EP1409615A1

EP1409615A1 - Method for reducing the emissions of fossil fuels

Info

Publication number: EP1409615A1
Application number: EP02727501A
Authority: EP
Inventors: Horst Dr. Med. Kief
Original assignee: Individual
Current assignee: Individual
Priority date: 2001-03-30
Filing date: 2002-03-28
Publication date: 2004-04-21
Also published as: WO2002079352A1; DE10116115A1

Abstract

The invention relates to the use of glyoxal in an aqueous solution or the acetals of said glyoxal in a mixture of ketone containing between 1 and 9 C atoms and an alcohol containing between 1 and 6 C atoms. The volumetric portions of ketone and alcohol are at least 0.5 to 5 times the quantity of glyoxal. Up to 10 vol. % of an additive of this type can be added to a mineral-oil fuel such as petrol, diesel or kerosene.

Description

Process for reducing pollutant emissions for fossil fuels

DE19920270A1 discloses an additive for reducing pollutant emissions in fossil fuels (hereinafter also referred to as mineral oil fuels, in contrast to biofuels made from vegetable or animal raw materials), the essential component of which consists of glyoxal in aqueous solution. The tendency towards phase separation of the glyoxal in aqueous solution from the hydrocarbons is solved there by using emulsifiers and solubilizers, including esterified alifates and polyethylene glycol, or by the acetal formation of the glyoxal, as a result of which the solution in hydrocarbons is properly guaranteed. Acetals are commonly considered stable compounds. Surprisingly, however, it has been shown that the 1, 1, 3,3-tetramethoxyethane, like the corresponding acetal formed with ethanol, are by no means stable compounds in the case of long-term storage. After about 3 to 4 months, the glyoxal acetals gradually decompose with the formation of glyoxal and absorption of water, which means that their sole use as a fuel additive inevitably involves risks. Possible damage to the engine by settling the aqueous phase from the acetal decay can be prevented by adding emulsifiers and solubilizers, but the emulsifiers already mentioned, such as various surfactants, polyethylene glycols and esterified alifates, are themselves relatively slow-reacting substances and are therefore responsible for the combustion process, e.g. of gasoline fuels by no means very suitable, since in principle they are emulsions. The same applies in principle to sorbitan monooleates, as are disclosed, for example, in DE3042124A1. Although the proportions of these substances in such a fuel-water mixture are relatively small, in principle the disadvantage of a relatively sluggish oxidative reaction also applies here.

These disadvantages are eliminated by the innovation to be proposed, both for the glyoxal acetals and for the aqueous solution of the glyoxal Use as an additive for fossil fuels. For this purpose, the aqueous glyoxal is first mixed with 0.5 to 5 times, preferably 2 to 3 times the amount of a ketone with 3 to 9 carbon atoms, acetone, methyl ethyl ketone, methyl isopropyl ketone and di-isopropyl ketone being preferred. After shaking briefly, a water-clear solution is formed without any phase separation. Then another 0.5 to 5, preferably 2 to 3 parts of mono- or polyvalent, linear or branched alcohol having 1 to 6 carbon atoms, preferably ethanol or isopropyl alcohol, are added. The alcohol added can also consist partly of methanol, methanol and isopropanol being relatively advantageous as octane boosters. Only methanol is not preferred because it lowers the boiling point of the mixture.

Commercially available glyoxal solution is usually supplied by the chemical industry as a 40% aqueous solution. In the case of diesel fuel in particular, it can be of considerable advantage to add pure water to the glyoxal solution, since a water-diesel emulsion in the combustion chamber is obviously better atomized by the injection nozzle, which makes combustion more homogeneous and therefore a reduction in pollutant emissions has also been reported. It is therefore of particular advantage to dilute the glyoxal solution and add up to 80% water in up to 15% by volume to the diesel fuel. The emulsifier and stabilizer from the group sorbitan monooleate, fatty alcohol ethoxylate and polyisobutene or mixtures thereof are preferably mixed in an amount of 0.1 to 2% of the H ₂ 0, the sorbitan monooleate should preferably make up two thirds of the emulsifier. A long-term stable water / fuel emulsion is formed if a water / ketone mixture in a ratio of 1: 2.5 or higher was used.

When using the glyoxal acetals described above as fuel additives, a third by volume of acetone with the corresponding parts by volume is sufficient alcohols described above to make the gradual decomposition of acetals risk-free.

The additive mixture described can be added up to 10% by volume to the respective fuel, be it gasoline as a gasoline or diesel oil. The use of such an additive mixture with a volume fraction of 1: 1000 to 1: 100 is particularly advantageous. In this order of magnitude, reductions in carbon monoxide unburned hydrocarbons and lowering of NOx are observed, as previously described in PCT / EP 99/06949, while controls with diesel engines were carried out by independent test institutes (Automotive Testing and Development Services Inc., Ontario, California 91761) however, significantly higher significant reductions in soot contents up to 54% were found with a mixture ratio of fuel to additive 500: 1.

Test results with a 1999 Freightliner FL70 truck with Caterpillar turbo diesel engine, type 3126 and the additive according to the innovation

Test Testidenti- THC NOx CO Opacity Consumption of soot fractions fiction no. (Turbidity) (FE) (PM)

B-1 N2C0453 0.173 9.91 2.325 4.5 7.922 0.212 B-2 N2C0454 0.167 10.588 2.369 3.97 7.808 0.21

Mean 0.170 10.249 2.347 4.235 7.865 0.211

A-1 N2C0456 0.153 10.418 2.341 4.2 7.548 0.097 A-2 N2C0457 0.175 10.065 2.304 4.23 7.459 0.097

Mean 0.164 10.242 2.323 4.215 7.504 0.097

Delta 4% 0% 1% 0% 5% 54% Test results with a 1996 Dodge RAM 2500 pickup truck with Cummins turbo diesel engine, type 12valve 5.9L and the additive according to the innovation

B-1 N2C0437 0.197 7.439 1.066 77.6 16.219 0.172 B-2 N2C0439 0.237 7.846 1.43 77.8 16.08 0.09 B-3 N2C0440 0.245 7.358 0.919 75.9 16.396 0.063

Mean 0.226 7.548 1, 138 77.100 16.232 0.108

A-1 N2C0441 0.202 6.59 0.857 81, 1 16.278 0.063 A-2 N2C0442 0.145 6.628 1, 232 74 16.238 0.093 A-3 N2C0443 0.216 6.828 0.75 72.6 16.307 0.055

Mean 0.188 6.682 0.946 75.9 16.274 0.070

Delta 17% 11% 17% 2% 0% 35%

In the tables above, THC = unburned hydrocarbons, NOx = nitrogen oxides, FE = gallons PM = particles as turbidity k [nrf ¹ ]

However, the process has the advantage over the previously described process that it is much cheaper to produce because of its simple miscibility, the risk minimization due to the ability to absorb water in the case of acetal decomposition, and the advantage of better energy utilization through the use of high-energy substances such as acetone and the alcohols described, while at the same time Avoidance of relatively unreactive substances such as the emulsifiers and solubilizers already described. The use of acetone and isopropyl alcohol is also cheaper due to their evaporation pressure in gasoline. Microscopic inspection of a 6% additive-gasoline mixture with glyoxal, H ₂ 0, acetone and isopropyl alcohol shows that the aqueous glyoxal solution in the Fuel is finely dispersed, although the fuel-additive mixture is macroscopically completely clear and shows no milky opalescent shimmer. In addition, the aqueous glyoxal solution must have a biocidal effect due to its aldehyde properties, for example in large-volume diesel tanks, for example in order to inhibit growth by the so-called diesel algae. The process also has the advantage that only large-scale industrial products are used.

Claims

claims

1. A process for reducing pollutant emissions in internal combustion engines with mineral oil fuels, characterized in that 0.1 to 5% glyoxal in aqueous solution or 0.05 to 2% acetals of glyoxal with alcohols of 1 to 4 carbon atoms in an additive mixture from ketone with 3 to 9 carbon atoms and a mono- or polyhydric, linear or branched alcohol with 1 to 6 carbon atoms are added to the fuel.

2. The method according to claim 1, characterized in that the ratio of the volume of the aqueous glyoxal solution to ketone and to alcohol such as

1: 2 to 5: 1 to 5.

3. The method according to claim 1 to 2, characterized in that the alcohol content of the additive consists of methanol and ethanol or isopropanol or mixtures thereof.

4. The method according to claim 1 to 3, characterized in that when using an aqueous glyoxal solution, a solubilizer is additionally used, which is selected from sorbitan monooleate, fatty alcohol ethoxylate and polyisobutene.

5. The method according to claim 1, characterized in that when using glyoxal acetals the fuel is a mixture of glyoxal. Ketone and alcohol are mixed in a ratio of 1: 0.2 to 5: 0.2 to 5% by volume.

6. The method according to claim 1 to 7, characterized in that when using an additive mixture of aqueous glyoxal solution and Glyoxalace- This mixture is dissolved in ketone and alcohols before it is added to the petroleum fuel.

Process according to Claims 1 to 8, characterized in that the additive mixture is added to the fuel in a ratio of 1:10 to 1: 10,000, preferably 1: 100 to 1: 1,000