DE695269C - Process for the production of hydrocarbon oils from coal, tars, mineral oils, their distillation, cleavage and pressure hydrogenation products - Google Patents

Description

Process for the production of hydrocarbon oils from coals, tars, Mineral oils, ° whose distillation, cracking and pressure hydrogenation products It is known that hydrocarbon oils are made from coals, teas, mineral oils, their distillation, Fission and pressure hydrogenation products by using catalytic pressure hydrogenation of manganese or metals of the iron group or their compounds as catalysts can win. It has also already been proposed to use these substances in pressure hydrogenation To supply halogens or halogen-releasing compounds.

It has now been found that the yield can be increased and the reaction product q Can be improved even further if one uses the metals mentioned or their compounds pretreated with alkaline, especially inorganic substances; and then used together with halogen or halogen-releasing compounds as catalysts.

The effect of the claimed catalyst mixture was surprising. If @ it was also known, iron coated with tin or nickel. By treatment to activate with alkalis, it could not have been foreseen that the special catalytic effectiveness, which manganese and metals of the Eisiengruppe in Do not have the presence of halogens due to pretreatment with alkaline substances destroyed, but even increased.

The main metals or metal compounds are manganese and iron or their compounds, e.g. B. the oxides or sulfides, as well as nickel and cobalt or their four bonds into consideration. These are made with alkaline substances, z. B. ammonia or alkali compounds, e.g. B. the oxides, sulfides or carbonates, pretreated. Particularly effective are those catalysts that. By treatment of manganese or metals of the iron group, expediently in finely divided state, with a solution of an alkali metal compound, e.g. B. a lye, at an elevated temperature were manufactured.

The catalysts pretreated in this way are mixed with the starting materials and this together with hydrogen under pressure to the desired Reaction temperature heated. The addition of the catalyst can also occur during or : take place after heating. With low-boiling starting materials, 'z. B. medium oils, the catalyst mixture is firmly arranged in the reaction furnace. The supply of halogen, z. B. chlorine, bromine or iodine, takes place advantageously in the form of its compounds, z. B. as an organic halogen compound, such as carbon tetrachloride, halogen compounds of e.g. benzene or toluene or methyl, ethyl, methylene, ethylene chlorides, iodides or bromides. It is advisable to only add the halogen when the to be treated Starting material has already reached a high temperature, e.g. B. before it occurs in the reaction furnace or in this. It can also be done at several points on the apparatus respectively.

The process is particularly suitable for working in the liquid Phase. When using solid, carbonaceous substances, one or more Components of the catalyst applied in soluble form to the starting material will. In some cases. it is appropriate to use the basic components of the coal neutralize or remove before pressure hydrogenation by treatment with acid.

Example i Lignite is finely ground and treated with dilute hydrochloric acid sprinkled in such an amount that the basic components are neutralized. The pretreated coal is then with i% finely divided iron, which is with a 150; 'treated with caustic soda at about 100 ° for 2 hours' and then at 10 ° was dried, mixed and with a heavy oil derived from the same coal pasted in the ratio i: i. The coal pulp is then made together with hydrogen heated to 430 ° under a pressure of Zoo at in a gas-heated preheater and passed into a reaction furnace. Before entering the reaction furnace, he is given o.6% Chlorine added in the form of carbon tetrachloride. The mining of coal is 97.5%. The liquefaction product obtained contains 4550/0 to 325 ° boiling components and 6% asphalt.

If the same reaction is carried out without the addition of chlorine, so one achieves a reduction of 96.60, 'o. The liquefaction product contains 38.40; o Components boiling up to 325 ° and 7, 8 o; `o asphalt.

On the other hand, the reaction in the presence of i 0, 'o iron, the has not been pretreated with caustic soda, and the same amount of chlorine under otherwise If the same conditions are carried out, the degradation is 95.3%. and the liquefaction product Contains 27.8% to 325 ° boiling constituents and i i 0.1o -'Asphalt.

Example 2 Finely ground coal is mixed with an ice, sulfate solution soaked in such a way that the coal is about. Absorbs 3.6% iron sulfate, then dried, treated with soda solution so that about 2.6% soda, based on coal, on the iron sulfate act, dried again and finally in shape after adding 0.75N chlorine made of solid ammonium chloride with coal tar oil in the ratio i: i. If this paste is hydrogenated at 44 ° under a pressure of Zoo at, one obtains the following results degradation 93.80; b, asphalt content of the product 6, i%, distillate up to 325 ° in the liquefaction product 39%.

Used in the same way, but without the addition of ammonium chloride ; worked, a little less degradation of the coal is achieved and a product with a higher asphalt content, degradation 92.20, 'o, asphalt content of the product is obtained 8.3%, distillate up to 325 ° in the liquefaction product 3 5 0, o.

The results are even worse when using the method described above Method of operation neither added ammonium chloride nor carried out a pretreatment with soda will.

Dismantling. 89.2%, asphalt content of the product 9.90b, distillate up to 325 ° in the liquefaction product 290ö.

Example 3 Lignite is made with a nickel sulfate solution in the manner soaked that: the charcoal absorbs 7.2% of this compound, then dried and with Soda solution treated with consumption of about 0.8% soda (based on coal). To the repeated drying is added to 0.6% chlorine in the form of solid ammonium chloride and the coal pretreated in this way with the residue of a brown coal tar in Ratio i: i ground to a pulp. In the hydrogenation at 43o ° below one Pressure from Zoo at gives you a coal breakdown of 98.6%. The extracted oil contains 2.90 o asphalt. On the other hand, if the lignite is used in the manner described only with nickel sulphate treated and then hydrogenated in the same way, there is only a degradation of 970; o achieved, and the extracted oils contain 4.2% asphalt.

Claims (1)

PATENT CLAIM: Process for the production of hydrocarbon oils from cabbage, tars, mineral oils, their distillation, cleavage and pressure hydrogenation products by catalytic pressure hydrogenation in the presence of manganese or the metals of the Iron group or its compounds together with halogen or halogen-releasing .den Compounds, characterized in that: the metals or metal compounds mentioned, after dealing with alkaline substances. are pretreated as catalysts used.