DE677104C - Process for the production of, in particular, low-boiling hydrocarbon oils from coals, tars, mineral oils, their distillation or extraction products, or residues - Google Patents

Description

Process for the production of, in particular, low-boiling hydrocarbon oils from coals, tars, mineral oils, their distillation or extraction products, or residues One can extract from coals, tars, mineral oils whose distillation and extraction products and residues and similar carbonaceous materials by . Treatment with hydrogen or hydrogen-releasing gases in the presence valuable carbons from catalysts at elevated temperature and pressure, especially liquid in nature, which can be used as gasoline or diesel oil for themselves or in a mixture with other fuels ,, or as a solvent and distribution medium or can be used as a lubricant.

It has now been shown that this: method is excellent Yields of valuable, especially low-boiling hydrocarbons, when under increased pressure, e.g. B. at 5oat, useful at i oo at and more, and with flowing gases while maintaining a large excess of hydrogen works at temperatures above 3oo ° and uses catalysts which the Metalloids of the 5th and 6th groups which form solid oxides at ordinary temperature of the periodic table phosphorus, arene, selenium or tellurium or their compounds contain. The metalloids mentioned or their compounds can be used with advantage along with other elements of z. to B. Group, especially the metals of the 6. Use group or its connections. The catalysts can, for example contain the following acids or their salts: phosphoric acid, arsenic acid, selenious Acid; also include: for example calcium phosphate, molybdenum phosphate, tungsten phosphate, Iron phosphate, ammonium phosphorus molybdate and tungstate, arsenous acid together with molybdenum and tungsten, Eden charcoal annealed at 8oo °, that with phosphoric acid is soaked, or molybdic acid with an addition of sodium selenate.

It is advisable to work in a cycle. Such raw materials, which easily lead to detrimental deposits on treatment become advantageous subjected to a pretreatment with hydrogen under pressure with or without catalysts and converted into products of the type of middle oils, which then are best treated further in gassed or finely divided form, with in one, in particular in the second, or both stages, catalysts of the aforementioned Kind of used.

It is useful to ensure that those with the hot reactants apparatus parts that come into contact do not have any harmful effects, i.e. z. B. do not promote methane formation and coke deposition and no premature Cause condensation. The equipment material is best chosen so that it is also not attacked under the working conditions, e.g. B. is used high-alloyed Steels or aluminum.

It has already been suggested, one or the other of Catalysts claimed here in hydrogenation or dehydrogenation of hydrocarbons to use. These reactions are, however, at temperatures from about 150 to 200 degrees and mostly under normal or slightly increased pressure executed. During these processes the addition or elimination of hydrogen concern for hydrocarbons with toxic-sensitive hydrogenation catalysts, take place in the present process using temperatures above 3oo ° hydrogenations or others, e.g. Sometimes even more extensive changes with catalysts, those usually contained in the raw materials used, the Catalysts harmful constituents are not adversely affected. It is about thus other conditions which do not occur with the known processes and in which also more severe conditions of temperature and mostly also of pressure than present there.

It has also been suggested to use tars, mineral oils and fractions to distill such with the addition of phosphoric acid at ordinary pressure, whereby a split is to take place. But there is usually such a thing without the addition of Phosphoric acid enters, nothing could be inferred from the known case about what happens when working under hydrogen pressure and at temperatures above 300 °.

It is also known to treat naphthalene under pressure and at high temperature to liquefy in the presence of selenium by hydrogenation. This is done in the autoclave worked. The present method differs from this in that at Gases flowing to him are used in the event of a large hydrogen shot, whereby the Continuous work is possible, for technical purposes alone comes into consideration. Incidentally, the known autoclave process is expressly stated said that there are already abuses when working on a laboratory scale.

The splitting hydrogenation of naphthalene or hydrogenated naphthalene using .von- fully or partially bound to phosphoric acid or its conversion products or metal oxides according to patent 664386 should not be protected here. Examples i. Elwerath crude oil, to which aluminum phosphate has been finely divided, is treated with excess hydrogen at a pressure of 420 degrees. 60 to 700 per cent of the starting product is obtained as middle oils, the vapors of which are passed in a stream of excess hydrogen at 60 ° over a catalyst consisting of charcoal produced by annealing Erhenholz impregnated with phosphoric acid. The hydrogenation gases are circulated while maintaining the pressure and replacing the used gas with fresh gas. When cooling down behind the furnace, a pale, thin-bodied product is obtained which contains about 80 to 90 2 / o low-boiling hydrocarbons.

2. Molybdic acid and zinc oxide are mixed with a 100% phosphoric acid solution pasted, dried at 10 ° and then gradually in a stream of hydrogen at 2ooat pressure heated up to 46o °. One passes over this catalyst at 480 ° together with hydrogen Medium oil obtained at 2ooat pressure by pressure hydrogenation of lignite tar. After the gases leaving the reaction vessel have cooled down, a product is obtained with 60% to co 'boiling proportions. The catalyst thus prepared is very effective and has remarkable mechanical strength.

3. Central German brown coal is produced with a pressure hydrogenation high-boiling oil obtained from lignite made into a paste and put together with excess hydrogen at 43o to 45o ° under a pressure of 2ooat continuously passed through a high pressure apparatus. 1 to 2% of the coal pulp is finely ground Rock phosphate (pebble phosphate) added. 7o to 8o% of the ash-free coal substance are converted into valuable hydrocarbons.

4. By digesting equal parts of tungstic anhydride and 3.5% phosphoric acid, evaporating the pulp to dryness and then heating up to about 400 ° a solid mass is obtained, which after grinding into grains is filled into a high pressure pipe. Then in the hydrogen stream under zoo at pressure at a temperature slowly rising to 45o ° and then reduced at 420 ° a medium oil of a German petroleum in an hourly amount 2.5 times the volume of the catalyst in, introduced the gas stream. When cooling down behind the furnace, you get a liquid one Half of the product consists of hydrocarbons boiling below 18o °. The latter contain more than 30% hydrocarbons boiling below 100 °.

5. American gas oil is used in large excess together with hydrogen, z. B. 6 cbm H. per i kg of oil, passed at 200 at pressure and 486 'over a catalyst, made from a mixture of 1.5 moles of tungsten selenide and 1 mole of zinc selenide is. When the vaporized products are cooled, a liquid product is obtained Product containing 50% to 180 ° boiling parts; these shares can be used without further Refining can be used as motor fuel while the higher boiling fractions represent a valuable diesel oil.

If, instead of tungsten zinc selenide, one uses aluminum oxide as a catalyst, in this way, under otherwise identical conditions, a liquid product is obtained that only contains 20% until i 8o 'contains boiling fractions.

6. In an electrically heated high-pressure rotary kiln there is a centric Rotating pressure-resistant sleeve for thermocouples attached. At this one is Wire sieve, which is filled with selenium pressed into pieces, attached so that the catalyst is located alternately in the liquid and vapor space during the drifting. This oven, heated to: 125 °, produces crude Venezuelan oil, which is produced by distillation was freed from the portions boiling up to 325 ° (specific weight 0.944, 1100 ', asphalt content : about 9%) together with hydrogen of 8 o atm. Pressure passed through. The den Products leaving the oven are caught in a cooled scraper and separated from the gas.

The product obtained contains 33.3% to 180 °, 78.2% to 325 ° and 1.2% asphalt. If lumpy aluminum phosphate is used instead of the selenium, a product is obtained which contains 27.4% to 180 ° and 54.40 / 0 to 325 °. Its asphalt content is 2.70 / 0.

If one uses one made from tungstic acid and phosphoric acid Catalyst, a product is obtained with otherwise the same experimental conditions 31.6 0/0 to 18o °, 63.5% to 325 ° and 1.8% asphalt.

Claims (1)

PATENT CLAIM: Process for the production of especially low-boiling hydrocarbon oils from coals, tars, mineral oils, their distillation or extraction products, or residues by treatment with hydrogen or hydrogen-releasing gases in a flowing state and in large excess at temperatures above 300 ° and under pressure, expediently in the circuit , characterized in that catalysts are used which contain phosphorus, arsenic, selenium i or tellurium or their compounds, the splitting hydrogenation of naphthalene or hydrogenated naphthalenes using hydrogen-attaching metals or metal oxides wholly or partially bound to phosphoric acid or its conversion products according to patent 664386 is excluded.