JP2892500B2 - Fuel additives and fuel compositions - Google Patents

Abstract

A reodorant additive for use in a liquid petroleum fuel, for example a middle distillate fuel such as a heating oil or a diesel oil, comprises a fuel-soluble ester having up to 25 carbon atoms. The ester may be in admixture with a perfume oil.

Description

The present invention relates to the use of reodorants in liquid petroleum fuels, for example intermediate fuel oils such as heated fuel oils.

Middle distillates are fuels obtained as crude kerosene and fractions between jet fuel fractions and heavy fuel oil fractions in crude oil refining. They are typically used as diesel fuel and heated fuel oil. A problem with middle distillate fuels is their odor, which can vary from acceptable to completely unacceptable to those near the oil, such as the user, depending on the source of the oil. Accordingly, there is a need to provide a method for reducing or neutralizing such oil odors.

It is known to mix esters into fuel oil.
For example, US-A-4,353,710 describes the addition of ester fuel extenders to hydrocarbon fuels heavier than gasoline. GB-A-2,115,004 is an aliphatic (C _{1 to} C
₆ ) Describes a hydrocarbon fuel additive composition comprising a mixture comprising an ester, the additive being for improving fuel efficiency and providing clean combustion.

The invention relates to the use of a flavoring additive for oils as described above, wherein said additive is or comprises an ester,
If desired, have a synergistic effect in combination with balm,
It is used without adverse effects in combination with components commonly used as additives to heated fuel oils, such as fuel oil burners and metal deactivators.

The invention relates in a first aspect to the addition of an additive comprising a first-mentioned ester which is soluble in a fuel, said ester having up to 25 carbon atoms and consisting of a carboxylic acid and an alcohol. A use in liquid petroleum fuels wherein the agent masks or reduces the odor of the fuel oil.

The finding that said esters can mask or reduce the odor of fuel oils is surprising as the latter odor is caused by the effect of many components. Thus, it would not have been expected that the use of the esters according to the invention could mask or reduce the odor of fuel oils.

If desired, the ester can be used in admixture with one or more aldehydes, ketones, alcohols and esters, and possibly a perfume oil containing a terpene, where the ester in the perfume oil is different from the first ester. The combined concentration of the ester and balm in the fuel required to produce an individual scented effect can be much less than the concentration of the ester or balm alone in the fuel required to produce a similar scented effect. That is, the ester and the balm can act synergistically.

The findings of the present invention can be economically important when balms are much more expensive than esters. Thus, the cost of a substance to produce a certain scenting effect will be lower with the present invention than when the perfume oil is used as the sole scenting agent.

In a second aspect, the present invention provides a liquid petroleum fuel body,
A first ester, which is soluble in the fuel, has up to 25 carbon atoms, and is composed of a carboxylic acid and an alcohol, is a perfume oil containing one or more aldehydes, ketones, alcohols and esters. (A different from 1 ester) in a mixed state with a small amount of a flavoring additive.

The first ester in the present invention has up to 25 carbon atoms as described above. Preferably, it has up to 20 carbon atoms, for example 4 to 14, especially 6 to 12, carbon atoms.
The carboxylic acids, preferably having 1 to 4 carbon atoms, can be, for example, saturated aliphatic monocarboxylic acids. Alcohols having preferably 3 or 4 to 10 carbon atoms can be, for example, saturated aliphatic monohydric alcohols. Preferred esters are (C ₄ ~C ₁₀₎ alkyl esters of acetic acid. Individual esters or mixtures thereof, for example n-heptyl acetate or n-hexyl acetate and n-acetate
Equimolar mixtures with octyl can be used. Esters, as would be known in the art, can be made, for example, by reacting a carboxylic acid with a suitable alcohol.

"Perfume oil" herein is any substance other than the first ester that has an odor that can mask the odor of the liquid petroleum fuel being treated when used alone. Perfume oils do not always impart a sweet or pleasant odor to the fuel. As noted above, such oils may include one or more aldehydes, ketones, esters and alcohols. For example,
It can be a blend containing all of the above and can include other components such as organic nitrogen compounds, lactones, ethers (including acetals and ketals), hydrocarbons, and other organic materials. Perfume oils can be, for example, proprietary blends. Examples of perfume oils can be proprietary blends and other proprietary fumes manufactured by Bush, boake and Allen.

In the practice of the present invention, the fuel can be a liquid petroleum product boiling between LPG and heavy fuel oil, for example, in the range of 100-500 ° C (eg, 150-400 ° C). It is preferably a diesel oil or a heated fuel oil, wherein the diesel oil is a middle distillate fuel as per ASTM standard, and the heated fuel oil is a middle distillate fuel used for heating, for example according to ASTM standard D-396-80. is there. It can include other components, if desired, such as fuel oil burners and / or metal deactivators, examples of which are known in the art. In addition, flow enhancers as known in the art can also be included.

Fuel oil auxiliary agents are compounds, such as organometallic compounds, that support the burning of heated fuel oil droplets by releasing chemically active metals at flame temperatures during use of the heated fuel oil. In this way, the catalyst surface is still provided for unburned hydrocarbons, resulting in a high conversion of soot generated. An example of such a fuel oil booster is an organometallic sandwich compound such as dicyclopentadienyl iron, commonly known as ferrocene, wherein each cyclopentadiene ring can be unsubstituted, or one or more. It can be independently substituted with further alkyl, cycloalkyl, aryl or heterocyclic groups.

Metal deactivators are components for deactivating metals that would otherwise degrade the oil during storage. Such degradation is due to unstable substances in the oil, such as unsaturated aliphatic hydrocarbons, resulting in sediments and gums that form, which can be caused by clogging of the fuel filter during use of the oil in the heating device. And disturb the fuel spray pattern when deposited in the burner nozzle, affecting overall performance. The cause of such degradation is the presence of copper from use as a component in the heating device; such copper catalyzes the degradation process. Examples of metal deactivators are secondary amine functionalities that permit the circulation of metal ions and macrohydrophobic side chain (s) sufficient to provide solubility in fuel.
Is a compound containing A particular example is a Mannich condensation product in the form of an alkylated phenol having a secondary amine side chain.

An example of a flow improver known in the art is ethylene /
Vinyl ester copolymers, fumarate / vinyl ester copolymers, phthalic acid derivatives, ethylene propionate and terpolymers containing ethylene and vinyl esters.

If desired, the fuel can further include components.
Some examples are dispersants and detergents such as polyisobutylene succinic anhydride polyamine blends known in the art and macrocyclic compounds as described in US-A-4,637,886 and US-A-4,880,923. Is referred to.

The ester, or the ester and the balm, can be provided in the fuel by the addition of the ester or a concentrate containing the ester and the balm. In a third aspect, the invention relates to a method for preparing a first ester comprising a carboxylic acid and an alcohol, which is soluble in a fuel, has up to 25 carbon atoms, and comprises one or more aldehydes, ketones, alcohols and esters. A perfume concentrate for addition to a liquid petroleum fuel, in a mixed state with a perfume oil (ester in the perfume oil is different from the first ester), and in a mixed state in a solution in a solvent therefor. I do. The solvent must be compatible with the fuel; examples are aromatic solvents such as those having an average C number of 9.

Concentrate has other components, such as fuel oil burner,
Metal deactivators, flow improvers, or dispersants / detergents as described above may be included. By way of general example, the composition of the concentrate may be in the following ranges in percentage by weight / weight: ester (1-25%), perfume oil (0.5-25%), fuel oil auxiliary (1-50%), metal Deactivator (2 to 25%)
And solvent (25-80%).

In all aspects of the invention where a balm is present, the relative proportions of the ester and the balm can be significant. Therefore, the ratio of ester to oil (weight of ester: weight of oil) is
It can be in the range of 1:20 to 20: 1, such as 5: 1 to 20: 1. In the first and second aspects in which the balm is present, the combined total proportion of the ester and the balm is, for example, up to 500 ppm (weight: weight), for example 5-200 ppm, for example 25-200 ppm
Can be

 The following are examples of the present invention.

Example 1 Preparation of Concentrate The following ingredients were mixed in the indicated proportions (all percentages are by weight: weight). The brand name and / or source will be given in parentheses.

Ester: n-heptyl acetate; VP 0.5 kPa ＠ 38
° C (9.6%) Aromatic oil: Proprietary oil containing a mixture containing one or more aldehydes, alcohols and esters (1.2%) (manufactured by Bush Bokeh &Array; Reference 11598) Fuel oil auxiliary agent: Ferrocene ( 3.66%) [Pluto] Metal deactivator: alkylated phenol having a secondary amine side chain (10%) Solvent: aromatic liquid with an average C number of 9 (75.54%) Use of concentrate Add the concentrate (1 liter) prepared in (1) to heated fuel oil (2000 liters) which has an unpleasant odor, and mix it thoroughly with shaking to make the concentrate 50 in the oil.
It gave 0 ppm, ie 48 ppm of ester and 6 ppm of perfume oil.

Test A sample of the heated fuel oil treated above was placed in a container and evaluated independently for odor by each of six people on each of five consecutive days each day for the odor, and the container was kept sealed during the evaluation. Each person rated the odor on a scale of 1-6 each day: 3 represents neutral odor; 3
Higher numbers represent an unpleasant odor, higher numbers represent a more unpleasant odor; less than three represent a more pleasant odor, and lower numbers represent a more pleasant odor. The average score is between 2 and 3,
It showed that the concentrate completely masked the unpleasant odor under the heated fuel oil.

Example 2 The procedure of Example 1 was repeated, except that the perfume oil was a proprietary oil designated BBA 11597 (manufactured by Bush Bokeh & Array), and the heated fuel oil contained 30 ppm of ester and 6 ppm of perfume oil after processing. did.

The average rating for the odor was as follows: Day: 1 2 3 4 5 Rating: 2 1/2 2 1/2 2 1/2 2 1/2 2 1/2 Example 3 The procedure of Example 2 was followed. Again, the perfume oil was a proprietary oil designated by BBA 11622 (manufactured by Bush Balk & Array).

The average rating for the odor was as follows: day: 1 2 3 4 5 Rating: 2 2 2 1/2 2 2 Example 4 The procedure of Example 2 was repeated, but the perfume oil is designated BBA 11621. It was a proprietary oil (made by Bush Bourke and Array).

The average rating for odors was as follows: Day: 1 2 3 4 5 Rating: 3 1/2 2 1/2 3 2 2 The above results should be to mask or improve unpleasant odors under heated fuel oil. 2 shows the effectiveness of the present invention. In each example,
The perfume oils and esters could not separately mask the unpleasant odor of the heated fuel oil at the above concentrations.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C11B 9/00 C11B 9/00 C (72) Inventor Hein Andreas Germany DE-5010 Bergheim im Gressen am Kirschgarten 34 Road 500 ( 72) Inventor Geschwentner Wolfgang Wilhelm Josef D-5000 Cologne, Germany 71 Am Schmiedgrun 74 (56) References JP-A-60-42493 (JP, A) JP-A-52-106809 (JP, A) U.S. Pat. No. 4,163,737 (US, A) West German Patent 78643 (DE, C) (58) Fields investigated (Int. Cl. ⁶ , DB name) C10L 1/18

Claims (17)

(57) [Claims] Claims: 1. An additive for middle distillate fuels, comprising a fuel-soluble first ester having up to 25 carbon atoms and comprising a carboxylic acid and an alcohol, and one or more aldehydes, ketones and alcohols. The additive as described above, wherein the additive comprises a mixture with a perfume oil, which is a perfume for a fuel, including an ester, wherein the ester in the perfume oil is different from the first ester. 2. The additive according to claim 1, wherein the first ester has 4 to 14 carbon atoms. 3. The additive according to claim 1, wherein the carboxylic acid has 1 to 4 carbon atoms. 4. The additive according to claim 1, wherein the alcohol has 3 to 10 carbon atoms. 5. The additive according to claim 1, wherein the acid is a saturated aliphatic monocarboxylic acid. 6. The alcohol of the first ester is a saturated aliphatic 1
The additive according to any one of claims 1 to 5, which is a polyhydric alcohol. 7. The additive according to claim 1, wherein the first ester is an alkyl ester of acetic acid. 8. The additive according to claim 1, wherein the fuel is a heating oil. 9. The weight ratio of the first ester to the perfume oil is 5: 1 to 20: 1.
The additive according to any one of claims 1 to 8, wherein 10. A fuel composition comprising a large proportion of a middle distillate fuel and a small proportion of a scented additive, wherein the additive comprises up to 25 carbon atoms and comprises a carboxylic acid and an alcohol.
Contains a mixture of a fuel soluble first ester and a perfume oil that is a fragrance to the fuel, including one or more aldehydes, ketones, alcohols or esters, and wherein the ester in the perfume oil is different from the first ester Wherein the total concentration of the first ester and the balm in the fuel is by weight
The above composition, wherein the composition is 500 ppm or less. 11. The composition according to claim 10, wherein the fuel is a heating oil. 12. The composition according to claim 10, wherein the first ester has 4 to 14 carbon atoms. 13. The composition according to claim 10, wherein the carboxylic acid has 1 to 4 carbon atoms. 14. The composition according to claim 10, wherein the alcohol has 3 to 10 carbon atoms. 15. The method according to claim 15, wherein the acid is a saturated aliphatic monocarboxylic acid.
A composition according to any one of claims 10 to 14. 16. The composition according to claim 10, wherein the alcohol of the first ester is a saturated aliphatic monohydric alcohol. 17. The composition according to claim 10, wherein the first ester is an alkyl ester of acetic acid.