DE1244316B - Process for the production of hydrocarbon oils suitable in particular as fuel for diesel and nozzle units - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Clog

German class: 23 b -1/04

Number: 1 244 316

File number: T 26774IV d / 23 b

Filing date: August 10, 1964

Opened on: July 13, 1967

In the thermal and / or catalytic cracking of petroleum hydrocarbons, which in large Extent is carried out, more or less large amounts of unsaturated hydrocarbons are formed Products that are either gaseous or have a low boiling point. To make them economically usable too make, they were subjected to a treatment with acidic catalysts. For example, one has for this! high-percentage orthophosphoric acid used and working temperatures above 150 ° C recommended. The gaseous or low-boiling products mentioned are converted into hydrocarbon oils um, which are quite suitable as carburetor fuel. However, you have to keep the temperatures Keep relatively low, because with increasing temperature by largely unexplained and Overlapping reactions result in oily products which can hardly be used as fuel and can at most serve as heating oil.

It has now been found that thermal treatment of the cleavage of petroleum fractions originating, gaseous or boiling in the gasoline range, containing unsaturated hydrocarbons Products in the presence of acidic catalysts are excellent fuels for diesel engines or jet units obtained when the thermal treatment in the presence of acidic catalysts at temperatures up to about 400 ° C and the resulting products after separation of the im Gasoline range is subjected to catalytic hydrogenation.

The catalysts to be used are those based on phosphoric acids. Particularly good High-percentage orthophosphoric acid has been shown to be. The temperatures should be above 150 to 200 ° C. It is generally advantageous to work between 180 and 350 ° C., but this is achieved also still usable results at temperatures up to 400 ° C.

The process leads satisfactorily to the goal even in the case of a discontinuous procedure. However, it is far more advantageous to run it continuously. By means of a suitable arrangement, the thermal treatment in the presence of the acidic catalyst, the separation of the fractions boiling in the gasoline range and finally even the subsequent catalytic hydrogenation can be carried out in one continuous operation. By removing the portions boiling in the gasoline range and subsequent cooling in stages, the gasoline portion that can be used as carburetor fuel from the unconverted starting products can also be used as a method of production, in particular as a
Fuel for diesel and nozzle units
suitable hydrocarbon oils

Applicant:

Technochemistry G. m. B. H., process engineering,

Heidelberg, Heiligenbergstr. 1 b

Named as inventor:
Dr. Friedrich Asinger, Aachen;
Dr. Othmar Pauer, Beuel;
Dr. Bernhard Fell, Aachen

separate, so that the latter in turn fed into the circuit for catalytic treatment can be.

In the known process mentioned at the beginning, working temperatures between 50 and 200 ° C. are recommended for the preferred catalysts, because otherwise high-boiling or heavy tar-like polymers are formed that can only be used as heating oils are. You therefore have to obtain the desired in the known process, in the boiling range For polymers boiling in gasoline, special cooling measures are indicated as necessary. as well a temperature range between 100 and 200 ° C is proposed for the second polymerization stage. For each reaction vessel, conditions are prescribed under which any high-boiling points are formed Polymers can be separated and discarded.

So you couldn't make any promises about it, the starting materials for a treatment with acidic To subject catalysts to temperatures of up to about 400 ° C, because only minor ones arise here Amounts of gasoline and also unusable high-boiling or tarry products. First if you work according to the invention and the resulting unusable at a higher temperature Products are catalytically hydrogenated after removal of the boiling components in the gasoline sector Fuels with the particularly valuable properties mentioned, which are particularly useful for diesel engines, but also nozzle units are very suitable.

Further appropriate measures for the technical implementation of the new process are in the the following working examples.

709 610/465

example 1

In an autoclave with copper insert, stirrer and heating 600 parts by volume 100 filled ⁰ / o phosphoric acid; the catalyst is prepared by dissolving 50.6 parts by weight of phosphorus pentoxide in 100 parts by volume of 89% orthophosphoric acid.

The autoclave is now closed, flushed with nitrogen and heated to 300.degree. With a dosing pump 600 parts by volume of olefin-containing cracked gasoline with boiling points of 40 to 160 ° C are then used (95% according to ASTM) and with an olefin content of around 50% metered in within 15 minutes and the Pressure brought to 75 at with nitrogen. After about 2/2 hours exposure with stirring at 300 ° C the reaction product is pressed off through a dip tube. After separating the catalyst sludge The greenish-brown hydrocarbon oil that is formed is transferred via separating bottles or centrifuges fractionally distilled. A fraction goes over up to about 180 ° C, which immediately becomes high-octane Carburetor fuel can be used. The amount is around 55%.

The higher-boiling portion freed from the gasoline components is, if necessary after a distillation, subjected to catalytic hydrogenation in the presence of Raney nickel or tungsten sulfide. Man thus receives a kerosene fuel, which is very suitable for the operation of diesel engines as well as of Nozzle units are suitable.

Example 2

600 parts by weight of a _{gas fraction consisting mainly of C 4} -CoIi lenwasserstoffen from the catalytic cracking of petroleum, consisting of

η-butane 9.7%

isobutane 41.2%

n-pentane 0.2%

51.1%

Butene- (l) 12.0%

Transbutene- (2) 11.6%

cis-butene- (2) 7.2%

isobutene 18.1%

48.9%

are in the manner described in Example 1 with the catalyst mentioned there for 3 hours heated to 250 ° C. This results in a pressure of 79 at. The contents of the autoclave are as in Example 1 worked up. Based on the olefin content of the starting gas, 69.5 percent by weight of one is obtained saturated, high-octane gasoline fraction and 40.5% kerosene, which after catalytic hydrogenation as Diesel or turbine fuel can be used.

The volatile gas content consists of 99.5% predominantly saturated, mainly 4 carbon atoms containing hydrocarbons. It can be used directly as cylinder gas or as an additive to town gas Find.

Claims (1)

Claim: Process for the production particularly suitable as fuel for diesel or nozzle units Hydrocarbon oils through thermal treatment from the splitting of petroleum fractions originating, gaseous or boiling in the gasoline range containing unsaturated hydrocarbons Products in the presence of acidic catalysts, characterized in that the thermal treatment is carried out in the presence acid catalysts at temperatures up to about 400 ° C and the products obtained after removal of the boiling components in the gasoline sector, a catalytic hydrogenation subject. Considered publications:
German patent specification No. 896793.