DE722405C - Process for the pressure hydrogenation of carbons, tars, mineral oils and the like like - Google Patents

Description

Process for the pressure hydrogenation of carbons, tars, mineral oils and the like. In the production of especially low-boiling hydrocarbons from coal, Tars, mineral oils, their distillation and extraction products and residues by pressure hydrogenation it is already known to use catalysts that contain halogen, possibly in bound form.

It has been found that particularly good results are achieved when halogen compounds containing solid metalloids are used as a catalyst together with Compounds of metals of the 5th and 6th group of the periodic table or oxides, Sulfides or phosphates of other metals are used. These catalysts draw differs from known ones by an increased splitting and hydrogenation effect. Latter occurs particularly with the highest molecular proportions of the starting materials. The method is e.g. B. when processing high-boiling raw materials on medium oil under-recirculation of the proportions lying above the final boiling point of the middle oil of importance, since when using the catalysts mentioned, even at high Temperatures in addition to the cleavage, an extensive hydrogenation takes place, so that in the portion to be continuously returned to the reaction vessel no 'low in hydrogen Condensation products occur. Another advantage of the catalysts is there in that the resulting in the reaction, below the boiling range of the starting materials lying fission products are not saturated with hydrogen. So z. B. when processing medium oils in the gas phase, low-hydrogen gasoline and low-hydrogen when processing high-boiling raw materials in the liquid phase Middle oils and lower boiling hydrocarbons are obtained while the higher ones boiling products have a much higher hydrogen content than the starting material exhibit.

Carbon and primarily come from halogen compounds Hydrogen-containing, so the organic halogen compounds, in particular the bromine and chlorine compounds, for example carbon tetrachloride, Chloroform, iodoform, bromoform, the chlorine, bromine or iodine compounds of benzene, Naphthalene, toluene, xylene, phenol, cresol, anthraquinone and nitrobenzene as well as methyl, ethyl, methylene, ethylene chloride, bromide or iodide, also fluoroform, Fluorobenzene and. Fluoronaphthalene or substances containing these compounds.

The halogen compounds of other solid metalloids than carbon, in particular of phosphorus, sulfur, selenium, tellurium, arsenic, antimony, silicon, titanium, Zircon, or boron, have very good catalytic effects because they are a happy one Contain a combination of two active catalytic components. As such Compounds are for example: phosphorus trichloride, phosphorus tribromide, Phosphorus pentabromide, phosphorus sulphon chloride, phosphorus iodine, phosphorus triiodide, sulfur chloride. Sulfur tetrachloride, selenium chloride, selenium tetrachloride, selenium bromide, selenium tetrabromide, Selenium iodine, selenium tetra iodide, tellurium chloride, tellurium tetrachloride, tellurium bromide, tellurium tetrabromide, Tellurium iodine, tellurium tetraiodide, arsenic trichloride, arsenic tribromide, arsenic triiodide, antimony trichloride, Antimony pentane chloride, antimony tribromide, antimony triiodide, boron trichloride and metal or ammonium tellurium bromide, iodide or chloride or the corresponding antimony compounds or silicon tetrachloride, silicon fluoride, silicon fluoric acid.

According to the invention, the halogen compounds are used together with compounds of the metals of the 5th and 6th group of the periodic table or oxides, sulfides or phosphates of other metals are used. Examples are the oxides, Sulphides, nitrides, phosphates and halides of vanadium, molybdenum, tungsten, chromium and uranium and the oxides, sulfides or phosphates of copper, silver, magnesium, zinc, Tin, cadmium, aluminum, silicon, titanium, manganese, rhenium, nickel, or cobalt Iron.

As starting materials are z. B. named: lignite, hard coal, peat, Oil shale, tars, mineral oils or their fractions or fission or pressure hydrogenation products. Also for processing asphalt and resins as well as for refining or improving of hydrocarbon oils, such as. B. gasoline, benzene, medium oils or lubricating oils, furthermore, the catalysts are advantageous for the dehydrogenation of hydrocarbons suitable.

The reaction carried out in both liquid and gas phases can be, takes place under the known conditions of temperature and of pressure, e.g. B. at temperatures from 25o to 6oo ° and pressures from ao to iooo at.

The catalyst is added either before it enters the Heating zone or during the heating or during the reaction. The parts of the catalyst mixture can with the substances to be treated at different Bodies of the procedure are brought together. Also the use of carriers, such as active charcoal, pumice stone, active silica, or pottery shards, is beneficial. It can also be advantageous to use the non-halogen-containing component of the catalyst, if it is solid, to be arranged in the reaction vessel by itself and the starting materials with volatile halogen compounds to conduct over it. Halogen compounds found in in liquid form can simply be mixed with the substances to be treated will. You can z. B. soak coal with the liquid halogen compounds, whereby excellent distribution in the material to be hydrogenated is always guaranteed.

The amount of catalyst to be added is within the limits of o, or to 10 ° ia, preferably o, ot to 3 ° / a.

It has also proven to be advantageous to the hydrogenation gas that is used for Achieving particularly high yields is to be used in the flowing state, for example 0.5 to 511 /, hydrogen halide, e.g. B. bromine or hydrogen chloride to be added. In the presence of metal sulfides, the hydrogenation gas can also be advantageous Add small amounts of hydrogen sulfide.

The present catalysts are particularly effective in working in the gas phase. Mainly middle oils are used as starting materials Consideration. Another advantage of the catalysts is that the starting materials mixed with them do not form any polymerization products, as it does when using free halogen, e.g. B. iodine, is often the case. Through the Use of the described catalysts in medium oils gives a special Knock-proof gasoline and extremely hydrogen-rich middle oil, which is used as luminous oil or Diesel oil used or in the reaction vessel for complete conversion into gasoline can be returned again.

Although it is known to use metalloids such as carbon, phosphorus, arsenic, Tellurium or halogens, in free or bound form, as catalysts in pressure hydrogenation of coals, tars and mineral oils to use at high temperatures. In contrast According to the present invention, certain halogen compounds, namely those with solid metalloids, used in conjunction with certain other compounds. The particular advantages of these catalysts emerge from the following examples. Compared to the well-known Possess turn of metal halides they have the advantage of a lower polymerizing effect, especially when Treatment of materials containing asphalt.

Example i means German brown coal is finely ground un.d impregnated with a Ammonmolvbdatlösung, so that the coal o containing o2% molybdic acid. The coal powder is then made into a paste with an oil boiling above 300 ° and obtained by pressure hydrogenation of the same coal in the ratio i: i and passed through a gas-heated preheater together with hydrogen under 25o at pressure, in which -the reactants are heated to q.55- ' . Chlorobenzene is added to the reaction furnace in such an amount that o, i ° / o chlorine is present in the carbon paste in the reaction furnace. 95 % of the carbon introduced is converted into valuable hydrocarbons. As a result of the catalytic effect of the chlorobenzene, the asphalt content of the residue is reduced to about half.

In place of the above-mentioned chlorobenzene, one can also use chlorinated Use paraffin.

Example e The middle oil fraction is made from Volkenrodaer petroleum by distillation won. This is combined with hydrogen under a pressure of Zoo at in one Gas heated preheater heated to 48o °. Before entering the reaction furnace is the reactants i% ethylene chloride, based on the middle oil, was added. This mixture is then made of molybdenum bromide over the firmly arranged in the reaction vessel existing catalyst led. One obtains a single pass through the Reaction furnace consists of medium oil, the hydrogen content of which is higher than that of the starting oil and can be used as luminous or diesel oil.

Ethylene bromide, bromoform, Methylene bromide can be used.

Example 3 Hard coal is finely ground and finely divided with i% Iron sulfide added. The catalyzed carbon powder is then mixed with a heavy oil originating from the same coal in the ratio i: i mixed and together with hydrogen under a pressure of 25o at in a gas-heated coil preheater heated to 46o °. The reactants then get into an expanded high-pressure vessel, where 0.1% arsenic trichloride (based on the carbon paste) is added to them on entry will. 94% of the carbon in the coal is converted into valuable hydrocarbons transferred and the / a knock value corresponding to a mixture of 76% Isooctane and 24% normal / 'a product made up half of gasoline with heptane and the other half from an asphalt content of the residue, opposite working without addition of arsenic trichloride, reduced by about 40%.

Example 4 Lignite is finely ground and mixed with an aqueous solution soaked in ammonium molybdate, @so that there is 0.02% molybdic acid on the carbon. The coal is then in proportion with a heavy oil derived from the same coal i: i mixed and together with hydrogen under a pressure of 25o at in one Preheater heated to 455 °. The reactants then get into a hydrogenation vessel, after o.51 /, sulfur chloride (based on carbon paste) was added to them beforehand. 97 per cent of the carbon in coal turns into valuable, mainly liquid, hydrocarbons convicted. The asphalt content of the residue is around 40% less than that of the Execution of the reaction without the addition of sulfuric chloride. Example s hard coal is fine ground and impregnated with a solution of tin oxalate, so that the charcoal is 0.06% tin oxide contains. The charcoal powder is then made with one of the same charcoal by pressure hydrogenation recovered heavy oil in the ratio i: = pasted and put together in a preheater heated to 46o ° with hydrogen under a pressure of 25o at. In the subsequent Reaction furnace is added to the carbon paste to be treated, 30/0 selenium tetrabromide. In this process, 961/0 of the carbon in coal is converted into mainly liquid hydrocarbons convicted. Compared to carrying out the reaction without adding selenium tetrabromide the asphalt content is reduced by 35%.

EXAMPLE 6 A Hanoverian crude oil boiling above 325 ° is mixed with 20% aluminum oxide and heated to 47 ° together with hydrogen under a pressure of 25 ° at and passed through a reaction furnace. Before the reactants enter the preheater, 1.5% ethylene bromide is added to the crude oil to be treated. 10% of the product leaving the furnace consists of a high-boiling residue and 90% of a distillate boiling between 50% and 325 °. If the reaction is carried out without the addition of ethylene bromide, only 85 % of the starting material to be treated can be enforced per unit of space and time in order to obtain the same results. Example? A Thuringian crude oil boiling above 325 ° is mixed with i% r odbenzene and added heated together with hydrogen under a pressure of 25o at to 465 ° and passed through a high pressure vessel. The liquid reaction product consists of 8% of a high-boiling residue and 92% of a distillate that boils to 45% up to 325 °. In order to achieve the same yield in the absence of iodobenzene, the throughput of the starting material per unit of time and space could be only 75%.

Example 8 Ruhrgas flame coal is finely ground and coated with a tin oxalate solution soaked, so that o, o5% tin oxide is accounted for by the charcoal. This col = le then becomes with a heavy oil obtained from the same coal by pressure hydrogenation in proportion i: i pasted and combined with hydrogen under a pressure of 25o at in one Gas-heated preheater heated to ..f.1.5 °. Immediately before the preheater is the carbon paste o, 851 / "carbon tetrachloride (based on coal) added Reactants then get into an expanded high-pressure vessel in which sets a temperature of 46o °. The mining of coal is 96 0/0; the received Oil consists of 95% gasoline and medium oil, and the heavy oil contains 80% asphalt. If the reaction is carried out without the addition of carbon tetrachloride under otherwise identical reaction conditions carried out, the degradation is only C91 Olp, and the heavy oil contains 12% asphalt.

Example 9 The vapors of one are passed through over tungsten hexachloride Pressure hydrogenation of medium oil obtained from German petroleum together with hydrogen at Zoo ae pressure at a temperature of 43o ° and sets the starting material before entry adding i o / o ethylene chloride to the reaction furnace, a product with 52% is obtained proportions boiling up to i85 °. If you use tungsten hexachloride alone, you get one a product with 40%, and one uses ethylene chloride without further addition, one with only 15% to 185 ° boiling proportions.

Claims (2)

PATENT CLAIMS: i. Process for the pressure hydrogenation of coal, tars, mineral oils, their distillation, cleavage and extraction products and residues in the presence of halogen-containing catalysts, characterized in that the catalyst used is solid metallo = de-containing halogen compounds together with compounds of the metals of 5th and 6. Group of the periodic table or oxides. Sulfides or phosphates of other metals are used. 2. The method according to claim i, characterized in that the solid metallo = de-containing halogen compounds used those containing carbon and hydrogen.