JPS5920712B2 - liquid hydrocarbon fuel composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a novel liquid hydrocarbon fuel having excellent dispersibility and anti-icing and anti-corrosion properties.

More particularly, this invention relates to a fuel composition comprising a large amount of a liquid hydrocarbon fuel and a small amount of at least one Mannitz base or derivative thereof dissolved or substantially stably dispersed therein. BACKGROUND OF THE INVENTION Due to the ever-increasing demands placed on internal combustion engines in terms of performance, cleanliness, etc., it has become necessary to develop even better fuels for use therein.

In particular, it is desirable that such fuel have the following properties: In other words, in order to eliminate the deposition of insoluble impurities on the engine parts and the subsequent wear, such insoluble impurities can be dispersed, there is no icing at low temperatures, and there is no rust on the engine parts. It has less tendency to corrode. To this end, various additives have been developed to provide fuel with these properties. It is an object of this invention to provide a liquid hydrocarbon fuel composition for use in internal combustion engines and others. Another object of the present invention is to provide a fuel composition that has excellent dispersibility and anti-corrosion properties and is less prone to icing at low temperatures. A further object of the present invention is to provide a fuel composition containing an additive that imparts the above-mentioned properties to &A fuel.

As stated above, the above objects &L are achieved by providing a fuel composition containing certain Mannitz bases or derivatives thereof.

This Mannitz compound has the formula R1 (H2N<nini)c(
In this formula, R1 is a mono- or polyhydroxy-substituted aromatic group, an alkyl aromatic group, or a substituted alkyl aromatic group, R2 is a hydrogen group, a lower alkyl group, or a hydroquine-substituted lower alkyl group, and R3 is a hydroxy-substituted lower alkyl group or -R4N (group, R4 is a lower alkylene group, R5
is a hydrogen group, a lower alkyl group or a hydroxy-substituted lower alkyl group, R6 is a hydroxy-substituted lower alkyl group, and X is the valence number of R1).

As mentioned above, R1 is a hydroxy-substituted aromatic group or the like. Therefore, it is phenol, catechol,
It may be derived from compounds such as resorcinol, alpha-naphthol or beta-naphthol. Particularly preferred are alkyl aromatic groups derived from these compounds, particularly those containing at least about 30 alkyl groups, preferably about 1 alkyl group.
Monoalkylaromatic radicals containing up to 00 carbon atoms are preferred. In this invention, substituted alkyl groups are considered to be completely equivalent to the above-mentioned alkyl groups.

A "substituted alkyl group" in this sense refers to an alkynole group containing a substituent that does not significantly change the properties or reactivity of the alkyl group. Examples of such substituents are listed below. Ether group (especially lower alkoxy group), keto group, ester group (especially lower carbalkoxy group), aminoacyl group (amide group), nitro group, thioether group, sulfonic group, sulfonic acid ester, amide, etc.

Generally, there will be no more than about 3, and preferably no more than 1 such substituent for every 10 carbon atoms of the alkyl group.

In preferred compounds for use in the fuel compositions of this invention, R1 is a monohydro-closed monosubstituted alkyl aromatic group in which the alkyl group contains about 10 to 20 carbon atoms.

The integer X is usually 1 or 2 (although it may also be the number of aromatic carbon atoms unless substituted), preferably 1, so that the preferred additive compounds of the invention are aromatic or similar It is one of the substances (Mannitsu bases). In preferred compounds, each of R2 and R3 is a hydroxy-substituted lower alkyl group.

As used herein, "lower alkyl" refers to an alkyl group having 7 or less carbon atoms. Preferably, this group is a hydroxyethyl group. Any valences of nitrogen atoms not filled by such groups are filled by hydrogen or lower alkyl groups. Similarly, the compounds used in the fuels of this invention are such that R3 is -R4N (where R4
is a lower alkylene group (usually an ethylene group), R5 is hydrogen or a lower alkyl group or a hydroxy-substituted lower alkyl group, usually a hydroxyethyl group, R6
is a hydroxy-substituted lower alkyl group, usually a hydroxyethyl group). Compounds of this type are derived from hydroxyalkyl-substituted alkylene diamines such as 2-(2-aminoethylamino)ethanol. The Mannitz bases used in the fuel compositions of this invention include suitable hydroxyaromatic compounds, formaldehyde or its reversible polymers (e.g., paraformaldehyde, trioxane), and formula
is conveniently obtained by Mannitz reaction with an amine.

This reaction is carried out at room temperature to about 225°C, usually about 50°C to about 225°C.
The amount of each reagent was such that the molar ratio of hydroxyaromatic compound to formaldehyde to amine was approximately 1.
:1:1 to about 1:3:3. To facilitate this reaction, it is often convenient to use inert diluents such as aliphatic or aromatic hydrocarbons (eg petroleum fractions, toluene, xylene).
Suitable methods for making Mannitz bases are described in US Pat. No. 2,033,092 and US Pat. No. 3,297,597.

Also suitable for use in the fuels of this invention are adducts of at least one epoxide with one or more of the above Mannitz bases.

Such additives impart demulsifying properties to the fuel in addition to the properties described above. The epoxides used to prepare the adducts are, for example, commercially available mixtures of ethylene oxide, propylene oxide, glycidyl ethers, butyl epoxy stearate or alpha olefins containing about 11 to 14 carbon atoms. Manufactured epoxy resin.

Lower alkylene oxides, especially ethylene oxide and propylene oxide, are preferred (for the preparation of Mannitz base-epoxide adducts, these may be mixed in proportions of up to about 20 moles of epoxide per mole of Mannitz base, with a sufficient amount for the reaction to occur). at a suitable temperature (usually about 25 to 125°C) for a certain period of time.
This is done by keeping the

For details of this reaction, see U.S. Pat.
See No. 7. The following examples describe typical compounds useful in the fuels of this invention and methods of making them.

All parts are by weight. Example 1 79 parts of tetrapropene-substituted phenol in 900 parts of xylene
A solution of 8 parts (3 moles) was heated to 100°C and 462 parts (4.5 moles) of diethanolamine were added.

This mixture was further heated to 120° C., and 198 parts (6 mol) of paraformaldehyde was slowly added to the mixture to avoid foaming as much as possible. After the addition of paraformaldehyde had ended, the mixture was heated to 140° C. for 10 hours, during which water was removed by distillation. This was then filtered to obtain a 40% xylene solution of the desired Mannitz base. This solution contained 2.65% nitrogen. Example 2 79 parts of tetrapropene-substituted phenol in 989 parts of xylene
A solution of 8 parts (3 moles) was heated to 100°C and 598 parts (4.5 moles) of diisopropanolamine were added.

The mixture was heated to 120°C and 198 parts (6 moles) of paraformaldehyde was slowly added. Temperature 21
The temperature was increased to 0°C and held for 8 hours, and the water was removed by distillation. This was filtered to obtain a 60% xylene solution of the desired product. This solution contained 2.13% nitrogen. Example 11 (1-2-3) 798 parts (3 mol) of tetrapropene-substituted phenol in 900 parts of xylene at 100°C
468 parts (4.5 mol) of 2-(2-aminoethylamino)-ethanol was added to the heated solution.

The mixture was heated to 120°C and 198 parts (6 moles) of paraformaldehyde was slowly added. After the water evolution was complete, the mixture was cooled and xylene was added to produce a 60% solution of Mannitz base. After filtration, add 2.
The desired product containing 0% was obtained. Example 4 1257 parts of polyisobutene substituted phenol (the molecular weight of this polyisobutene substituted product is about 300) in 1321 parts of xylene (
3 mol) solution was heated to 90° C., 630 parts (6 mol) of diethanolamine was added, and then 198 parts (6 mol) of paraformaldehyde was slowly added to avoid foaming as much as possible.

The mixture was heated to 145° C. for 9 hours, during which water was distilled off. This was then filtered to obtain a 60% solution of the desired Mannitz base in xylene. This solution is 2.49
% nitrogen. Example 5 625 polyisobutenylphenol (molecular weight approximately 1000) in 489 parts of mineral oil
Heat the solution of 1 part to 120°C and add 2 parts of paraformaldehyde.
5 parts (0.75 mol) were added slowly.

The mixture was heated to 160° C. for 1 hour, during which water was removed by distillation. This was then cooled to 90°C and 79 parts (0.75 mol) of diethanolamine was added. The temperature was increased to 120°C, and paraformaldehyde 33
(1 mol) was added. The temperature was increased to 160°C and held for 6 hours while water was removed by distillation. The mixture was then filtered to obtain the desired Mannitz base in mineral oil.
% solution was obtained. This solution contained 0.7% nitrogen. Example 6 910 parts of hebutylphenol in 1358 parts of xylene (
A solution of 4.74 mol) was heated to 80° C. and 997 parts of diethanolamine were added.

The mixture was heated to 110° C. and 313 parts (9.48 moles) of paraformaldehyde was slowly added. The mixture was then heated to 140° C. while water was removed by azeotropic distillation. The residue was cooled and filtered to give the desired product as a 60% solution in xylene (containing 3.93% nitrogen). Reference Example A mixture of 423 parts (1.59 moles) of the product of Example 1 and 205 parts of xylene was heated to 100° C. and 185 parts (3.18 moles) of propylene oxide were added.

This mixture was heated at 100°C for 16 hours, then at 160°C.
Stripping was performed at °C/1011 Hg. Xylene was added to make a 60% solution of the product. This solution contained 4.9% hydroxyls after filtration. In addition to the Mannitz bases or derivatives thereof described above, the fuel compositions of the present invention contain highly hazardous and normally liquid hydrocarbon fuels, such as aircraft or motor gasoline, diesel fuel as defined in ASTM Specification D396. Contains petroleum distillates such as fuel or fuel oil.

Particularly preferred is gasoline, i.e., an ASTM gas with a 10% distillation point of about 60°C to a 90% distillation point of about 205°C.
It is a mixture of hydrocarbons with a boiling point. Such gasolines are further described in ASTM Specification D439-68T. In the compositions of this invention, the Mannitz base is dissolved or substantially stably dispersed in the fuel. This base is normally dissolved, but
The invention is also intended to include fuel compositions that are stable dispersions (eg, sols or similar colloids), especially those containing residual fuel. The amount of Mannitz base used is sufficient to disperse solids, prevent icing, and prevent rust formation. Usually this amount is about 1 to 10,000 parts by weight, preferably 4 to 1,000 parts by weight per million parts by weight of the final composition. The Mannitz base can be included in the fuel by simply mixing it with the fuel at the desired concentration.

Alternatively, it is first dissolved in a flammable solvent, preferably a hydrocarbon solvent having a boiling point below about 250° C., such as naphtha, benzene, toluene, xylene, gasoline or light mineral oil, containing up to about 80% Mannitz base. A flowable concentrate may be created and then added to the fuel to obtain the final fuel composition. In addition to the 3 Mannitz base or its derivatives, the fuel compositions of the present invention may contain other additives well known to those skilled in the art.

These additives include anti-knock agents such as tetraalkyl lead compounds, lead scavengers such as haloalkanes, anti-adhesion agents and modifiers such as phosphoric acids, 4-aryl compounds, dyes, and 2,6-di-tertiary aryls. - antioxidants such as butyl-4-methylphenol, auxiliary rust inhibitors such as alkylated succinic acids, auxiliary dispersants such as reaction products of polyalkylene polyamines and alkylated succinic acids,
These include bacteriostatic agents, gum inhibitors, metal deactivators, upper cylinder lubricants, demulsifiers, de-fogging agents, etc. A typical fuel composition of this invention includes gasoline (leaded or unleaded) and the following additives:

The amounts of additives below are parts by weight per million parts of final composition. This composition is applied to [Chevrolet, carburetor, clean up and exhaust emission,
submitted to the test.

This test was conducted on a 1968 Chevrolet - 307 cubic inch V
-8 engine and a 1-cylinder 4-stroke Briggs & Stratton engine. The exhaust gas from the Blitz & Stratton engine is replaced by Chevy's best air system.
Cleaner to promote deposit formation only in the deposit formation phase of this test. The Chevrolet engine operates at medium load speed conditions. The one cylinder engine is operated at 2000 rpm and is not continuously loaded during the deposit formation period.

Approximately 20% of the supply to the Chevrolet engine is exhaust gas from the one cylinder engine. This type of deposit-forming operation produces strong deposits in the vaporizer within 10 hours.
The idle speed of the Chevrolet engine is below 375 rpm (
When the initial speed is reduced to 700 rpm), deposit formation stops. Once the deposit formation phase is complete, hydrocarbon emissions are generally below the initial level of about 6000 ppm.
The amount increases from 40,000 ppm to 40,000 ppm.

The deposit formation phase is followed by a purification phase using dispersant treated fuel. The evaluation of this test is based on the degree of reduction of emissions (hydrocarbons and carbon oxides) during the purification phase. Calculate emissions improvements for hydrocarbons and carbon monoxide. It also calculates improvements in idle speed. When the above fuel composition was subjected to this test, the percent emission reduction was 74% for hydrocarbons and 25% for carbon oxides.

The improvement rate in idle speed was 100%. In the above composition, substantially the same results were obtained when the products of Examples 2 to 6 were used instead of the product of Example 1.

Claims (1)

[Scope of Claims] 1. A large amount of liquid hydrocarbon fuel and a small amount of formulas dissolved or substantially stably dispersed therein ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (Here, R^1 is monohydroxy a substituted alkyl phenyl group containing from 7 to about 70 in total in the alkyl group;
R^2 is an alkanol group having 2 or 3 carbon atoms, R^3 is an alkanol group or aminoethyl group having 2 or 3 carbon atoms) A liquid hydrocarbon fuel composition comprising one type of compound.