amounts of acetaldehyde (CH3CHO) and acetic acid (C2H4O2) are also formed for water-contaminated ethanol combustion. Of these partial combustion products, formic acid is responsible for the majority of the rapid increase in engine wear.

Engines specifically designed for FFVs employ soft nitride coatings on their internal metal parts to provide resistance to formic acid wear in the event of water contamination of E85 fuel. Also, the use of lubricant oil (motor oil) containing an acid neutralizer is necessary to prevent the damage of oil-lubricated engine parts in the event of water contamination of fuel. Such lubricant oil is required by at least one manufacturer of FFVs even to this day (Chrysler).

For non-FFVs burning E85 in greater than 23.5% E85 mixtures (20% ethanol), the remedy for accidentally getting a tank of water-contaminated E85 (or gasoline) while preventing excessive engine wear is to change the motor oil as soon as possible after either burning the fuel and replacing it with non-contaminated fuel, or after immediately draining and replacing the water-contaminated fuel. The risk of burning slightly water-contaminated fuel with low percentages of water (less than 1%) on a long commute is minimal; after all, it is the low temperature combustion of water contaminated ethanol and gasoline that causes the bulk of the formic acid to form; burning a slightly-contaminated mix of water (less than 1%) and ethanol quickly, in one long commute, will not likely cause any appreciable engine wear past the first 15 miles of driving, especially once the engine warms up and high temperature combustion occurs exclusively.

For those making their own E85, the risk of introducing water unintentionally into their homemade fuel is relatively high unless adequate safety precautions and quality control procedures are taken. Ethanol and water form an azeotrope such that it is impossible to distill ethanol to higher than 95.6% ethanol purity by weight (roughly 190 proof); regardless of how many times distillation is repeated. Unfortunately, this proof ethanol contains too much water to prevent separation of a mixture of such proof ethanol with gasoline, or to prevent the formation of formic acid during low temperature combustion. Therefore, when making E85, it becomes necessary to remove this residual water. It is possible to break the ethanol and water azeotrope through adding benzene or another hydrocarbon prior to a final rectifying distillation. This takes another distillation (energy consuming) step. However, it is possible to remove the residual water more easily, using 3 angstrom (3A) synthetic zeolite pellets to absorb the water from the mix of ethanol and water, prior to mixing the now anhydrous ethanol with gasoline in an 85% to 15% by volume mixture to make E85. This absorption process is also known as a molecular sieve. The benefit of using synthetic zeolite pellets is that they are essentially comparable to using a catalyst, in being reusable and in not being consumed in the process, and the pellets require only re-heating (perhaps on a backyard grill, in a solar reflector furnace, or with heated carbon dioxide gas collected and saved from the fermentation process) to drive off the water molecules absorbed into the zeolite. Research has also been done at Purdue University on using corn grits as a desiccant. [4] Once the ground corn becomes water logged, the corn grits can be processed much as the zeolite pellets, at least for a number of drying cycles before the grits lose their effectiveness. Once this occurs, it is possible to run the now water-logged corn grits through the natural fermentation process and convert them into even more ethanol fuel.
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