DE767240C - Lubricating oils - Google Patents

Description

Process for the production of knock-proof gasoline from gasoline, heavy gasoline or middle oils It is known that gasoline, heavy gasoline or middle oils in Can transfer knock-resistant gasoline if you use them at temperatures above 4oo ° in the presence of hydrogen, advantageously under increased pressure, over active alumina conducts those with compounds of heavy metals, especially those of the second and fourth to eighth groups of the periodic table.

It has now been found that this process gives higher yields and / or fuels of better quality are obtained by using an alumina used by precipitating alumina hydrate from an aluminum salt solution Temperatures above 80 ° while maintaining a pH value between about 7 and Io and post heating was made.

In the precipitation of the alumina hydrate, temperatures are generally preferred from 9o to 100o °. The aluminum salt solution can be added before the precipitant is added Heat accordingly high or the aluminum salt solution and the precipitant without pre-heating in a correspondingly highly heated vessel or in a correspondingly Pour highly heated liquid. You can also use temperatures above the boiling point of Apply reaction mixture at atmospheric pressure by painting in a closed vessel, for example under pressures of 3 2at and more, works. The amount of precipitant is measured so that the solution during the disfigurement of the precipitate always has a pH value within the stated range.

The precipitate is removed from the liquid, which is expediently still empty. generally hot temperatures not below about 40 to 30 °, separated and then iais washed. In contrast to those precipitated in the usual way at lower temperatures Clay hydrate precipitates can easily be precipitated in proportion Wash salt-free with hot water for a short time.

The alumina substrate thus produced can, after drying, preferably at Ioo to I3o °. Processed on moldings in a press without difficulty which are derived from moldings made from alumina hydrates produced in another way. i.a. differ by greater hardness. By heating to temperatures above 3oo °. especially to 33o to 6o0 @. disfigures active clay from the hydrate.

The active clay obtained in this way is then mixed with heavy metal compounds, especially those of molybdenum. Chrome. Tungsten. Vanadium, nickel, cobalt. Iron, Zinc, lead, tin or mixtures of these. provided, expediently by soaking with solutions soluble salts of the metals mentioned, and then heated, for example to temperatures between 3oo and 6oo ° or even higher, e.g. B3. to 8oo °, where in in many cases the corresponding oxides are formed from the salts. The addition of the Metal compounds can also add to the still moist alumina wire before drying. Forming and heating take place.

The clay can also be used in an amount of 1 to 3o%. advantageous 3 to 3o% '0. in particular 3 to 15% finitely active silica, kieselguhr or silicates, especially those of aluminum, magnesium. Beryllium, zinc. Thorium. Cerium and hzw. or iron, provided sirr. alkali-free silicates are advantageously chosen. You can use the clay z. B. with fuller's earth or artificially. z. B. according to the information of the French patent code 8dI 898, which are expedient are still pretreated with hydrogen fluoride. This is done z. B. in the Make sure that the compounds forming the silicic acid or these silicates are used or solutions such as water glass solutions, silica sols or silicon halides arid optionally also the metal salt solutions required for the formation of silicate the heated or moist clay is applied and the silicate or silica gel on top of it generated. The mixture is then exposed to higher temperatures.

As starting materials for there, the present processes come first Line petrol with bad knocking behavior as well as heavy petrol or middle oils, which are produced by distillation from soil or tars or by pressurized extraction of cave. Tars, mineral oils were obtained. into consideration.

Carrying out the dehydrogenation or cyclization of the starting materials generally takes place in a manner known per se. For this purpose, the starting materials in the vapor state for the purpose of hydration or cyclization at temperatures from 42o to 7oo, in particular 47o to 55o via the oil-level catalog directed. One works here in the presence of hydrogen. It is appropriate increased pressure, e.g. B. 2 to 3o 2at or more, apply. But Ma2nr can also carry out the reaction under the conditions of the aromatizing pressure hydrogenation. pressures of 150 to 500 2at or even more can be used.

The review is to be chosen in such a way that dehydration and / or cyclization occurs. To achieve defydration only, use the general throughputs of more than 1 kg of starting material per liter of catalyst space and hour on. If, on the other hand, a cyclization, in particular aromatization, is sought, a throughput of 0.2 to 2 kg, advantageously 0.3 to 1.2 kg, in particular, is chosen 0.2 to 0.6 kg per liter of catalyst space and hour. The throughput is advantageous adapted to the reaction temperature in such a way that it increases with increasing temperature increases. This is how you work B3. hot about 500 to 330 ° or higher, e.g. B. 550, with Flow rates from 0.3 to 1.1 kg. at lower temperatures, flat throughputs apply from 0.3 kg and less. Generally one works under such conditions that more than 3o% 0, expediently 4o% and more, e.g. B3. 3o% and more. aromatic plank hydrogen develop.

It is particularly advantageous to run the process under total pressure of more than Io. At most, however, too 2at, advantageously 2o to 9o 2at, in particular 3o to 7 3 2at, and a hydrogen partial pressure which is about 2o to 8o% of the total pressure and is below 4o 2at, expediently below 3o 2at, with dir Hydrogen-containing (-jase leaving the reaction space without any further Zugalm from fresh water stoti. given: if necessary after Al) sclieidting von Verlreini-ungI'n. z. P. by _washing out of gaseous hydrocarbons, in one Amount of 0.3 to 4.5, in particular 0.6 to 2.0 cbm per kilogram of starting material again be returned to the reaction chamber. The method is advantageously carried out in several stages as the temperature rises.

The recycled gas generally has a hydrogen content from about 25 to 90%, in particular from 30 to 75%. It is beneficial to the returned Gases a small amount, e.g. B. 0.05 to 3% sulfur, expediently in the form of gaseous or volatile sulfur compounds.

To regulate the temperature one can use part of the vaporous Branch off reaction products before the condensation and, if necessary, after the previous one Return the heating to the reaction vessel. The heating can be done in one special preheater or the preheater itself, which is upstream of the reaction vessel be made. When using several reaction vessels with intermediate ones It is advantageous to preheat some of the reaction products at least after a reaction vessel, e.g. B. after the first and or or second, branch off and returned to the preheater. At least 10% is passed, expediently 20 to 9o %, in particular 40 to 90%, of the vaporous reaction products.

The starting materials can be refined before the treatment described subjected to known refining agents or refining pressure hydrogenation will. The reaction products can also be refined in this way. It is particularly advantageous to combine them with hydrogen, expediently with the hydrogen-containing gas used in the present process, at temperatures between 15o and 4o0 °, especially 25o and 35o °, about one for the refined To conduct pressure hydrogenation known catalyst. The throughput is about 1.5 to 5 kg of gasoline per liter of catalyst space and hour. Incidentally, there are such conditions must be observed that the aromatic hydrocarbons remain unchanged stay. Example aluminum nitrate solution, the concentration of which has an Al2O3 content of 8% 'o, and an i 5% ammonia solution are simultaneously in a poured some water with the pH value 7 containing, heated to 95 ° vessel, so that the mixture of the solutions in the vessel has a pH of 7. That is still hot Mixture of solution and precipitate is placed on a filter press and the Filter cake washed with water at 70 to 80 degrees for 3 to 4 hours. That so obtained alumina hydrate is crushed after drying, pressed into pills and then heated to 3oo to 35o °. The mass has a bulk weight of 0.35 to 0.4 kg per liter. It is soaked in an ammonium molybdate solution and within 8 Heated steadily increasing to 45o ° for hours and at this temperature for 6 hours held. The amount of molybdate is calculated so that in 1 liter of mass 55 g MOO3 are included.

The catalyst thus produced is placed in a reaction furnace, and at a temperature of 50 'the vapors of a fraction of a naphthenic gasoline boiling from 130 to 180 ° are passed over it together with hydrogen. A throughput of 0.5 kg of gasoline per liter of catalyst space and hour is selected under a total pressure of 50 at and a hydrogen partial pressure of 25 at. 1 cbm per kilogram of starting material with a hydrogen content of about 50% of the gaseous reaction products obtained is returned to the reaction space . The catalyst is revived after 36 hours.

The gasoline obtained contains 72% aromatic hydrocarbons.

In the case of a catalyst precipitated at 50 °, after 24 hours - In addition, in this case contains the accumulating: Gasoline only 430/0 aromatic hydrocarbons.

Claims (1)

PATENT CLAIM: Process for the production of knock-proof petrol Gasoline, heavy gasoline or middle oils, characterized in that the starting materials are used at temperatures above 400 ° in the presence of hydrogen, advantageously under increased Pressure, through active alumina conducts, caused by the failure of. Alumina hydrate from a Aluminum salt solution at temperatures above 80 ° while maintaining a PH value between about 7 and io and subsequent heating established and with Heavy metal compounds were provided: To delimit the subject matter of the invention from the state of the art are in the process of being granted. the following publications into consideration drawn: U.S. Patent No. 2o96769; French patent specification no. 811,792; 841 898, 862 ö9 i.