DE1770834A1 - Process for desulphurising and dearomatising petroleum distillates - Google Patents

Description

PATENT LAWYERS

DR.-ING. BY KREiSLER DR.-ING. SCHONWALD 1770834 DR.-ING. TH. MEYER DR. FUES

COLOGNE 1, DEICHMANNHAUS

Cologne, July 5th, 1968 Ρα / Αχ

The Britiah Petroleum Company Limited, Britannic House, Moor Lane, London, E, C. 2 (England).

Process for the desulfurization and dearomatization of petroleum distillates

The invention "refers to the desulfurization and dearomatization of petroleum distillates boiling in the range of 60 to 25O ⁰ C ·

Fractions of petroleum distillates used as solvents, laocbenzines, luminous oil and the like is known to have a sometimes considerable content of aromatic hydrocarbons, which is necessary for certain applications are disadvantageous. It has already been proposed to use these aromatic hydrocarbons by catalytic hydrogenation to convert and, if the hydrogenation catalyst is a sulfur-sensitive reduced nickel catalyst, the feed of a previous hydrocatalytic Subject to desulfurization to reduce the sulfur content to a maximum of 50 parts by weight per million parts by weight. However, since the poisoning effect of sulfur on nickel is cumulative, even small amounts of sulfur are present On the order of a few parts per million in a feedstock is harmful.

The German patent specification. (Patent application P

45 251.4) of the applicant describes the desulfurization of

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Straight-run petroleum fractions containing up to 2.0% by weight of 96 sulfur contain, naoh a process which is characterized in that the fraction is subjected in a first stage of the catalytic hydrogenating desulfurization and thereby converts the greater part of the sulfur into hydrogen sulfide, the hydrogen sulfide is removed and then the fraction with reduced sulfur content with one off elemental nickel on a carrier brings together existing catalyst under conditions under which the remainder Sulfur is adsorbed by the nickel essentially without releasing hydrogen sulfide · By this Process, the sulfur content can be reduced to 1 ppm or less. The present invention combines one two-stage desulfurization similar to that described in the above-mentioned patent with a subsequent dearomatization process using a reduced Nickel catalyst.

The invention, accordingly, the desulfurization and dearomatization of petroleum distillates boiling in the range of 60 to 25O ⁰ C and containing up to 2 wt .- # sulfur and up to 25 wt .- # aromatics, according to a method which is characterized that the distillate is subjected in a first stage to the catalytic hydrogenating desulphurisation and thereby converts the greater part of the sulfur into hydrogen sulphide, the hydrogen sulphide is removed, the fraction with reduced sulfur content in a second stage with a catalyst consisting of elemental nickel on a carrier under conditions Combined, under which the remaining sulfur is adsorbed by the nickel essentially without liberation of hydrogen sulfide, without substantial hydrogenation of the aromatics and without significant hydrogenative cracking of the feed, and the aromatics in a third stage over a catalyst consisting of elemental nickel on a carrier hydrogenated.

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Any available petroleum fractions can be used, but dearomatization is necessary, especially with certain boiling limit solvents (SBF solvents), laokbenzines and high-quality kerosene, which is used as light petrol. The specifications for special boiling point petrol prescribe a narrow boiling range, for example 60 to 8O ⁰ C, 60 to 90 ⁰ O, 80 to 110 ⁰ C and 100 to 140 ⁰ C Invention to be disassembled. If all of the feed is processed and then distilled, only one distillation is required. If it is fractionated / and the individual sections are processed, each section must be stabilized for itself.

According to the invention, a two-stage desulfurization is proposed because it is with the usual method of catalytic hydrogen desulfurization is difficult, remove the last traces of sulfur from a feedstock. These traces of sulfur are most likely Ring compounds, e.g., thiophenes and substituted thiophenes. With the usual hydrogenating desulphurisation, the existing sulfur is converted into hydrogen sulphide, which is then removed and the ring joints are more resistant to such treatment.

The catalytic hydrogen desulfurization conditions can be selected according to the usual practice. For example, the fractions at 204 to 510 ⁰ C and 3.5 to 105 atm at a space flow rate of 0.1 to 20 V / V / hour. w ith hydrogen in an amount of 36 to 900 Nnr / m *. The hydrogen can be circulated or carried out with a straight passage. Catalysts which are suitable for such a process can contain one or more oxides or sulfides of elements of Groups VIa and VIII of the Periodic Table on a support consisting of one or more

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refractory oxides of elements of groups II to Y of the periodic system, e.g. from cobalt and molybdenum oxide insists on aluminum oxide

The one during the catalytic hydrogenating desulphurisation The hydrogen sulfide formed is removed before the second desulfurization stage so that the desulfurization like nickel is not wasted on this easily removable sulfur. The greater part of the hydrogen sulfide can be removed in the high pressure and low pressure separators, which are normally a reactor or a zone in which the catalytic hydrogenation desulphurisation is carried out As an alternative or in addition to these separators, the hydrogen sulfide can be removed by any known method, e.g. by stripping with inert gas, alkalis » washing with sodium hydroxide, by adsorption on one Adsorbents such as zinc oxide, clay or molecular sieves, or by treatment with a solvent such as a Glycol-amine solution

The product freed from hydrogen sulfide from the catalytic hydrogenating desulfurization is in the second Desulfurization stage passed over a catalyst consisting of elemental nickel on a support, which the absorbs residual sulfur and is gradually sulfided · It was found that the presence of a slight Hydrogen amount is advantageous, even if it is not a hydrogen desulfurization, because none Hydrogen sulfide is formed. The hydrogen must of course be sulfur-free. The beneficial effects of the Hydrogen is attributed to the fact that the sulfur is present in the form of organic sulfur compounds and that during the adsorption of the sulfur Unsaturated organic radicals are formed on the nickel, which tend to polymerize on the nickel surface and reduce the catalytic activity of the nickel. if

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When hydrogen is present, these radicals become saturated into harmless saturated hydrocarbons. The amount of hydrogen required for this purpose can be calculated. It is very low, especially for the reason that the product from the first stage only has one contains a small amount of sulfur. For example, the amount of hydrogen required for a feedstock is which contains 50 ppm sulfur, only 9.3 x 10 1 (based on normal conditions) per liter of feed material · The present The amount of hydrogen must not be too high for a substantial hydrogenation of the aromatics present or a hydrogenation To avoid caking of the paraffins under pressure. Accordingly, any large excess of hydrogen from the first ' Stage can be removed before entering the second stage. This can expediently be done in the separators above in connection with the removal of hydrogen sulfide were called. As an alternative or in addition, other means of removing the hydrogen sulfide can be used be applied. When working with the hydrogen cycle in the catalytic hydrogenated desulphurisation no gaseous hydrogen escapes from this stage. In this case it is appropriate to the second stage To supply hydrogen separately in an amount that prevents deactivation.

The amount of hydrogen supplied to the second stage must be so be regulated so that it is above the minimum required to prevent the deactivation of the nickel on the carrier is necessary, with the maximum amount of hydrogen supplied depends on whether the niokel is fresh, i.e. not sulphided. The nickel can be considered fresh, if the sulfur / nickel atomic ratio at any point in the catalyst bed is below 0.06j1, i.e. if the Niokel has hydrogenation activity at every point in the * βtt. If the The catalyst is fresh, the molar ratio of the hydrogen supplied to the hydrocarbon (based on

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Total input) do not exceed 0.3: 1. During operation may be the molar ratio of hydrogen supplied to hydrocarbons, based on total input, to none Time to exceed 10: 1. Preferably the molar ratio is from supplied hydrogen to hydrocarbon at 0.001 to 0.2: 1.

The feedstock for the second stage can be used depending on whether the nickel is sulfided or not Vapor phase or liquid phase are present, the criterion being the above-mentioned sulfur / nickel atomic ratio of 0.06: 1 · If the catalyst is not sulfided, the feed must be in the liquid phase, where the amount of hydrogen supplied is limited to the amount that the feedstock at the working temperature and at Working pressure saturates · In this case there is essentially no hydrogen partial pressure. With increasing Sulphide formation on the catalyst, the amount of hydrogen supplied can be increased so that a hydrogen partial pressure is available. The feedstock in this latter case can be vapor or liquid, whereby Liquid phase operation is preferred. When in the liquid phase is being worked, it is appropriate to lead the feedstock from bottom to top.

The solubility of hydrogen in the feed depends on the type of feed, the ambient temperature and on the ambient pressure. From the table below, the influence of increasing pressure is in the range from 7 to 70 kg / cm for the solubility of two pure paraffinic hydrocarbons at a molar ratio of primary hydrogen to hydrocarbon of 0.1: 1.

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Druok. Hydrogen mole fraction in the liquid phase kg / om H ₂ / butane at 37.8 ⁰ O \ H ₂ / ootane at 37.8 ⁰ C

7 0.004

28 0.025

70 0.057

0.005 0.021 0.050

You values show that the solubilities are at the two Are similar to hydrocarbons. With increasing temperature one would expect an increase in solubility, unless the critical temperature of the heavier Component is achieved. The following table shows the influence of heating the liquid phase from the vapor-liquid equilibrium mixture at constant pressure shows that this is indeed the case.

Pressure, Hydrogen mole fraction in the liquid phase H ₂ / 0ctan at 115.6 ⁰ C. kg / cm H ₂ / butane at 115.6 ⁰ C. System only
fluid 7th System only
in vapor form dto. 28 0.018 dto. 70 System only
fluid

The table shows that the phase conditions change more easily at lower pressures and with lower boiling components. The feedstock is a relatively complex mixture of components of different G _s C-number, and of different type of molecule, and the influence of changes in the reaction conditions are also complex. However, if the reaction conditions are carefully chosen according to the kind of the feed, it is possible to avoid hydrogen pressure in the system when the catalyst is fresh.

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Naphthenes can be added to the feed to the second stage be added when the aromatics content of the feed is high, i.e. above 15% by weight. This has the Purpose to avoid the rapid hydrogen uptake that the consequence of the hydrogenation of such an amount of aromatic hydrocarbons would be by / a substantial Causes fluctuation in the concentration of the hydrogen present and an excessive rise in temperature could become. The naphthenes can be produced by the direct addition of a suitable material or, more expediently, by circulation leadership of the third stage (hydrogenation stage) of the process according to the invention are added.

In the foregoing, it has been shown that the temperature and pressure can be determined by taking the hydrogen / hydrocarbon ratio into account must be chosen. It is also useful in the second stage at fairly high temperatures to work, since the sulfur absorption capacity and the desulfurization activity of the supported nickel catalyst with the Increase in temperature. In practice, the temperature is determined by the use of side reactions, e.g. cracking, isomerization and possible ring opening, an upper limit is set. Of these reactions, cracking is the most important. With With increasing sulphidation of the nickel, the working temperature can be increased without the formation of by-products takes place. The space velocity of the second Level depends on the amount of sulfur present and on the value to which it is to be lowered, but taking into account of these requirements, it should expediently be as high as possible.

In view of the above considerations, the Reaction conditions other than the ratio of supplied hydrogen to hydrocarbon from the following ranges to get voted:

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Temperature 50-316 ⁰ C,

preferably 75-250 ° C

Pressure 0-350 atm,

preferably 7-140 atm

Room flow rate 0.002-10 V / V / hour, speed preferably 0.1-5 V / V / hour. (■ based on the liquid state)

The temperature rise that takes place must be within the stated range. The outlet temperature of the The reactor of the second stage must therefore not be above the upper limit of the range, and the inlet temperature must be above the lower limit. The upper limit also applies to the elevated temperature that is possible when the nickel is partially sulfided in the second stage.

The sulfur content of the first stage product depends on the original sulfur content and the boiling range of the Feed and the conditions of the catalytic hydrogenating desulfurization. Preferably the The sulfur content in this first stage is reduced as much as possible and thereby the service life of the nickel in the second stage extended. Suitably the sulfur content of the first stage product should be 50 ppm, preferably Do not exceed 10 ppm. The sulfur content of the product the second stage is preferably less than 1 ppm, in particular less than 0.5 ppm and can be below 0.1 ppm lie. The above sulfur levels apply to both bound and unbound sulfur, but are expressed as an element.

The desulphurized product from the second stage is in the last stage of the process according to the invention, preferably in the vapor phase or mixed phase (steam / Liquid) hydrogenated on entry into the last stage. The reaction conditions can be from the following ranges to get voted:

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Temperature 25-35O ° C,

preferably 50-300 ° C

Total pressure 1 * 75-140 atm,

preferably 7-105 atm

Space flow velocity
(based on liquid state) 0.1-10 7 / V / hour.

Excess hydrogen, ■ * ■ *

based on total effort 9-900 hm / m, · »■ *

preferably 36-180 Nm / nc

Liquid (product) cycle can be used to control the temperature of the third stage, especially if the aromatics content of the feed is above the stage 5 wt .- # is. The application of fluid circulation means that the volume of material passing through the reactor is increased and to achieve the same contact time it would be necessary to use a larger reactor. Alternatively, if cooling is necessary, this can be achieved by using a cooled tubular reactor in which the catalyst is contained in the tubes that are surrounded by a coolant. In this Reactor type, a higher mean catalyst bed temperature can be achieved for a given hydrogenation rate, than is possible with an adiabatic reactor. Any substance in the temperature range is suitable as a coolant of the process is thermally stable. If a refrigerated tubular reactor is used, the third stage is used preferably operated exclusively in the vapor phase, otherwise distribution difficulties may occur If, however, one is working with product circulation, the fact that the product is entering the reactor means that in the plus phase, that the heat of evaporation contributes to the cooling effect and the minimum of liquid, which is necessary to achieve the cooling effect can be used. This means that the total stake in the Final stage reactor enters at as low a temperature as possible, provided that the temperature is so high that that the catalyst is sufficiently active to remove the aromatics in the

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Hydrogenate feedstock.

The process conditions selected from the ranges mentioned above depend on the required degree of hydrogenation (i.e. dearomatization), which in turn depends on the Aromatics content of the feed to the stage

desired

and the type of at · product depends. For certain types of Siedegrenzenlösungsmitteln aromatics, for example, less than 100 ppm be required and this can use with materials of the process to achieve that contain up to 25 wt. -I »aromatics. When kerosenes the original aromatic content may be up to 25 wt. -Is, and cutting down on an aromatic narrower M halt of less than 1 wt .- # is possible. The temperature of the final stage can be increased as needed during processing to compensate for a decrease in the activity of the catalyst over time.

The above description was limited to the one-stage implementation of the catalytic hydrogenation Desulphurization, the adsorption of sulfur on the supported nickel catalyst and hydrogenation, but these can Measures are carried out in several stages. In particular, in the process according to the invention, the hydrogenation be carried out in several stages. Furthermore, any number of reactors can be used in each stage. J

A possible mode of operation in the second stage of the method according to the invention is illustrated by the figure shown schematically.

In the embodiment shown, a product from the first stage (catalytic hydrogenative desulfurization) pumped into a saturator 21 by the pump 2. The valves 15, 17, 18, 24 and 25 are closed. Excess Hydrogen leaves the saturator 21 through lines 22, 26 and 28. The valves 23 and 27 are open. The latter

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is effective as a pressure control valve, with the excess Gas is blown off and suitably used in the other stages of the process according to the invention. In the saturator 2 * 1 the feed is saturated with hydrogen, and the feed, which contains only dissolved hydrogen, enters then through lines 4 and 6 and the open valve 5 and enters the reactor 7, which contains fresh catalyst. Liquid product emerging from the reactor 7 goes through lines 3, 10 and 12 and the open valve 11 to open valve 13i from which there is a regulated amount through the Line 14 reaches the output stage · Cooling takes place in the cooler 9.

When the activity of the catalyst has decreased, further hydrogen is fed to the reactor 7 by the Valves 6, 23 and 11 closed and valves 15, 17, 18, 24 and 25 are opened. In this pail the input material passed through the saturator 21 and from there through the valve 24 to the reactor 7. Excess hydrogen will not blown off through valve 23 as before, but goes into the reactor with the feedstock. The ones from the Liquid emerging from the reactor is cooled in the cooler 9 as before, but not directly to the product, but through Line 10 and valve 15 are fed into a high-pressure separator 16. Secondary hydrogen is passed through the separator 16 the valves 25 and 18 and the lines 20, 26 and 19 ^ supplied to maintain the pressure in the system. Excess Gas is discharged from the stage through the pressure regulating valve 27. The liquid product from the separator 16 goes through the valve 17 and the line 12 to the quantity control valve 13 and from there to the product (i.e. to the output stage).

The supported nickel catalyst used in the second and third stage may contain any known natural or synthetic carrier such as the refractory oxides of Elements of groups II to V of the periodic table or kieselguhr, pumice stone or sepiolite. Preferred as a carrier

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becomes sepiolite, and the preferred catalyst for that second and third stages are nickel on sepiolite and are manufactured in accordance with British Patent 899,652 and activated. Sepiolite is preferred as a carrier because it is under reducing or oxidizing high temperatures Can withstand conditions that contain nickel in finely divided form and with a large surface area and relatively cheapest.

The supported nickel catalyst produced and activated according to the said British patent can contain 1 to 50 wt. Nickel (expressed as elemental nickel), in particular 5 to 25 wt .- ^ nickel contained. Am such a catalyst has a large nickel surface area and high activity and selectivity. It was found that he sulfurized up capable of adsorbing to a sulfur / nickel atomic ratio of at least 0.75: 1. Because the sulfur absorption capacity of the supported nickel catalyst is high and well known, a sufficient amount can be provided in order to achieve an economical To achieve catalyst life.

The hydrogen used in all stages of the process according to the invention may or may not be technically pure a gas mixture from a refinery process, e.g. the residual gas from a reforming plant operated with steam, which also contains methane, or exhaust gas from catalytic reforming can be used. The hydrogen however, it must be sulfur-free. The exhaust gas of the catalytic reforming is preferred, since the work in the Liquid phase allows the use of relatively high pressures and the exhaust gas of the catalytic reforming is available at around 28 atm. The gas preferably contains at least 50 mol- #, especially 70-99 mol- # hydrogen.

According to usual practice, the hydrogen can be fed to each stage in a single pass or circulated. When working with circulation using a gas

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Mixture, e.g. a methane-containing gas mixture, can do this Methane through extraction from the cycle gas or through separation removed from the liquid products.

example 1

a) First stage: catalytic hydrogenative desulphurisation

A conventional catalyst containing cobalt oxide and molybdenum oxide on aluminum oxide was ^{pretreated with hydrogen at 332 °} C. and then presulfurized at 332 ^° C. with carbon disulfide in n-heptane. A straight-run jöeatillate fraction from Kuwaitro oil, which boiled in the range of (C, - Ms) HO ⁰ C and contained 120 ppn sulfur, was desulfurized over this catalyst under the following conditions:

Temperature 204-316 ° C

Pressure 28 ^ tU

Room flow velocity 4.0 V / V / h (based on the liquid state)

Hg circulation volume 70 Nnr / nr

Make-up gas 70 mol-ji H ₉ ,

30 MoI-Jt CH ₄

The sulfur content of the product ranged from 0.1 to 1.5 ppm.

b) Second stage: desulphurization using a supported nickel catalyst

Straight-run distillate that is described in a) Way had been desulphurized, was over a fresh catalyst containing 10 wt. passed in the liquid phase, in the flow system described and illustrated under the following conditions was worked:

Temperature 204 ⁰ C

Pressure 28 atm

Room flow velocity 2.0 V / V / h (based on liquid state)

Make-up gas to saturator molar ratio of hydrogen supplied Hydrogen to hydrocarbon 0.02: 1

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177083A

- TP -

In this experiment, the sulfur content of the straight run distillate decreased from 1.1 to 0.1 ppm.

The aromatic content of the distillate was 5% by weight and existed from different amounts of Cg to Cg aromatics. No change in the aromatic content was detected by the analysis by gas-liquid chromatography. After an operating time of 1000 hours, the experiment still ran satisfactorily

0) Third stage: dearomatization rune

The product obtained from step (b) was over a catalyst containing 10% by weight nickel on sepiolite hydrogenated to convert the aromatics to naphthenes. The following working conditions were applied: Temperature 204 ° C

Pressure 28 atm

Room flow velocity 1.0 V / V / hour. (based on liquid state)

Straight pass gas 70 mole-96 Hp,

30 mol # CH ₄

Molar ratio of gas supplied

to hydrocarbon 0.3 to 0.6: 1

In this way the aromatics content of the distillate to a very low value, namely 50 ppm. This attempt was still satisfactory after 1500 hours in progress.

Example 2

a) and b) first and second stages: Catalytic hydrodesulfurization and desulfurization over Nickelträgerkataly sator

A boiling in the range (Cc) to 170 ⁰ C straight-run C ^ - distillate fraction was desulfurized over a cobalt oxide and molybdenum oxide on aluminum oxide catalyst containing as provided in Example 1 (a). To the

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Then thiophene was added to increase the sulfur content to 22 ppm · This material was then transferred to a fresh 10 percent by _e - # desulfurized nickel on sepiolite-containing catalyst in the liquid phase under the following conditions:

Temperature 204-260 ⁰ C

Pressure 28 atm

Room flow velocity 2.0 V / V / h (based on liquid state)

Supplementary gas to the saturator hydrogen

Molar ratio of added

Hydrogen to hydrocarbon 0.02: 1

The sulfur content of the product was 0.2 ppm · the catalyst still had its old activity after 700 hours.

Example 3

a) First stage: catalytic hydrogenating desulfurization

The sulfur content of straight-run kerosene was increased from 1700 ppm to 2.2 ppm by hydrative desulfurization Cobalt oxide-molybdenum oxide reduced to aluminum oxide.

b) Second stage: desulphurization via Niokelträgerkatalyaator

The product of step (a) was over a fresh, 10 wt .- # nickel on sepiolite containing catalyst in the liquid phase in the described and illustrated Desulfurized flow system under the following conditions:

temperature
pressure

Room flow velocity (based on the liquid state)

Supplementary gas to the saturator hydrogen

Molar ratio of fed

Hydrogen to hydrocarbon 0.02: 1

238 ° C. 28 atü 0.25 V / V / h

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In this experiment, the sulfur content of the straight run kerosene decreased from 2.2 to 0.3 ppm.

The aromatic content of the kerosene was 18% by weight, determined by infrared spectroscopy. With this analytical method, there was no change in the aromatic content after desulfurization to be established.

This experiment still ran flawlessly after a duration of 2233 hours.

o) Third stage: dearomatization

The product from step (b) was over a 10 wt .- # Catalyst containing nickel on sepiolite for converting aromatics into naphthenes in the liquid phase, among the following Conditions hydrogenated:

Temperature 218 ⁰ C

Pressure 28 atm

Space flow velocity
(based on liquid state, fresh use) 0.25 V / V / hour.

Space flow velocity

( Product cycle)

(based on liquid state) 0.5 V / V / hour.

Straight-pass gas 70 mol- # Hg,

30 MoI-Jf CH ₄

Molar ratio of inlet gas to
Total bet 0.6: 1

In this way the aromatic content of the kerosene was reduced by 18 reduced to 0.8 wt .- ^.

This experiment still ran flawlessly after a running time of 2200 hours.

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Claims (1)

Claims 1.) A process for desulfurizing and dearomatization of boiling in the range between 6O ° and 250 ⁰ C petroleum distillates containing up to 2 wt.% Sulfur and up to 25 wt.% Aromatics, characterized in that the distillate in a first stage subjected to the catalytic hydrodesulfurization, thereby converting the greater part of the sulfur into hydrogen sulfide, which is removed, the fraction with reduced sulfur content in a second stage with a catalyst consisting of elemental nickel on a carrier under conditions such that the remaining sulfur passes through the nickel is adsorbed with essentially no liberation of hydrogen sulfide, without substantial hydrogenation of the aromatics, and without substantial hydrogenative cracking of the feed, and in a third stage the aromatics are hydrogenated over a catalyst consisting of elemental nickel on a carrier. 2.) A process according to claim 1, characterized in that as the distillate a boiling in the range between 60 ° and 170 ° C naphtha a boiling in the range between 150 ° and 190 ⁰ C mineral spirits or in the range between l8o ° and 250 ⁰ C boiling kerosene is used. 3.) Process according to claim 1 or 2, characterized in that the catalyst is a first stage lncer! Cobalt oxide-molybdenum oxide used on alumina-containing catalyst. h.) Process according to Claims 1 to J, characterized in that the sulfur content of the distillate is reduced in the first stage to not more than 50 parts by weight per million parts by weight. 1 09883/1381 5.) Method according to claim 1 to 4, characterized in that that in the second stage hydrogen in an amount of not less than 9.3 χ 10 1 per liter of feed used under normal conditions wherein the amount of hydrogen is not more than a molar ratio of supplied hydrogen to hydrocarbons from 0,; 5: l, based on the total input, with a sulfur / Nickel atomic ratio of less than 0.06: 1, and not greater than 10: 1, based on the total input, for one Sulfur / nickel atomic ratio of not less than 0.06: 1. 6.) Method according to claim 1 to 5j, characterized in that that you always use a molar ratio of hydrogen to hydrocarbon fed from 0.001 to 0.2: 1 is working. 7.) The method according to claim 1 to 6, characterized in that one works in the second stage in the PlUssigphase with an amount of hydrogen not exceeding the maximum amount that of the feed at process temperature and pressure would be released with a sulfur / nickel atomic ratio of less than 0.06: 1. 8.) Process according to claim 1 to 6, characterized in that in the second stage in the liquid or vapor phase works with an increase in the amount of hydrogen to a value at which there is a hydrogen partial pressure, with a sulfur / nickel atomic ratio of not less than 0.06: 1. 9.) Process according to claim 1 to 8, characterized in that the feedstock is up through the catalyst bed directs. 109883/1381 10.) Method according to claim 1 to 9, characterized in that that naphthenes are added to the feedstock in the second stage if the aromatic content is greater than 15% by weight. 11.) The method according to claim 1 to 10, characterized in that one works in the second stage under the following reaction conditions except for the ratio of supplied hydrogen to the hydrocarbon temperature 50 ° to j5l6 ° C, preferably 75 ° to 250 ⁰ C pressure 0 to 550 atmospheres, preferably 7 to 140 atmospheres Room flow 0.002 to 10 V / V / hr, preferably speed, 0.1 to 5 V / V / hr. based on the liquid state 12.) The method according to claim 1 to 11, characterized in that one works in the third stage in the vapor or mixed phase under the following reaction conditions temperature 25 ° to 350 ⁰ C, preferably 50 ° to 300 ⁰ C total pressure 3J5 to 140 atü, preferably 7 to 105efcü room flow rate 0.1 to 10 V / V / hour. speed, related to the fluid state., -j. Hydrogen ^{over- 9 to 9} °° ^Nm ^ <preferably shot, based on 3 ° to 180 NmVm the total use 13 ·) Method according to claim 1 to 12, characterized in that that the liquid product of the third stage to regulate the temperature of this third stage in the reactor of third stage. 14.) The method of claim 1 to 13, characterized in that one uses a supported nickel catalyst in the second and third stages is calculated, contains 1 to 50 wt.% Nickel as elemental nickel on sepiolite. 109883/1381