DE1243916B - Fuels with a high liter calorific value based on hydrocarbons - Google Patents

Description

Hydrocarbon-based fuels with a high calorific value per liter Die The invention relates to high-calorific value fuels based on hydrocarbons.

Fuels for spark ignition and compression ignition internal combustion engines, Combustion turbines and jet engines are mostly hydrocarbons or hydrocarbon mixtures, in particular hydrocarbon mixtures obtained from petroleum, such as gasoline, kerosene and gas oil. Aviation turbine fuels are often mixtures of heavy gasoline and kerosene. These petroleum hydrocarbon mixtures, which are often used as fuels, have a relatively low liter calorific value.

The object of the invention is to produce fuels based on hydrocarbons to create that have relatively high liter calorific values.

This object is achieved by the fuels according to the invention with a high liter calorific value based on hydrocarbons, which are characterized in that they are a substituted fulvene of the general formula in which RI is an unsubstituted or C1-C4-alkyl-substituted phenyl radical, R2 = RI or a C1-C4-alkyl radical, R3 is a C1-C4-alkyl radical and n = 0 or 1, and / or a derivative of a fulvene of the above formula , in which one or two of the fulvene double bonds are hydrogenated, and / or a cyclopentyl compound of the general formula in which R1, R3 and n have the meaning given above, contained as a high-energy component.

The fuels with a high calorific value preferably contain one larger proportion of a distillate fuel, for example under atmospheric pressure a boiling range of 25 to 350 ° C and preferably a boiling range of 120 up to 300 ° C.

Examples of as a high-energy component in the inventive Fuels suitable fulvene are methylphenyl, ethylphenyl, propyl and isopropylphenylfulvene, the butylphenylfulvene and the corresponding fulvenes, in which the cyclopentadienylidene radical carries a methyl, ethyl, propyl, isopropyl or a C4-alkyl group, furthermore the corresponding fulvenes, in which the phenyl radical with a methyl, ethyl, Propyl, isopropyl or C4-alkyl radical is substituted, the corresponding fulvenes, in which both the cyclopentadienylidene radical and the phenyl radical with a Methyl, ethyl, propyl, isopropyl or a C4 radical is substituted, diphenylfulvene and its derivatives in which one or both of the phenyl radicals and / or the cyclopentadienylidene radical substituted by a methyl, ethyl, propyl, isopropyl or C4-alkyl radical are, and also the partially hydrogenated derivatives of the fulvenes according to the above Definition, also the cyclopentyl compounds according to formula II.

Preferred high-energy components are diphenyl, methylphenyl, Diphenyl-2-methyl-, diphenyl-3-methylfulvene, 2-methylcyclopentyldiphenylmethane, 3-methylcyclopentyldiphenylmethane, cyclopentylidenediphenylmethane and cyclopentylidenemethylphenylmethane.

Those suitable according to the invention as high-energy fuel components Fulvenes and partially hydrogenated, substituted fulvenes and the cyclopentyl derivatives according to formula II have higher heating values in liters than cyclopentyldicyclohexylmethane and Cyclopentylmethylcyclohexylmethane, which as fully hydrogenated substituted fulvenes can be understood, as well as higher liter calorific values than cyclopentylmethylphenylmethane. This can be seen from Table I.

Table I. Melting point liter calorific value (HU) ° C Cal / liter Diphenylfulvene ............................. 79 10 060 <-2Q IQ 080 Mixture of diphenyl-2-methylfulvene and Diphenyl-3-methylfulvene ...................... liquid at room temperature 10 090 Cyclopentylidenediphenylmethane ............... 63 10 075 Cyclopentyldiphenylmethane 9 550 Cyclopentyldiphenyhnethane ........................ 36 10030 Cyclopentyldicyclohexyl methane ................ <43 9450 Cyclopentyhnethy 160 Cyclopentytmethylcydohexylmethane ................ <-609 070 The level of the liter calorific values of these high-energy components becomes particularly clear when they are compared with those of conventional distillate fuels such as gasoline, kerosene or gas oil fractions, whose liter calorific values are in a range of around 7770 to 8880 Cal / liter (HU).

The high energy components of the fuels according to the invention speak on the conventional oxidation stabilizers. Your resistance to oxidation can therefore, if necessary, by adding conventional antioxidants in customary concentrations be improved.

These high energy components are made with conventional fuels miscible on a hydrocarbon basis and, when admixed, increase their Liter calorific values. The high-energy components can be used in any of the fuels Concentration are added. The concentration in which they are added often depends on the permissible freezing point of the mixture. For example, one has Solution of 2 percent by weight of cyclopentylidenediphenylmethene in jet fuel a freezing point of -40 ° C if the freezing point of jet fuel even -50 ° C.

A solution with a content of 10 percent by weight has a freezing point from-about-10 ° C.

The addition of another high-energy component, cyclopentyldiphenylmethane, which has a melting point of 36 ° C, affects in amounts up to about 30 percent by weight obviously not the freezing point of jet fuel.

Table II below shows the freezing points and liter calorific values of blends of jet fuel and cyclopentyldiphenylmethane.

Table II Weight percent liter calorific value Cyclopentyldiphenyhnethane (HU) freezing point in aviation turbine fuel Ca, liter ° C 0 8160-52 2,8195-56 5 8260-56 10 8350-56 20 8550-56 30 8730-56 40 8920 11 The high-energy components according to the invention can be added to distillate fuels such as gasoline, kerosene, gas oil fractions and mixtures of these fuels. The fuels according to the invention with a high liter calorific value can also contain other compounds such as anti-knock additives, detergent additives, metal deactivators, conductivity improvers, anti-icing additives, antioxidants, corrosion protection additives, pour point depressants and other known fuel additives.

The substituted fulvenes suitable as high-energy components or partially hydrogenated derivatives of these fulvenes can be prepared according to any known Methods are made. Diarylmethylfulvene and diarylfulvene can, for example by the known reaction of methylcyclopentadiene or cyclopentadiene with a Diaryl ketone are produced.

The partially hydrogenated derivatives of these fulvenes can be prepared by using the abovementioned fulvenes using known hydrogenation processes, z. B. by catalytic hydrogenation in an autoclave in the presence of z. B. Raney nickel as a catalyst, hydrogenated.

For the production of those contained in the fuels according to the invention No protection is claimed in the context of the invention. a) Making a Mixture of diphenyl-2-methylfulvene and diphenyl-3-methylfulvene A mixture of 182 g (1 mol) of benzophenone, 23 g of sodium and 300 g of ethyl alcohol are heated to 30.degree. 80 g (1 mol) of methylcyclopentadiene are then added over the course of half an hour. The reaction mixture is then kept at a temperature of 30 ° C. for 1 hour. The reaction mixture is then worked up by distillation and gives 40 ° / 0 a mixture of diphenyl-2-methylfulvene and diphenyl-3-methylfulvene, the one Boiling point of 184 to 185 ° C at 0.5 mm Hg and a purity of over 98 °%.

The purity was determined by gas chromatography.

ClsHi6: Calculated ... C 93.4%, H 6.6%; ' found .. C 93.2%, H 6.7%. b) Partial hydrogenation of the substituted fulvenes which, as above A solution of 56 g of the mixture of the substituted Fulvene from a) in I I ethyl alcohol is used in the presence of Raney nickel as a catalyst at a temperature of 20 ° C for 2 hours with hydrogen under a pressure of 50Atm treated. When the reaction product is distilled, 85% of one is obtained Mixture of 2-methylcyclopentyldiphenylmethane and 3-methylcyclopentyldiphenylmethane. Boiling point of the mixture 114 to 117 ° C at 0.1 mm Hg, melting point 53 ° C.

Cl9H22: Calculated ... C 91.2 °%, H 8.8 °%; found .. C 91.7 ° / o, H 8.1%. c) Production of cyclopentyldiphenylmethane 500 g of diphenylfulvene will be dissolved in 11 ethyl alcohol. Then 25 g of Raney nickel are added.

The mixture is in a 1-1 autoclave at a temperature of 110 ° C and a print of 50Atm hydrogenated until the pressure remains constant, i.e. H. no more hydrogen is consumed.

Hydrogenation takes about 2 hours.

The reaction mixture is then used to remove the catalyst filtered and the solvent removed from the filtrate under vacuum.

This gives 435 g of a liquid crude product that is 95 percent by weight Contains cyclopentyldiphenylmethane.

The product is purified by fractional vacuum distillation. This gives 371 g of pure cyclopentyldiphenylmethane with a boiling point of 123 ° C at 0.3 mm Hg and a melting point of 36 ° C.

Claims (2)

Claims: 1. Fuels with a high liter calorific value based on hydrocarbons, characterized by the fact that they are a substituted fulvene of the general formula in which R1 is an unsubstituted or C1-C4-alkyl-substituted phenyl radical, R2 = RI or a C1-C4-alkyl radical, R3 is a C1-C4-alkyl radical and n = 0 or 1, and / or a derivative of a fulvene of the above formula , in which one or two double bonds are hydrogenated, and / or a cyclopentyl compound of the general formula in which R1, R3 and n have the meaning given above. 2. Fuels according to claim 1, characterized in that they 5 up to 40 percent by weight of the substituted fulvene and / or a derivative thereof and / or a cyclopentyl compound.