CZ303291A3 - fuel mixture containing additive based on side products from cyclohexanone preparation process - Google Patents

Abstract

The fuel composition comprises a hydrocarbon component in an amount 60 to 99.9 wt. and a by-product additive from the production of cyclohexanone in an amount of 0.1 to 40 wt. Ingredient is a mixture of C.sub.5 .n.a and C.sub.6. C.sub.3. C.sub.5 to C.sub.7.cyclic alcohols, C.sub.3 C.sub.7 .n.al. Dehyd, C.sub.5 .n.and C.sub.6 .n.cyclic ketones, esters of C.sub.1 to C.sub.3 % acids with a content of up to 5 wt. water.

Description

The present invention provides a fuel composition comprising an antiphase and / or homogeneous additive based on a mixture of hydrocarbons, alcohols, aldehydes, ketones and esters obtained as a by-product in the manufacture of cyclohexanone.

In the oxidation process of cyclohexane production by air, in addition to the main products of cyclohexanone and cyclohexanol, a diverse mixture of by-products is formed. This mixture was separated by distillation into various fractions. A fraction of so-called " alcohol fractions at the top of the atmospheric rectification column at temperatures of 120 to 155 ° C. The mixture contains 0.1 to 6 wt% C5 and C6 hydrocarbons, 15 to 92 wt%. % aliphatic C3 to C6 alcohols, 0.2 to 40 wt. % cyclic C5 to C7 alcohols, 0.3 to 21 wt. % C3 to C7 aldehydes, 0.5 to 50 wt. % cyclic C5 to C6 ketones, 0.2 to 10 wt. % of C1 to C3 carboxylic acid esters and 0.1 to 5 wt. water.

BACKGROUND OF THE INVENTION

A number of uses of the fraction are known. Without further physicochemical treatment, it is calculated according to C 8. A0 240 329 uses paints and varnishes as an organic solvent and / or diluent and / or a component thereof, most often in a mixture with butyl acetate and amyl acetate. Similarly, this fraction * is used for the production of diluents and / or solvents in admixture with cyclohexane and cyclohexanol distillation residues (CS.PV 3802-89 and rV 05078-89 K). A disadvantage of the application of these untreated alcohol moieties as a solvent and diluent component is the unpleasant odor inherent in the fraction itself.

The use of these diluents and solvents is problematic for this reason, especially for interior coatings. This drawback is overcome by hydrotreating and the alcohol fraction to remove unsaturated hydrocarbons and aldehyde compounds (C & AO 270 520, 1991 f / AO 271 537, 1991).

Another way of utilizing the fraction of alcohol fractions from rectification refining and containing up to 28 wt. The water is, after the sedimentation of water, its application as a component of gasoline. Protected is the use of said fraction as a component for low-leaded gasoline up to 0.3 g Pb / l and unleaded gasoline in an amount such that the resulting gasoline mixture contains 0.2-10% by weight. %, preferably 1 to 5 wt. alcohol fraction.

A modification of this application of said alcohols is their use as a component over low-lead and unleaded gasoline in an amount of 0.1 to 10% by weight. together with a C2 to C4 fraction of aliphatic alcohols which are ethyl alcohol, n-propanol, isopropanol, π-butanol, isobutanol, or mixtures thereof.

When searching for further application resp. usage of so-called. The alcohol fractions from cyclohexanone production were further worked out. One of them is their use for the production of individual components, mainly amyl alcohol and its subsequent use for the production of amyl acetate as one of the basic components of solvents and diluents. The amyl alcohol may be used alone as part of the solvents or may be used to produce 1-pentene. However, such processing of alcohol fractions is investment and energy intensive even though the products are of interest to other applications.

For this reason, a method for applying said mixture as an additive for motor fuels has been reworked. From the study of the application of the leading alcohol fractions to the additivation of low-lead and unleaded gasoline as well as the problems of homogeneity of diesel fuels at temperatures below -5 ° C, mainly and higher water content, petrol. For various reasons, motor fuels may contain higher water concentrations or higher boiling hydrocarbons. Water is the cause of the phase separation of the fuel into the aqueous and hydrocarbon phases. Higher boiling hydrocarbons cause the solidification point of the fuel to rise. In the case of a higher water content, water crystallization occurs at low temperatures and a slurry of water crystals is formed in the hot fuel causing clogging of the fuel lines. These problems are overcome by the application of the alcohol moieties of the present invention.

3 Summary of the Invention

The present invention provides a fuel composition comprising an antiphase and / or homogenizing additive characterized in that it is comprised of a hydrocarbon component in an amount of 60 to 99.9 wt%, preferably 80 to 90 wt%, and an antiphase and / or homogenizing additive in the % of 0.1 to 40% by weight, preferably 10 to 20% by weight, the antiphase and / or homogenizing additive comprising 0.1 to 6% by weight. % C5 and C6 hydrocarbons, 15 to 92 wt. aliphatic C 1 to C 2? % of alcohols, 0.2 to 40 wt. cyclic to C? % of alcohols, 0.3 to 21 wt. to C? % aldehydes, 0.5 to 50 wt. % cyclic and C? ketones, 0.2 to 10 wt. % of carboxylic acid esters and 0.1 to 5 wt. water. The hydrocarbon component is diesel fuel with a boiling point of hydrocarbons between 130 and 370 ° C or low-lead and unleaded motor gasolines.

The anti-phase and / or homogenizing additive is a by-product from the manufacture of cyclohexanone. The oxygenated compounds present in the additive promote fuel combustion, improve economy and reduce harmful emissions. In the case of diesel fuels which are a mixture of higher boiling hydrocarbons and a higher pour point and which have a lower ability to dissolve water into a homogeneous mixture than autobenzines, they can be additive to a mixture containing up to 40% by weight. alcohol fractions. The amount of alcohol content that is added to diesel fuel depends on the water content of the fuel, the temperature of operation of the diesel engines (at lower temperatures a mixture with a higher content of alcohol content is preferred) as well as the water content of the alcohol content. Preferably, the alcohols contain up to 1 wt. water. Then, e.g. by addition of 15% alcohol, lower the freezing point from -4 ° C to -26 ° C.

For automotive gasoline, the use of more than 10% alcohol fractions is advantageous in view of their ability to synergize fuel quality.

It is also suitable to add an antioxidant of up to 1% by weight to the fuel composition prepared according to the invention. to the total amount of the mixture.

The following examples illustrate the invention.

Examples of embodiments of the invention

21.0 mg / 100 cm below -55.0 ° C 0.02 ° C;

Example 1 *

The mixture of by-products resulting from the production of cyclchexanone contained:

2,61% by weight of C5 and C6 hydrocarbons,

67.62% wt. aliphatic C3 to C6 alcohols,

15.20 wt. cyclic C5 to C6 alcohols,

3.84 h. C3 to C7 aldehydes,

7.38% wt. cyclic C5 to C6 ketones,

2.70 wt. carboxylic acid esters,

0.65% wt. waters

The mixture was 15% by volume. mixed with 85% vol. with gasoline from the commercial network, which had OCMM and OCMM 81. For the mixture thus obtained, the octane numbers of OCMM 91.7 and OCMM 81.9 were determined. Further analyzed results: Resin content

Crystallization point Sulfur content Distillation test:

- start of distillation

- 10% vol. distills up to τ 50% vol. distills into

- 95% vol. distills into

- end of distillation Distillation residue Distillation loss

The analyzes found show that the addition of a mixture of the compounds of the present invention achieves the same and even better octane numbers than the autobenzine without the mixture. The addition of a mixture of oxygen compounds improves fuel combustion efficiency and reduces emissions.

28,0 ° C 39,0 ° C 103,0 * C 177,0 ° C 191,0 ° C 1,0¾ Vol. 1,0% vol.

- 5 Example 2

The mixture of by-products resulting from the preparation of cyclohexanone of the same composition as in Example 1 was 15% by volume. mixed with diesel fuel NM-4 (ČSN 65 6506) in the amount of 85% vol. The mixture thus prepared has the following values:

Cetane index 45 Flash point 41 'C Pour point - 26 ° C Filterability point - 21 ^e C Sulfur content (XRF) 0.36% wt. Distillation test: - start of distillation 122 * C - distils up to 170 ° C 21,0% vol. - distills up to 350 ° C 98,5% vol. - end of distillation 346 * C Total distilled 98,5% vol.

The analyzes found show that the addition of a mixture of oxygen compounds to diesel fuel according to the invention is a very advantageous use of the by-products of cyclohexanone production. At the same time, their presence improves diesel fuel parameters, in particular by promoting the combustion of fuel in the engine, thereby increasing engine performance, improving its economy and reducing emissions.

Claims (4)

CLAIMS 1. A fuel mixture comprising an anti-phasic or homogeneous additive based on by-product from cyclohexanone production, characterized in that it consists of a hydrocarbon component in an amount of 60 to 99.9% by weight, preferably 80 to 90% by weight. and an antiphase and / or homogenizing additive in an amount of 0.1 to 40 wt%, preferably 10 to 20 wt%, the antiphase and / or homogenizing additive comprises 0.1 to 6 wt%. % C5 to C6 hydrocarbons, 15 to 12 wt. % aliphatic C3 to C7 alcohols, 0.2 to 40 wt. cyclic C5 to C5 % C7 alcohols, 0.3 to 21 wt. % C3 and C7 aldehydes, 0.5 to 50 wt. % of cyclic C5 and C6 ketones 0.2 to 10 wt. esters of C1 to C3 carboxylic acids and 0.1 to 5 wt. water. 2. The fuel mixture of claim 1, wherein the hydrocarbon component is a mixture of liquid hydrocarbons boiling in the range of 120 to 370 ° C. 3. The fuel composition of claim _14, wherein the hydrocarbon component is motor gasoline in an amount of 65 to 89.9% by weight. to the total amount of fuel. 4. The fuel mixture of claims 1,2 and 3, wherein said fuel composition comprises an antioxidant in an amount of 0.001 to 1% by weight. to the total amount of the mixture.