NO832023L - PROCEDURE FOR MANUFACTURING LONG OIL, BITUMEN AND SIMILAR - Google Patents

Description

The invention relates to the use of porous, carbonaceous disposable catalysts, especially carbon black, from heavy oil gasification in sump or combined sump and gas phase hydrogenation of heavy oil, bitumen and similar output products such as residues of overhead and vacuum distillation of crude oil.

It is e.g. from W. Kronig "Die katalytische Druckhydrierung von Kohlen, Teeren und Mineralolen", Berling/Gottingen/Heidelberg 1950 it is known that heavy oils, bitumen and other residues can be converted into low-boiling hydrocarbon mixtures by mixing them with hydrogen and catalyst, possibly also with a return oil derived from the product and heats this mixture at a pressure of 50-700 bar, preferably 100-325 bar in a heater to 200-500°C, preferably 350-450°C. After passing the preheater, the mixture is fed from below through a reactor system, where at temperatures between 250 and 550°C, preferably 380-480°C, hydrocracking reactions take place which lead to the splitting of larger molecules as well as to their partial desulphurisation, denitrification and deoxygenation.

From the top of the reactor system comes the reaction mixture

into a heat separator which can also consist of a system^

of several separators connected in series and operated at temperatures of up to 100 K, preferably 20-40 K below the reaction temperature. From the top of the heat separator, gaseous and vapor-form reaction products are removed, from the bottom of the heat separator unreacted used material, asphaltenes, catalysts and a certain heavy and medium oil part as thermal sludge. With suitable precautions, e.g. by means of centrifugation, distillation or extraction, further hydrogenation heavy oil can be recovered from this hot sludge by separating the hydrogenation residue.

At the top of the heat separator, the removed gas or vapor-form products are either deregulated in a cold relaxation system and added to it for further processing or are brought under reaction pressure a short way from above in a system of reactors, in which the gas or vaporized products on solid storage catalysts are further desulfurized, denitrified, deoxygenated and decomposed (compare W. Urban "Erdolver-arbeitung in der Scholvener 300 at-Kombi-Hydrierkammer" in Erdol und Kohle, 8 (1955), pp. 780-782). The products of this "Combi-Cracking" are also deregulated via a cold separator system and fed to further processing. v i

It is r—-k^-en-tr~-§e^c%-ydrregen'e-ring—of--tungu^je-~and^Mrtume'n~±±in the sump phase to use disposable catalysts that on a carrier as aletive coal or especially coke contain catalytically active metal compounds, for example tungsten,

molybdenum, lead, tin, chromium, cobalt and nickel, especially of iron. These catalysts are used in quantities of up to 10% by weight with reference to the product used, especially 1-6% by weight. Iron compounds which, under the reaction conditions, turn into iron sulphide as iron sulphate in amounts of 2-7% by weight on

activated carbon or coke.

According to the invention, the disposable catalysts mentioned above can be substituted with adsorbents that are extracted from the soot produced by gasification or partial combustion

of liquid and/or solid fuels. As an application

in such a gasification resp. partial combustion comes on

speech next to those in the refineries or petrochemical

either formed oils or oily residues resp. extracts from coal, shale and sand, especially from the above-mentioned hydrogenation formed residue or also the combined hot sludge without previous separation of the hydrogenation heavy oil.

In case of gasification or partial combustion of these substances up-

standing soot, which is determined by the process, is washed out by gas

the stream with water. This sewage forms permanent suspensions. It is possible e.g. according to the method mentioned in DE-OS 25 54 235, whereby by adding oil to produce soot agglomerates which can easily be separated from oil/water and can be activated with different media such as e.g. CO, C0~or H~0 at high temperatures. Specific surface area of over 600 m 2 /g is easy to achieve.

The disposable catalyst according to the invention can due to "their large internal surface" adsorptively bind the coke particles formed during the sump-phase hydrogenation. Thereby, crusting of the reactor system is strongly prevented" and thus a significant process improvement is achieved. The charged single-use catalyst is discharged via the heat separator system and supplied with the hot sludge or the other hydration residue for restriction, especially in a gasification or delfo incineration plant. By this return of the single-use catalyst-containing hot sludge is enriched in the soot pellets the heavy metals originating from the oil, especially the catalytically active components vanadium and nickel, whereby an improved product refinement is achieved.

In special cases it may be necessary further

to increase the catalyst activity, as the soot is impregnated with salts of one or more catalytically active metals.

As catalytically active, the metals from the first to eighth subgroup of the periodic system as well as the fourth main group are to be considered, preferably titanium, chromium, iron, cobalt, nickel, zinc, tin and lead. The soot should preferably be charged with 0.1-10

% metal by weight. This can take place simultaneously with the activation of the soot pellets.

Example

In a vertical tube reactor of 4.5 liter content was

the hydrogenated 4.0 kg/h of a residue from vacuum distilla-

tion of Arabian light crude oil with 3 Nm~V t of hydrogen at 450°C and 280 bar. In experiment I no catalyst was used, in experiment II 5% by weight of dried soot pellets from heavy oil gasification was used as a disposable catalyst.

The following table shows that when the disposable catalyst is used, the residue conversion and asphalt degradation are enhanced and a shift in the product spectrum in the direction of the desired light products is observed.

Claims (6)

1. Method for hydrogenating heavy oil, bitumen or the like at temperatures between 250 and 550°C, preferably between 380 and 480°C and pressure between 50 and 700 bar, preferably between 100 and 325 bar, in the presence of 0.1-10 % by weight of an optionally catalytic metal-salt-containing carbon-containing catalyst, separation of the hot sludge at temperatures up to 100 K, preferably 20-40 K below the hydrogenation temperature, characterized in that soot from a heavy oil gasification or partial combustion is used as catalyst. 2. Method according to claim 1, characterized in that the soot is recovered from gasification or partial combustion that the residue formed by hydrogenation. 3..' Method according to claim 1, characterized in that the soot is extracted in by gasification or partial combustion of the hot sludge. in 4.. Method according to one of claims 1-3, characterized in that the soot is activated, e.g. with CO, CO2/H^O at temperatures above 200°C. 5.<.>Procedure according to one of claims 1-4, characterized in that the soot as catalytically active metal compounds contains one or more of the elements titanium, chromium, iron, cobalt, nickel, zinc, tin and lead. 6. Method according to one of claims 1-5, characterized in that the soot contains 0.1-10% by weight of metal compounds.