DE2054771A1 - Process for catalytic hydrogenation converting a residue of carbon to hydrogen oil - Google Patents

Description

Shell Internationale Research Maatschappij N.V., The Hague, Netherlands

¹¹ Process for the catalytic hydrogenative conversion of a residual hydrocarbon oil "

Priority: November 18, 1969 »Great Britain, No. 56 357/69

The invention relates to a method for catalytic hydrogenating Conversion, in particular hydrated desulphurisation, a residual oil, which process is essentially liquid Phase is carried out.

\ In view of the problem of increasing air pollution by sulfur dioxide from the combustion of fuels and fuels with a relatively high sulfur content, more and more laws and regulations are being passed that limit the sulfur content of fuels. Crude oils, residual oils and oil fractions which contain relatively high proportions of sulfur compounds are therefore becoming increasingly difficult to sell compared to corresponding oils with a low sulfur content and must therefore be desulphurized before they are used

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puts on the market. The catalytic one carried out directly hydrogenating desulphurization of the aforementioned heavy oils and crude oils, however, are still problematic in terms of both catalyst and engineering.

Light petroleum fractions and other hydrocarbon distillates which contain sulfur compounds can easily be desulfurized with the aid of a fixed bed process in which these oil fractions and distillates are passed in the presence of hydrogen over catalysts suitable for hydrogenating desulfurization. The technological problems with this type of process have already been solved. The hydrogenated desulfurization of residual oils and crude oils carried out using a fixed bed is, however, regarded as impracticable or at least uneconomical, since the reactor in question has to be shut down very frequently in order to replace the used catalyst with fresh one. There are two main reasons for this requirement. Crude oils, such as distilled or below atmospheric pressure was distilled under reduced pressure crudes _f and other heavy hydrocarbon oil fractions, such as "black oils from plants flowing out of the" visbreaking "(" visbreaking ") oils or tar sand, is known to contain various high molecular weight metal-containing and metal-free components. These components interfere with the catalytic hydrogenation desulfurization process to which such crude oils or heavy hydrocarbon oil fractions are subjected and damage the catalyst used in the aforementioned process, as will be explained below.

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The aforementioned metal-free components include high proportions of resins, polyaromatics and asphaltenes. In particular the asphaltenes have a disadvantageous effect in the aforementioned process because they have high molecular weight, non-distillable, oily compounds represent with sulfur, nitrogen and / or oxygen atoms and form oil-insoluble coke precursors. The Asphaltene are generally in crude oil or the oil fraction in colloidal dispersed form, and they have a tendency to flocculate and deposit on the catalyst particles when heated. At the high temperatures used in the conversion, this flocculation occurs during hydrodesulfurization also promoted because the aromatic character of the liquid phase, in which the aforementioned asphaltenes in colloidal Form are dispersed, by the hydrogenation and hydro-cracking of the ("poly '^ - aromatic compounds also decreased will.

Of the metal-containing impurities, the best known are those containing nickel and vanadium. One at reduced pressure According to known data, distilled vegetable oil can exceed 0.05% by weight Vanadium and over 0.01 wt% nickel, each expressed as Metal. In general, these metals are in the form of thermally stable organometallic complexes, such as metalloporphyrins, available. A significant proportion of the organometallic complexes is associated with the asphaltenes and is thus enriched in the residue fraction.

The main difficulty in hydrodesulfurization of

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Crude oils of the heavy oil fractions of the aforementioned type are based on the above-mentioned asphaltene deposition on the catalyst particles, as this is due to the degradation of the asphaltenes results in severe coke formation. The simultaneous

verririforfc Deposition of the heavy metals on the catalyst particles together with the formation of coke from the aforementioned asphaltenes the effectiveness of the catalyst with regard to the conversion of, in particular, sulfur-containing compounds. Further effect the carbonaceous deposits formed during the flocculation of the asphaltenes bind the catal, vs ° gate particles to one another, what a clogging of the fixed catalyst bed and This results in an ever greater drop in pressure, which may also be due to the formation of coke. The rising one Pressure drop requires a particularly strong pressure force, which is often not available in practice, and he. can after all " become high that no remedial action is possible. The process must then be interrupted and the catalyst replaced or if possible to be completely regenerated.

As mentioned, the formation of coke and metal deposition reduce the activity of the catalyst, as a result of which the process equilibrium is disturbed. The lower the catalyst activity is, the higher is that to achieve a sufficient degree of desulfurization of the residual oil or just treated the temperature required for the corresponding heavy oil fraction. In practice, the general procedure is that the Starts the process at the lowest possible temperature,

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in which the desired conversion is just about to take place «Ob- ■ probably in accordance with this method of working in hydrated desulphurisation a product with an essentially constant sulfur content is obtained, there are other properties of the desulphurized product, like the viscosity, by no means constant due to the increasing temperature. As the temperature rises, the hydrocracking reactions decrease too, so that the oil to be desulfurized in always higher amounts of gases and low boiling oil fractions,

Easily as ^x petrol, heavy petrol or kerosene is converted.

As a result, a heating oil with variable properties and variable quality is obtained. In addition, the service life is of the catalyst relatively short in such a process.

According to a modified method, the hydrogenative desulphurisation can in principle close to the maximum permissible temperature be started, in this case, however, because of an excessively high catalyst activity, too profound takes place hydrogenated desulphurisation and because of pronounced hydro-cracking reactions only a little heating oil is obtained. Such a process is also difficult to regulate because of the hydrogen consumption is not constant because the degree of sulphurisation changes in the course of the Deactivation of the catalyst changes.

You can see that there is still a need for a technical

hvdrenden feasible and economical / desulphurisation process for residual hydrocarbon oils.

1705

The object of the invention was to develop a new, hydrogenating en * tsehwe— To provide felling process available, in which the flow period between two successive catalyst exchanges / is as long as possible and which, under essentially constant reaction conditions, is a desulphurized product of provides essentially constant properties. This object is achieved by the invention.

The invention is therefore a method for catalytic hydrogenating Fm * rindling, in particular hydrogenating desulphurization, of an Eüekstands hydrocarbon oil in an im essential liquid phase, which process is characterized in that hydrogen sulfide is added to the oil at the beginning of the process and / or a hydrogen sulfide supplying compound is added in a proportion which is at least 0.05% by weight HpS » based on the fresh oil, is and / or corresponds to and which continuously or gradually during the process a value less than $ 80 based on the amount added at the start of the procedure.

Although the most important application of the invention Process based on direct, catalytic, hydrogenated desulphurisation based on residual hydrocarbon oils, this process can also be applied to other catalytic, hydrogenating Conversions of residual hydrocarbon oils like that Hydro-cracking, for example to make

with high VI
Base oils for lubricating oils / from long or short residues.

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The proportion of hydrogen sulphide and / or the hydrogen sulphide-yielding compound used at the beginning of the process of the invention is and / or preferably corresponds to at least 0.1% by weight, in particular at least 0.5% by weight, in each case based on the fresh oil. During operation, the proportion of hydrogen sulphide and / or the hydrogen sulphide-supplying compound added to the feed is reduced in order to keep the degree of hydrodesulphurisation essentially constant. This proportion is preferably reduced in the course of the process to a value of less than 65%, in particular less than $ 50, of the amount added at the beginning of the process. Any sulfur compound which readily supplies hydrogen sulfide under the prevailing conditions can be used as the hydrogen sulfide-supplying compound, which should be present in a proportion corresponding to the required amount of hydrogen sulfide. Specific examples of suitable compounds which provide hydrogen sulfide are sulfur dioxide, carbon disulfide and the alkyl mercaptans with up to 8 carbon atoms in the molecule.

Due to the presence of the hydrogen sulfide or the hydrogen sulfide donating compound, the hydrogenative desulfurization process of the invention is more stable and a more constant degree of desulfurization is achieved. Of even greater importance, however, is that the catalyst service life is extended considerably and that the catalyst can withstand a higher proportion of deposited metals before ^his: Activity

loses for the hydrogenating desulphurisation. Because of the strong The sulfur-containing hydrocarbon oil under substantially constant reaction conditions is improved catalyst stability hydrogenated desulfurized, and the desulfurized product therefore has an essentially constant quality.

The pronounced effect of the hydrogen sulfide or the hydrogen sulfide supplying compound on the stability and service life of the catalyst is all the more surprising since the starting material to be hydrogenated to be sulphurized in general itself has a high sulfur content (at least 1.0 wt .- ^) and there in the desulfurization of this starting material Hydrogen sulfide is set free. To achieve the effects described above, you must. Hydrogen sulfide or a compound which yields hydrogen sulfide obviously be present immediately when a hydrogenating desulphurisation reaction is taking place he follows.

It is known that hydrogen sulfide is used in hydrocarbon conversion processes can be used. In these known processes, the hydrogen sulfide or the HpS are supplied Compound, however, either for presulphidation of the sulfur-resistant catalyst or used for this catalyst in the sulphidated state as the hydrocarbon oil to be converted is low in sulfur. The addition of sulfur compounds pursues the general purpose in such a case, the to activate the catalyst used. According to the procedure of

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- y -

Invention, however, the hydrogen sulfide improves the catalysis. sator stability by having the activity of the sulfur-resistant Catalyst decreased.

The process according to the invention is essentially liquid Phase carried out. This "means that during the hydrating Desulfurization at least 80 $ by volume of the desulfurized Residual hydrocarbon oil is in the liquid phase. Eventually the process of the invention also becomes complete carried out in the liquid phase. In such a case, all of the residual oil to be desulphurized is in the liquid phase before, and it is not used for desulphurisation more hydrogen is used than dissolved in the liquid hydrocarbon phase under the prevailing reaction conditions v / can ground., whereby the formation of a gas phase is prevented.

The hydrogen required for hydrated desulphurisation may be in the form of a hydrogen-containing gas stream, such as a reformer waste gas stream, or as essentially pure hydrogen can be supplied. The hydrogen-containing gases preferably have an Hp content of 60 vol .- $ on.

The required proportion of hydrogen sulfide or the sulfur

, _ "_.", ..,. , either.as such, -. ,, hydrogen-supplying compound can / the to be desulphurised Residual oil or the hydrogen-containing gas stream fed into the reactor can be added. If under product or gas recirculation is being used * the required

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Hydrogen sulfide content can also be supplied via these streams, An advantageous method for introducing hydrogen sulfide into the process of the invention consists in feeding via a product recycle stream. It was found that this rebound oil to supply the residue to be desulphurized

SchwpfpI— Oil with the required amount of HpS sufficient hydrogen content contains, if before the / the extracted desulphurized oil a part this oil is returned and the one to be desulphurised Residual oil is mixed.

The proportion of the hydrogen sulfide added to the residual oil to be desulfurized is to be reduced in the course of the process of the invention, as mentioned, to one fourth of less than 80 % of the amount added at the start of the process. If the hydrogen sulfide is introduced via a product recycle stream in the process, the lowering of the added to desulfurize residual oil amount of hydrogen sulfide can be "very practical achieved in that in the course of the process of separating a part of the hydrogen sulfide from the \ recycle stream, for example by a partially reducing the pressure and / or partially stripping off this return stream and / or by increasing the temperature in the high-pressure separation device used Amount of hydrogen sulfide can also be achieved very conveniently by increasing the gas velocity used in the course of the process.

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The "obtained from a hydrogenative desulfurization process Oil product is generally referred to as ^ (hydrogenating) desulphurized "product. However, this" does not necessarily mean that this product is essentially sulfur-free, rather "known only that it is compared to the fresh raw material has a reduced sulfur content. The sulfur content can depend on this original sulfur content of the desulphurized product, however, almost the value O have.

The method of the invention is preferably carried out using a plague bed. There can be both plague beds with both axial and radial flow direction is used. When using a plague bed with axial flow direction the process can be carried out either upstream or downstream. If the inventive method is completely in liquid phase is carried out, a plague bed is preferably used with a radial flow direction.

Any known catalyst can be used in the process of the invention can be used for hydrogenation desulphurisation. Sulfur-resistant catalysts are particularly preferred,

and / or before at least one metal of the VI * VII. and / or VIIL subgroup of the periodic table and / or sulfides and / or oxides of these metals on at least one amorphous, heat-resistant inorganic oxide of II. and / or III. and / or IV. Group of the Periodic Table. Specific examples preferred such catalysts are nickel / tungsten,

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Nickel / molybdenum, cobalt / molybdenum and nickel / cobalt / molybdenum on silicon dioxide, aluminum oxide, magnesium oxide, zirconium dioxide, Thorium Oxide, Boron Trioxide or Hafnium Oxide or combinations the aforementioned inorganic oxides, such as silicon dioxide / aluminum oxide, Silicon dioxide / magnesia or aluminum oxide / magnesia.

The catalyst used in the process of the invention can also contain other additives, such as boron phosphate or phosphorus, and / or halogens such as fluorine or chlorine. The boron phosphate can in a proportion of 10 to 40 wt .- $, preferably 15 to 30 wt .- ^, based in each case on the total catalyst, present while the halogens and phosphorus are used in a proportion of less than 10 wt .- ^.

Although the metal components of the catalyst can be present in any proportion, the catalyst used according to the invention preferably has a total metal content of 2 to 35% by weight, in particular 5 to 25% by weight. The metals of subgroup VIII of the Periodic Table are generally used in a lower proportion (about 0.1 to 10 wt .- $), the metals of VI. Subgroup of the periodic system is generally used in a higher proportion (about 2.5 to 30% by weight), while the total proportion of the metal components, as mentioned, is preferably less than 35% by weight. The atomic weight ratio of the metals of the VIII. Subgroup to those • of the VI. · Subgroup can be within a wide range, but is preferably 0.1: 1 to 5 ' i.

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According to the invention "particularly suitable catalysts are a commercially available catalyst for hydrodesulfurization containing 4» # 1 wt parts Co and 10.3 wt parts Mo # 100 ^G has ew.-AIPO parts, as well as a different catalyst, which contains 3.1 parts by weight of Ni, 11.7 parts by weight of Mo and 2.6 parts by weight of P per 100 parts by weight of Al ₂ O ₃ .

Instead of inorganic oxide carriers, carriers of the can also be used Zeolite type can be used. Particularly suitable aluminosilicate zeolites are the zeolites with a SiOp / AloO * molar ratio -

how
nis of at least 3: 1 »/ 'zeolite Y. These aluminosilicate zeolites can either be used as such or embedded in an inorganic. see oxide matrix, such as aluminum oxide, can be used. The proportion of this matrix "is generally from 20 to 80% by weight," based on the carrier.

The particle size of the catalyst used according to the invention is preferably less than 2 mm, in particular 0.4 to 1.5 mm. Particularly satisfactory results are achieved with a catalyst sieve fraction of 0.5 "to 1 mm.

Conventional reaction conditions suitable for hydrodesulfurization are used in the process of the invention. These conditions can vary widely, depending on the type of starting material. It is with temperatures of

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-H-

300 "to 475 ° C, preferably 385 Ms 445 ° C unl ^R / Wrucken from 30 to 350 kg / cm, preferably 75 to 225 kg / cm, is employed. ■ The weight hourly space velocity may also lie within a wide range and is in generally 0.1 and 10 parts by weight of fresh oil charge / part by volume of catalyst / h, preferably 0.3 to 5 parts by weight of fresh oil charge / parts by volume of catalyst / h. The hydrogenative desulfurization is preferably carried out under such severe conditions that a desulfurization of at least 40 ^, preferably 50 to 85 fo, is achieved.

That which is to be desulfurized by hydrogenation according to the process according to the invention Residual oil can be any sulfur-containing, Be petroleum containing residues. During the process there is also a partial nitrogen separation if the oil also contains nitrogen compounds. The method of the invention is applied with particular advantage to residual oils which Contain at least 0.002 wt .- $ vanadium and a sulfur ™ 'have a content of at least 1 wt .- #. It can be seen that the starting material can be entirely crude oil. Since the sulfur-rich Components of a crude oil and also the metal-organic However, compounds have a tendency to accumulate in the higher boiling fraction, the process of the invention becomes more commonly applied to sump fractions of a crude oil, i.e. to Fractions obtained by top distillation or distillation of a crude oil at atmospheric pressure or reduced pressure became. Typical such residues generally consist essentially of hydrocarbons and / or organic

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Compounds having at least one hetero atom, boiling above 36O ⁰ C and containing a substantial proportion of asphaltic substances. The aforementioned starting oil can thus have an initial boiling point or a boiling point of 5 ^ etv / as below 36O ⁰ C, provided that a substantial proportion, for example, boiling from 40 to 50 vol .- $, his hydrocarbons above 360 ⁰ C. In principle, the residual oil or the oil fraction can be a crude oil subjected to top distillation, a long or a short residue. The aforementioned starting oil can be subjected to a pretreatment, such as a plasma distillation and / or deasphalting and / or hydrogenating refining in the absence of a catalyst.

Examples of other heavy oil fractions, which after the process According to the invention, dark oils, oils flowing off from visbreaking systems, tar sand oils and mixtures can be used such oil fractions. These oil fractions can also be mixed with the aforementioned residual oils or oil fractions are processed.

The residual oil or oil fraction should preferably be one Alkali and / or alkaline earth metal content of less than 0.005 wt .- ^ have. This is preferably alkali and / or Alkaline earth metal content 0.0001 to 0.0025 wt. #. If the proportion of the aforementioned metals in the oil or the oil fraction that (the) is to be desulfurized by hydrogenation, the upper value of the aforementioned If it exceeds the range, it should preferably be lowered by a suitable treatment such as washing.

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if

It has already been mentioned that / the method of the invention is complete is carried out in the liquid phase, no more hydrogen should be used than under the prevailing reaction conditions dissolved in the liquid hydrocarbon phase can be, whereby the formation of a gas phase is prevented. A method of obtaining enough dissolved hydrogen for desulfurization to make available consists of recycling at least a portion of the recovered desulphurized oil product s and its mixing with residual oil to be desulphurized. The aforementioned oil product is preferably in one Share of at least 3 parts by volume, in particular from 5 to 30 parts by volume per part by volume of the residual oil returned.

ι t

For most hydrogen desulfurization processes there is a such a reflux ratio of 5 to 15 is sufficient.

In the method of the invention, a relatively long flow period is required or catalyst service life achieved when the hydrogenating desulfurization completely in the liquid phase carried out a fixed catalyst bed with radial flow direction is, whereby a catalyst with a lower than that conventionally used in the eaves 1-Ström method Grain size is used '. The actual catalyst service life achieved depends on the proportion of oil processed Heavy metals and asphalt are removed.

In order to avoid poor distribution of the liquid flow through the catalyst bed when a radial flow direction is used avoid, it should be ensured that at least 40

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preferably 45 to 50 volumes — 9% by volume — of the liquid phase — flow through the upper half of the catalyst bed. This desired flow can be achieved by using a perforated, centrally arranged tube in the catalyst bed, which has a relatively large diameter compared to the reactor diameter and / or by using such a central tube with a special shape, that is, a narrow tube at the upper end and wide tube at the lower end, and / or that more openings are made at the upper end of the central tube than at its lower end. The liquid phase lra. ¹ to flow · ι radially through the fixed bed of catalyst either from the bed arranged in the central tube or towards this tube. If the hydrative desulphurization is carried out completely in the liquid phase, the rate of introduction of the water or a hydrogen-containing gas is adjusted so that the process of the invention per kg of the total starting material is 5 to 30 Nl Hp, preferably 15 to 20 Nl Hp is supplied. "Entire starting material" is to be understood as meaning the fresh residual oil used, which is mixed with the recycled ent sulphurized oil product.

The hydrogen can be fed into the fresh starting material, the recycled oil product or at various points Catalyst bed are introduced. However, both the fresh oil used as the starting material and the recycle product together with hydrogen prior to treating the mixed feed with the catalyst for the hydrogenated desulphurisation through a hydrogen saturation zone

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directed. This saturation zone is preferably located in the Near the inlet of the reactor for the hydrogenating desulphurisation

- treatment and can either inside or outside this reactor be arranged. The hydrogen dissolves in this zone

■> the prevailing conditions completely in the entire starting material. The hydrogen is preferably supplied in proportions such that the entire starting material is essentially saturated under the respective conditions.

An advantageous embodiment of the method of the invention, in which the hydrogen desulfurization is completely in the liquid phase is carried out and a fixed catalyst bed with radial flow direction is used, is from the The flow diagram shown in the drawing can be seen.

According to the drawing, the residual oil to be hydrogenated and desulfurized is fed into the system via line 1 and pump 2. The pressurized oil flows via line 3 into the furnace 5, in which it is mixed with the hydrogen supplied via line 4 and with the desulphurised product returned via line 29. As will be explained below, this product still contains hydrogen sulfide, since it has not yet been depressurized after the hydrodesulfurization process. The heated mixture of fresh starting material, recycled product and dissolved hydrogen and hydrogen sulfide is transferred via line 6 into the reactor 9 operating with radial flow. The starting mixture is via ^: the line 10 provided with nozzles in the upper end of this reactor

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introduced. The oil flows over the saturation zone 11, which made of ceramic balls or another inert material, such as Raschig rings, into the. Distribution zone 12 for the ' gang material. The saturation zone 11 is designed so that a complete solution of the hydrogen fed into the system in the starting mixture before it comes into contact with the catalyst is ensured. That under the prevailing reaction conditions starting mixture still present in the liquid phase flows into the annular space 14 between the inner wall of the reactor and the perforated, cylindrical catalyst bed support eration 16. The catalyst zone 15 is provided with a suitable shaped, a zv / angular grain size having catalyst filled for the hydrogenating desulfurization. The starting oil is

into the catalyst bed through the openings made in the catalyst bed holder 16 / and flows through the bed to the central tube 13, in the interior of which it flows out of the reactor 9 via the line 17. The desulphurized product, which is still under the operating pressure, is partially withdrawn from the system and partially returned via line 27 _{} to} the recirculation pump 28 and line 29 into the reactor. The returned product is not relieved of pressure because it still contains hydrogen sulfide formed during the desulfurization and hydrogen sulfide not consumed during this process. If necessary, the returned product is diverted via line 30 to line 6, bypassing the furnace 5. Such a measure can be useful for regulating the temperature and for cooling the catalyst bed before the catalyst is replaced.

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The discharged via line 18, ent sulphurized product is first cooled in a heat exchanger 19 and then transferred to the high-pressure separating device 20. Via line is a gas phase formed in this separation device, mainly hydrogen, hydrogen sulfide, ammonia and the Contains light, gaseous hydrocarbons, withdrawn and fed to the use and / or treated in a conventional manner. (Return gas). The resulting liquid phase, which consists of the desulphurized product is made via the lines 22 and 25 deducted from the system. Line 23 eats with a valve 24, which is set automatically with the aid of the height control device 25 »

When the catalyst is replaced with fresh catalyst must be, the desulphurized product can be used to cool this DeschickuTg can be used. For this purpose, the valve 24 in the line 23 is closed, and the cooled product over Line 26, the pump 28 and line 30 returned to the reactor. The valve arranged in line 27 can also be kept closed so that all of the liquid product via the heat exchanger 19 and the high pressure separator 20 is directed.

The reactor 9 is equipped with devices for introducing an inert gas, like nitrogen. or additional hydrogen, in the Reactor (the lines 32 and 31 provided with the measuring device 33). The nitrogen is used to displace the Hydrogen needed before the. · - Reactor to be replaced the catalytic converter is opened.

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Since hydrogen sulfide has a beneficial effect on the hydrogenating Exercises desulfurization process, the withdrawn via line 21 can Gas phase the conventional for the separation of hydrogen sulfide Bypass used gas stripping tower and returned directly to the reactor 9 to be there together with the hydrogen sulfide to ensure the required hydrogen gas replenishment. The ammonia can in the conventional manner by washing either the liquid flowing out of the reactor with water Product before its flash distillation in the high pressure separator or the gas phase formed after the flash distillation can be separated off.

An advantage of the process of the invention is that the desulphurized products obtained can be used as such or as a mixture are relatively stable with other fuels, as indicated by a P value above 1 and a value for the hot

Piltration test below 0.10 wt .- ^ is illustrated (cf. the examples).

t
The examples explain the invention »

example 1

To illustrate the feasibility of hydrogenative residue desulfurization essentially in the liquid phase using a fixed bed catalyst, a long residue of a Caribbean crude oil is treated in the presence of a commercially available hydrogen desulfurization catalyst. The hydrogenative desulphurization is carried out in the semi-industrial use using an effluent procedure and a

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-Sending
Reactor with a catalyst capacity of 1000 ml. The length of the catalyst plague bed is about 90 cm. Among other things, the test facility is equipped with a device for returning the liquid, desulphurized product to the reactor. The recycled product is combined with fresh feedstock and the total stream is heated prior to introducing it into the top of the reactor. A separate hydrogen saturation zone is arranged outside the reactor. Top-up hydrogen is fed in together with the fresh starting material.

As a catalyst for the hydrogenated desulphurisation is a

Co / Mo / AlpΟ · * catalyst used, which has 4.9 parts by weight of CoO and 15.7 parts by weight of MoO, per 100 parts by weight of Al ₂ O, (on a dry basis). The grain size of this catalyst is 0.5 to 1 mm. The catalyst was measured using a hydrogen sulfide-containing gas mixture (10 vol .- $ H ₂ S) at a pressure of 10 kg / cm, with a gas space velocity of 400 l / lh and a gradual increase in temperature from room temperature to 350 ⁰ C. presulphided. The reactor is then flushed with hydrogen at a pressure of 50 kg / cm. The pressure is finally increased to 150 kg / cm, and the starting material to be hydrogenated and sulfurized is fed in.

The long residue obtained from a Caribbean crude is processed under the following conditions:

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Pressure, kg / cm x 150

Temperature, ⁰ C '4-20

Weight space velocity . (fresh load),

kg / liter.h 2.0

Feedback ratio

Product / fresh loading 10: 1

Inlet hydrogen gas _{ratio SjNl H 2} / kg fresh feed 250

Degree of desulfurization, $ p> 55

The hydrogenating desulfurization is carried out under the aforementioned conditions carried out essentially in the liquid phase. That Recycle product is withdrawn from the low pressure separator and prior to combining with the fresh feedstock with the help of nitrogen from hydrogen sulfide "freed.

The recovered, hydrosulfurized product has an average ε-sulfur content of about 0.8% by weight. After desulfurization of 2.1 t of starting material / kg of catalyst, rapid deactivation of the catalyst is determined and the service life test is terminated. After the pressure has been released and cooled, the spent catalyst is removed for analysis. There have about 22 wt .- # vanadium and 2.6 wt. -Fi nickel, relative to the fresh catalyst, the catalyst niederge-

beat. The sulfur content of the catalyst is 15.6 percent by weight.

From Table I are the properties of the starting material and, of the hydrogenated sulfurized product, which was obtained at the beginning of the experiment and near its end, reproduced.

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Table I.

Product analysis viscosity
at 99 ⁰ C, cS Starting
material product
at
Attempt
beginning product
at
Attempt
end Carbon, wt .- ^ relativ density
^(ä 7O / 4 ^} - 86.97 86.64 Hydrogen, wt .- ^ Pour point, ⁰ C. - 12.10 11.99 Sulfur, wt. - $> Flash point, ⁰ C 2.1 0.66 1.04 Nitrogen, wt .- ^ 0.52 0.2;> 0.26 Vanadium, wt. -Tfo 0.0212 0.0096 0.0142 Nickel, wt .- $ 0.003 0.0016 0.0022 Coking residue
according to Ramsbottom, Wt .- $ 2.9 5.8 6.6 57.1 16.25 16.89 0.9204 0.8935 0.8964 +23 + 17 +20 175 152 105

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Example 2

It becomes the influence of dissolved in the returned product Hydrogen sulfide illustrates the stability of the desulfurization process.

The whole, from the reactor of the pilot plant effluent of Example 1 liquid product is cooled by heat exchange with hot water at 7O ⁰ C. Part of the cooled desulphurized product is returned before the pressure is released. While pe is still under pressure, the recycled product is mixed with the pressurized, fresh hydrogen-containing fresh starting material and all of the starting material is heated and then fed into the reactor.

The starting material is obtained from a caribi crude oil long residue from Example 1 used. In the case of hydrated desulfurization, the following conditions worked:.

Pressure, kg / cm
Temperature, ⁰ o

Weight of room speed (fresh loading)

kg / liter.h

Product / fresh feed recycle ratio

Inlet hydrogen gas _{ratio. Nl H 2} / kg fresh feed

Degree of desulfurization, ° />

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150 - 420 410 0 2, : 1 10 125 50 approximately

A fresh Co / Mo / AlgO -, catalyst with the same grain size, presulphided in the manner described above, is obtained used·'

At the beginning of the experiment, the proportion of hydrogen sulfide is 1.1% by weight in the liquid reflux stream. During the trial

at the end of the test it decreases and finally reaches / a value of 0.8 wt .- ^.

Under the abovementioned conditions one works almost stably, and the catalyst loses its activity much more slowly than without the introduction of Söhweulfwassci'jtoff into the reflux stream. The proportion of freshly supplied hydrogen (purity about 99 _F 8. Vol ~ #) is quite low, however, the recycled product also contains in dissolved form hydrogen, which was not consumed in the desulfurization.

The recovered reductively desulfurized product has a constant sulfur content of 1.05 wt .- #, based on the total liquid product to _e on the catalyst can be employed to 3.2 t of oil / kg of catalyst to be processed, which corresponds to a service life of about 1050 hours is equivalent to. At the spent catalyst as have 29 "5 percent. -4> vanadium, 3 wt .- # nickel and 16 wt .- ^ carbon, based on fresh catalyst deposited.

From Table-II the properties, of the beginning, are to one middle point in time and properties of the desulphurized product achieved towards the end of the service life test.

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- 27 Table II

·) at
Attempt
beginning product at
Attempt
end *) Product analysis 86.74 at
Attempt
middle *) 86.51 Carbon, wt. - $> 11.91 86.65 11.97 Hydrogen, wt .- ^ 1.06 11.98 1.14 Sulfur, wt .- ^ 0.277 1.06 0.257 Nitrogen, wt .- # 0.0103 0.246 0.0102 Vanadium, wt .- ^ 0.0016 0.0102 0.0017 Nickel, wt. - $> 5.95 0.0015 6.12 Coking residue
according to Ramsbottom,
Weight # 5.11 viscosity 15.32 13.02 at 99 ⁰ C, cS 0.8977 14.54 0.8938 relativ density
^(d 70/4 ^} 0.8939 Resistance test 1.3 1.3 P value **). 1.5 ■ X - K · -
Hot filtration test,
Weight-96 <0.01 - a) <O, O1 <0.01 - b) *) At half-time of the attempt, 5
extracted from a Caribbean crude
rer origin passed over which
Properties like the first edition
of this, however, mainly j
viscosity (28.96 cS at 99 ⁰ G) and c
(0.294 GeWo- $) differs? dai
Deviations «, <0.01 sur processing one of
m long residue other-
3r roughly the same '
ingsmaterial owns itself
With regard to the vis-
len nitrogen content
? from that explain

109829/1705

**) The P (peptization) value is calculated according to the Equation ρ

P =

in which P denotes the peptization capacity of the oil medium and PR _ denotes the flocculation ratio of the asphaltenes at infinite dilution. A stable fuel has a P value above 1.0. The asphaltenes of the crude oil used have a J ¹ Rj _{310x value} of 35.

***) in the hot filtration test of the force and the fuel is heated to 100 ⁰ C and then filtered. The remaining on the filter residue is indicated in wt .- ^ and "actually vorhandcnei residue" (a) "After 24 hours at 100 designated G ⁰ is the force • or fuel filtered again and the residue thereby obtained is called" potential residue "(b). A stable fuel should have the lowest possible value for the "actually present" and "potential residue" f <0.1 wt .- ^).

Example 3

It will be the influence of the hydrogen sulfide content of the recycled desulphurized product on the catalyst service life and the degree of metal deposition on the catalyst closer illustrated.

semi-technical
The tests carried out in a / system with the

Long residue from Be i-Bpiel obtained from a Caribbean crude 1, which has a sulfur content of 2.1% by weight and one Vanadium content of 0.0212 wt .- $, are continued on the basis of an experiment in which the liquid return flow

is cooled and relaxed to atmospheric pressure. The hydrogen sulfide content in the liquid reflux stream "is 0.1 wt. $ at the start of the experiment and Ms increases" until the end of the experiment a value of $ 0.06 by weight. For the aforementioned experiment a fresh portion of the Co / Mo / AlpO ^ catalyst, which is based on a Grain size of 0.5 to 1 mm was crushed, used. It is carried out under similar experimental conditions as in Example 2, with the exception of the hydrogen gas ratio, which 200 Nl / kg freshly used oil is.

From Table IIIA are the properties of the test start and the desulphurized product obtained towards the end of the test can be seen.

109877/1705

Table III A.

product at trial
end Product analysis at trial
beginning 86.94 Carbon, weight -i » 86.81 11.90 Hydrogen, wt .- # 11.98 0.9 Sulfur, wt .- $ 0.8 0.263 Nitrogen, wt .- # 0.253 0.0119 Vanadium, wt .- ^ 0.0104 0.0018 Nickel, wt .- # 0.0016 5.1 Coking residue
according to Ramsbottom,
I wt .- ^ - Relativ density·
^(d 70/4 ⁾ 0.8931 +14 Pour point, ⁰ C +14 - Flash point, ⁰ C 80 Continuity always s P value 1.3 - Hot filtration test,
Weight # a) 0.02
0.01 *

Table III B

■ rtri
OP »
pq-ca
No. H ₂ S in the recirculated
th product, wt .- ^ at
Attempt
end By-
sectional
Sulfur-
salary
d. ent
sulfur
ten prod Catalysis
Brew! ätor-
duration Share of
at the Kataly
sator off
relaxed
Ni and V 1
2
3 at
Attempt
beginning 0
0.06
0.80 0.8
0.9
1.05 Tb-nne-r)
Loading
kung / kg
Kataly
sator H 25th
28
32 0
0.10
1.10 2.1
2.4
3.2 700
800
1050

10982? / 1705

Table IIIB shows the desulfurization according to the example 1 to 3 results obtained with regard to the catalyst life and the degree of metal deposition.

It can be seen from the values in Table IIIB that the increase in the hydrogen sulfide content of the return stream is an increase the degree of metal deposition on the catalyst and a prolonged catalytic converter service life. When applied of a return stream containing hydrogen sulfide, an almost constant degree of desulfurization is achieved without that the temperature needs to be increased.

Example 4

In order to reduce the influence of the temperature increase on the product properties, in particular to show the viscosity of the desulphurized product obtained, that is obtained from a Caribbean crude oil long residue from example 1 desulfurized at constant sulfur content by changing the temperature during the experiment is gradually increased. In a laboratory-scale device, a service life test with an amount of catalyst of 100 ml carried out. It becomes the same catalyst as in the above Examples used. Its grain size is 0.5 to

1 mm, and it was presulphided before use. It is at temperatures of 380 to 420 ⁰ C, a pressure of 150 kg / cm, a weight space velocity (fresh charge) of

2 kg / literJi, a reflux ratio of the hydrogen sulfide, free, desulphurized product for fresh loading of 10: 1, a hydrogen gas inlet ratio of 250 Nl H

1098 ?? / $ 170

fresh raw material and a sulfur content of the total liquid product from 0.9 "to 1 wt. worked -fo.

The service life test is canceled after about 1000 hours,. since the deactivation of the catalyst assumed such a degree has that the temperature has to be increased too much to maintain the desired sulfur content. Table IY shows the results obtained at several stages of the experiment.

109R ?? / 1705

Table IV

Product analysis

after 130 hours (temp. 380 ⁰ C)

after 446 hours (temp.

⁰ G)

after hours (temp.

⁰ C)

after

Hour (temp.

430 ⁰ C)

Carbon, wt .- $

Hydrogen, wt .- ^

Sulfur, wt. ~%

Nitrogen, wt .- $

Vanadium, wt .- ^

Nickel, wt. - $>

Coking residue according to EamslDottom,

viscosity
hot 99 ⁰ C,

cS

relativ density
^(d 70/4 ⁾
Pour point, ⁰ C

Flash point,

Resistance ste ot s

P value

Hot filtration test,

86.50 11.82

1.14

0.15

0.0132

3.98 27.65

0.9055

+ 23

138 *

2.6

a) 0.03

b) 0.03

86.64

11.92
0.92
0.268

.0.0115

5.13
21.30

0.8994

+ 20
114

2.0

0.01
0.01

86.74

11.96 0.97 0.267 0.0123 0.0018

5.95 20.49

0.8998

+ 20 120

1.9

<0.01 0.01

86.54

11.91 1.25 0.271 0.0146 0.0021

6.8 14.83

0.8970

+ 79

1.3

0.02 0.02

10982 ^ / 1705

The results shown in Table IV are obtained by treating the desulfurized product after a hydrogen stripping carried out degassing returns. The product is therefore free of hydrogen sulfide. Analysis of the product shows that For example, the viscosity is not constant at 99 ° C and rather with increasing temperature of the hydrating desulphurisation constantly decreasing. The sulfur content of the product obtained is also not as constant as that of the product according to the invention manufactured product (see example 2).

Example 5 ,

It becomes the influence of alkali metals present in residual oils on the activity of the catalyst for desulfurization shown.

A long residue obtained from a Middle East crude oil is desulphurized in a hydrogenated manner over a fixed bed, which consists of a fresh amount of the Co / Mo / AlpO ^ catalyst of Example 1 prepared became. The average grain size of the catalyst is 0.7 mm. To exclusively the effect of the alkali metal to show the liquid reflux stream at atmospheric pressure freed from hydrogen sulfide.

Both a long residue with a high sodium content graze as well as such a residue processed with a low sodium content. The two residues have the following Features on:

109827 / 1705-

analysis
of
Starting material , Wt. -1 ° Carbon, , Wt. -io Hydrogen, Weight - $> Sulfur, Weight -io Nitrogen, Weight -io Vanadium,

Weight?

Nickel,
Sodium,

Coking residue according to Ramsbottom, wt.

relativ density

viscosity cS at 99 ⁰ C, ⁰ C Pourροint, ⁰ C flash point,

- 35 -

Sodium content

high low 84.21 83.99 11.25 11.42 4.05 3.91 0.21 0.21 0.005 0.0049 0.0015 0.0013 0.0065 0.00035

7.7

0.9280

37.41

+ 11 172

8.6

0.9184

26.1

+

154

The aforementioned long residues are essentially in the liquid phase hydrogenated desulphurized, with an extensive external product recirculation is used. It becomes a presulphided Catalyst used. Table V shows the test conditions used and the results obtained evident.

Table V

Sodium content of the
Feeding, GeWo- $ 0.0065 0.00035 Procedural conditions Temperature, ⁰ G 420 420-435 2
Pressure, kg / cm 150 150 Weight space speed
capacity, kg / liter.h 1.0 0.75 Inlet Hydrogen Velocity
diness, Nl / kg fresh be
dispatch,
Return ratio HpS-free
Product / fresh supply 300
20: 1 300
about 20 Catalyst life, h
Catalyst utility value,
Tons of feed / kg kata
lyser 1400
2.1 4400
5.0 Average sulfur content
(entire liquid product),
Weight # 0.9 0.9 Deposited on the catalyst Metals Wt .- ^ (based on the
fresh catalyst) V + Ni 13th 27 N / A 4.6 1.2

1705

From the results given in Table V it can be seen that a low sodium content of the starting oil to be desulphurized extends the catalyst service life. If the sodium content of the starting material is not already less than 0.005% by weight per se, it is preferably reduced to this value

Example 6

A Caribbean crude oil subjected to distillation at atmospheric pressure (yield: 96.9 f ° _t based on the crude oil) with a sulfur content of 2.84% by weight, a vanadium content of 0.0393% by weight and a nickel content of 0.005% by weight 56 is essentially

a
chen in the liquid phase over / fixed catalyst bed hydrogenatively desulphurized, which was produced from a fresh portion of the Co / Mo / AlgO-z catalyst from Example 1 (grain size = 0.4 to 1.5 mm). The catalyst was presulphided. The hydrogenative desulphurization is carried out according to an upflow procedure

, carried out with product recycling. With a service life

^! - The return flow of the desulphurised product is tested

Atmospheric pressure freed from hydrogen sulfide. In another service life test, the liquid return flow is not relieved of pressure and not freed from hydrogen sulfide. In the latter case, the hydrogen sulfide content is the liquid Return flow at the start of the experiment 2.0 wt .- ^ and is up to

gradually humiliated.

End of the test / up to a value of 0.8 wt .- $ / is decreasing the hydrogen sulphide content of the liquid recycle stream through a gradual temperature increase of the high-pressure separator of 6O ⁰ C at start of the experiment at 8O ⁰ C for experimental

109827/1705

end achieved.

Table VI shows the conditions used and the results obtained.

109827/1705

* 59 Tatelle VI

HpS content of the return flow,
Wt .- ^ 0 2.0-0.8 Procedural conditions Temperature, ⁰ C 415-420 415-420 Pressure, kg / cm 150 150 Weight space velocity
(fresh supply)
kg / liter .h 1.0 Inlet hydrogen gas
ratio, Nl / kg 250 250 Repatriation ratio
Product / fresh supply 20: 1 10: 1 Catalyst utility value
Metric tons .
/ Charge / kg catalyst 0.7 1.8 Average desulfurization
grad, ok 70 50-55 Deposited metals (Ni + V),
Wt .- $ ("based on the
fresh catalyst) 15th 55

The inhibiting effect of hydrogen sulfide on activity of the catalyst for desulphurisation is from the table VI clearly recognizable. Perner shows, however, that the presence of the hydrogen sulfide in the return stream has a beneficial effect on the resistance of the cat-

1098 7 7/1705

lysators ", which has an extended catalyst life with an almost constant degree of desulphurisation. Under these conditions the catalyst can obviously have a higher amount of deposited metals before deactivation take up.

Example 7

A recovered from a crude oil caribischen long residue with a sulfur content of 2.1 wt .- $ is desulfurized in substantially the flü'ssigen phase over a fixed bed of catalyst by hydrogenation, which is composed of 1.5 mm extrudates of Co / Mo / A1 ₂ 0, catalyst of Example 1 consists. The catalyst was presulphided. The hydrogenating desulphurisation is carried out according to an upward flow procedure with product recirculation.In an endurance test, the return flow of the desulphurized product is freed from hydrogen sulfide at atmospheric pressure.In another endurance test, the liquid return flow is not depressurized and not freed from hydrogen sulfide. In ^{particular, the hydrogen sulfide content of the liquid reflux stream} at the start of the experiment is 1.4% by weight and gradually increases to one weight during the experiment

humiliated.

Final value of 0.3 wt. -Jo / - The lowering of the hydrogen sulphide content of the liquid reflux stream is achieved by gradually increasing the outlet gas ratio from 30 Nl / kg at the start of the experiment to 400 Nl / kg at the end of the experiment.

From Table VIl are the conditions used and those achieved Results visible.

- 41 Table VII

HpS content of the return flow,
Wt .- $ 0 1.4-0.3 Procedural conditions temperature, ⁰ C 420 420 p
Pressure, kg / cm 150 150 Weight space velocity
(fresh supply)
kg / liter, h ' 2.0 2.0 Outlet gas speed
Nl / kg 250 30-400 Feedback ratio
Product / fresh supply 10: 1 3: 1 Catalyst life, h 310 550 Catalyst utility value,
/ Charge / kg catalyst 0.9 1.6 Average sulfur content of the
desulphurized product, wt .- ^ 1.05 1.05

1098 ?? / 1705

Example 8

A long residue obtained from a Caribbean crude oil with a sulfur content of 2.1 wt crushed particles of the Co / Mo / Alρ0, catalyst of Example 1 consists. The catalyst was presulphided. The hydrating
Desulfurization is carried out according to an upflow procedure with product recirculation. In a service life test, the return stream of the desulphurized product is freed from hydrogen sulphide at atmospheric pressure. In another service life test, the liquid return flow is not
relieved of pressure and not freed from hydrogen sulphide · In the latter case, the hydrogen sulphide content is in the liquid
Return flow at the start of the experiment is 1% by weight and · becomes

gradually to a final value of

humiliated.

0.4% by weight * / The decrease in the hydrogen sulphide content of the liquid return flow is achieved by gradually increasing the outlet gas ratio from 80 Nl / kg at the start of the experiment to 225 Nl / kg
achieved at the end of the experiment.

From Table VIII are the conditions used and the
results achieved.

109827/1705

- 43 Table VIII

HpS content of the return flow,
Weight - $> O 1.0-0.4 Procedural conditions Temperature, ⁰ C 420 420 p
Pressure, kg / cm 150 150 Weight space velocity
(fresh supply).
kg / liter.h 2.0 2.0 Outlet gas velocity,
Nl / kg 250 80-225 Feedback ratio
Product / fresh supply 3: 1 3: 1 Catalyst life, h 700 1000 Catalyst utility value,
Metric tons .
/ Charge / kg catalyst 2.1 3.0 Average sulfur content of the
desulphurized product, wt .- ^ 0.7 1.06

The fourth given in Tables VII and VIII again show that by adding a certain amount of hydrogen sulfide to the Starting material and lowering this amount during the experiment a longer catalyst service life and a more stable one Working method can be achieved.

Claims (23)

Claims ι 1l process for the catalytic conversion of hydrogenation, especially / "special hydrogenation desulphurization, of a residue hydrocarbon oil in an essentially liquid phase, characterized in that hydrogen sulphide and / or a hydrogen sulphide-producing compound is added in a proportion to the oil at the beginning of the process which contains at least 0.05 wt. fo HPS, based on the fresh oil is una / or equivalent and which-during the process continuously or stepwise to a value of less than $ 80, based on the added at process beginning amount decreases is . 2. The method according to claim 1, characterized in that the proportion of the hydrogen sulfide and / or hydrogen sulfide-supplying compound added to the oil at the start of the process is at least 0.1% by weight H ₂ S, preferably at least 0.5% by weight HpS, based on the fresh oil, is and / or corresponds to. ^ 3. The method according to claim 1 or 2, characterized in that that the proportion of hydrogen sulfide added to the oil s- and / or hydrogen sulfide-yielding compound in the course of the process to a value of less than $ 65, preferably less than $ 50, of what was started added portion is decreased 4 · The method according to claim 1 "to 3 ·, characterized in that that part of the oil product obtained in the hydrogenating desulphurisation is fed back and is to be desulphurised with the Residual oil is mixed o 5. The method according to claim 4, characterized in that the returned, desulphurized oil product, which is to be mixed with the residual oil to be desulphurized, has not been relieved of pressure. 6. The method according to claim 4 or 5, characterized in that that the proportion of the residual oil to be desulfurized Hydrogen sulfide is lowered by the fact that in the course of the process a part of the hydrogen sulfide separated from the desulfurized oil product, which is returned for mixing with the residual oil to be desulfurized will, 7 «The method according to claim 6, characterized in that the Separation of part of the hydrogen sulphide from the one to be recycled ent sulphurized oil product by partial pressure release and / or partial stripping of the return flow and / or increasing the temperature is carried out in the high pressure separation device used. 8. The method according to claim 4 or 5, characterized in that that the amount of hydrogen sulfide added to the residual oil to be desulfurized is reduced by using the Gas ratio increased during the process. 1 09827/1705 9. The method according to claim 1 "to 7, characterized in that that the hydrogenating desulfurization with the help of a catalyst solid "bed is carried out. 10. The method according to claim 1 "to 9, characterized in that the catalyst is a solid, sulfur-resistant catalyst with a particle size of less than 2 mm, preferably 0.4 "to 1.5 mm. 11. The method according to claim ^ to 10, characterized in that that the residual oil has a sulfur content of at least | Has 1 wt .- $. ' - ί - 12. The method according to claim 1 "to 11, characterized in that the residual oil consists essentially of hydrocarbons and / or at least one heteroatom-containing organic carbon compounds with a boiling point above 360 ⁰ C and contains a significant proportion of asphaltic materials. 13. The method according to claim 11 or 12, characterized in that that the residue oil is a long residue. 14. The method according to claim 1 to 13, characterized in that the residual oil has a sodium content of less than 0.005 wt .- #, preferably from 0.0001 to 0.0025 wt .- ^, having. 109827/1705 205/1771 15 · The method according to claim 1 "to 14, characterized in that the hydrogenating desulfurization at temperatures of 500 to 475 ⁰ C, preferably 385 Ms 445 ⁰ C, and a Total pressure from 30 "to 350 kg / cm, preferably from 75" to 225 kg / cm. 16. The method according to claim 15, characterized in that that the desulfurization "at a weight space velocity from 0.3 "to 5 parts by weight residual oil / Part by volume of catalyst.h is carried out. 17. The method according to claim 1 Ms 16, characterized in that that a degree of desulfurization of at least 40 wt .- ^, preferably 50 to 85 weight percent. 18. The method according to claim 1 to 17 »characterized in that that it is carried out entirely in the liquid phase. 19 · The method according to claim 18, characterized in that the desulphurized product is recycled and in a portion of at least 3 parts by volume per part by volume of the residual oil to be desulphurized is mixed with this. 20. The method according to claim 19 »characterized in that the oil product in a proportion of 5 to 30 parts by volume, preferably 5 to 15 parts by volume per part by volume of the residual oil is returned. 1 09'ft 77/1705 21. The method according to claim 19 or 20, characterized in that in the hydrogenating desulphurization per kg of the residual oil to be desulphurized and of the returned, desulphurized oil product, 5 to 30 Nl H _2, preferably 15 to 25 Nl H ₂ , are used. 22. The method according to claim 19 to 21, characterized in that that that from the residual oil and the returned, desulphurized Oil product existing total raw material before the. Contacting the solid, sulfur-resistant catalyst together with hydrogen through a hydrogen saturation zone is directed, 23. The method according to claim 18 to 21, characterized in that the liquid phase radially through the catalyst plague bed flows. 24ο The method according to claim 23, characterized in that less liquid phase at least 40 vol. ~ $, preferably 45 to 50 vol .- $, / by the flow upper half of the catalyst bed. Process according to Claims 1 to 24, characterized in that that a desulphurized oil product with a peptization value of at least 1.0 and a hot filtration value of less than 0.1 wt. 109827/1705