NO143426B - ANALOGY PROCEDURE FOR THE PREPARATION OF NEW PHARMACODYNAMIC POLYENE COMPOUNDS - Google Patents

ANALOGY PROCEDURE FOR THE PREPARATION OF NEW PHARMACODYNAMIC POLYENE COMPOUNDS Download PDF

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NO143426B
NO143426B NO741144A NO741144A NO143426B NO 143426 B NO143426 B NO 143426B NO 741144 A NO741144 A NO 741144A NO 741144 A NO741144 A NO 741144A NO 143426 B NO143426 B NO 143426B
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oxide
hydrogen
zinc oxide
atmospheres
hydrocarbon
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NO143426C (en
NO741144L (en
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Werner Bollag
Rudolf Rueegg
Gottlieb Ryser
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Hoffmann La Roche
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    • C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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    • C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
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Description

Fremgangsmåte til avsvovling av hydrocarbon-oljer. Method for desulphurisation of hydrocarbon oils.

Foreliggende oppfinnelse vedrører avsvovling av hydrocarbonoljer. The present invention relates to the desulphurisation of hydrocarbon oils.

Hydrocarbonoljer, f. eks. slike man får Hydrocarbon oils, e.g. such as you get

ved fraksjonert destillasjon av petroleum, er ofte forurenset med svovelinneholdende forbindelser. For mange formål er det ønskelig at slike forurensninger fjernes. Avsvovling av hydrocarbon bestemt til matningsmateriale er f. eks. et nødvendig trinn by fractional distillation of petroleum, is often contaminated with sulphur-containing compounds. For many purposes, it is desirable that such contaminants be removed. Desulphurisation of hydrocarbons intended for feed material is, for example, a necessary step

ved fremstillingen av methanol fra en blanding av carbonmonoxyd og hydrogen fremstilt ved dampomformning (steam re-forming) av en «straight run» naftha. Ved denne fremgangsmåte er det viktig at nafthaen er i alt vesentlig fri for svovel, fordi hvis svovelinnholdet av nafthaen er over ca. 5 d.p.m., ødelegges katalysatoren som anvendes i dampomformningsprosessen raskt under vanlige tekniske betingelser. in the production of methanol from a mixture of carbon monoxide and hydrogen produced by steam re-forming a "straight run" naphtha. In this method, it is important that the naphtha is substantially free of sulphur, because if the sulfur content of the naphtha is above approx. 5 d.p.m., the catalyst used in the steam reforming process is rapidly destroyed under normal technical conditions.

Det er nå kjent en rekke avsvovlings-fremgangsmåter som forårsaker en stor nedsettelse av svovelinnholdet i hydrocarbonoljer. Svovelinnholdet av en «straight run» naftha kan f. eks. nedsettes fra 200— 1000 d.p.m. til 20—100 d.p.m. ved behandling med svovelsyre. Graden av avsvovling avhenger av den mengde syre som anvendes og av den grundighet hvormed syren og hydrocarbonet blandes. Alternativt kan man oppnå delvis avsvovling ved hydro-avsvovling. Det er f. eks. funnet at svovelinnholdet av en «straight run» naftha som koker i området opp til 165° C, kan nedsettes fra 357 d.p.m. til 10—26 d.p.m. ved å føre dampen blandet med et ekvimolekylært volum hydrogen ved 50 atmosfærers trykk over en katalysator bestående av koboltmolybdat på aluminiumoxyd ved 380° C. En lignende grad av avsvovling kan man oppnå ved å føre dampen, med eller uten hydrogen, over et kontaktmateriale bestående av zinkoxyd, manganoxyd eller jernoxyd ved 350—450° C. A number of desulphurization methods are now known which cause a large reduction in the sulfur content of hydrocarbon oils. The sulfur content of a "straight run" naphtha can e.g. reduced from 200 to 1000 d.p.m. to 20-100 d.p.m. by treatment with sulfuric acid. The degree of desulphurisation depends on the amount of acid used and on the thoroughness with which the acid and the hydrocarbon are mixed. Alternatively, partial desulphurisation can be achieved by hydro-desulphurisation. It is e.g. found that the sulfur content of a "straight run" naphtha that boils in the range up to 165° C can be reduced from 357 d.p.m. to 10-26 d.p.m. by passing the steam mixed with an equimolecular volume of hydrogen at 50 atmospheres pressure over a catalyst consisting of cobalt molybdate on aluminum oxide at 380° C. A similar degree of desulphurisation can be achieved by passing the steam, with or without hydrogen, over a contact material consisting of zinc oxide, manganese oxide or iron oxide at 350-450° C.

Ingen kjent avsvovlingsfremgangsmåte er i stand til i ett trinn å oppnå en nedsettelse til mindre enn 5 d.p.m. av svovelinnholdet i «straight run» nafthaer som er al-minnelig tilgjengelige. Det er imidlertid funnet at problemet med å oppnå denne grad av avsvovling på en økonomisk måte, er løst ved å anvende den fremgangsmåte som omfatter en ny kombinasjon av avsvovlingstrinn som beskrives i det følgende. No known desulfurization process is capable of achieving in one step a reduction to less than 5 d.p.m. of the sulfur content in "straight run" naphthas which are generally available. However, it has been found that the problem of achieving this degree of desulphurisation in an economical way is solved by using the method which comprises a new combination of desulphurisation steps which is described below.

I henhold til foreliggende oppfinnelse er det tilveiebragt en fremgangsmåte for avsvovling av hydrocarbonoljer som i alt vesentlig ikke inneholder ethylen- eller acetylen-umettede forbindelser, idet denne fremgangsmåte omfatter tre trinn; det første trinn omfatter å behandle hydrocarbonoljen med svovelsyre ved betingelser som angitt i det etterfølgende, og/eller fordampe oljen og deretter føre dampen som således er tilveiebragt, over et kontaktmateriale som omfatter zinkoxyd, manganoxyd eller jernoxyd (fortrinnsvis zinkoxyd) ved en temperatur mellom 350 og 450° C og ved et trykk mellom 1 og 50 atmosfærer, hvorved minst 70 % av svovelinnholdet i hydrocarbonoljen fjernes; det andre trinn omfatter å føre det fordampede hydrocarbon, sammen med hydrogen, ved en temperatur mellom 350 og 450° C og ved et trykk mellom 1 og 50 atmosfærer, over en hydroavsvovlings-katalysator; og tredje trinn omfatter å bringe produktet fra det andre trinn i kontakt med et hydrogensulfid-ab-sorberende materiale. According to the present invention, a method for desulphurisation of hydrocarbon oils which essentially do not contain ethylene or acetylene-unsaturated compounds has been provided, this method comprising three steps; the first step comprises treating the hydrocarbon oil with sulfuric acid under conditions as indicated in the following, and/or vaporizing the oil and then passing the vapor thus provided over a contact material comprising zinc oxide, manganese oxide or iron oxide (preferably zinc oxide) at a temperature between 350 and 450° C and at a pressure between 1 and 50 atmospheres, whereby at least 70% of the sulfur content in the hydrocarbon oil is removed; the second step comprises passing the evaporated hydrocarbon, together with hydrogen, at a temperature between 350 and 450° C and at a pressure between 1 and 50 atmospheres, over a hydrodesulfurization catalyst; and the third step comprises contacting the product from the second step with a hydrogen sulfide absorbent material.

Som angitt ovenfor, omfatter det første trinn av fremgangsmåten ett eller begge av to angitte avsvovlingstrinn. Det foretrekkes imidlertid at det første trinn omfatter begge disse trinn, dvs. å behandle hydrocarbonoljen med svovelsyre, deretter å fordampe den og føre dampen som er fremstilt på denne måte, over et kontaktmateriale bestående av zinkoxyd, manganoxyd eller jernoxyd (fortrinnsvis zinkoxyd) ved betingelser som er angitt i det foregående. As stated above, the first stage of the process comprises one or both of two stated desulfurization stages. However, it is preferred that the first step includes both of these steps, i.e. treating the hydrocarbon oil with sulfuric acid, then vaporizing it and passing the vapor thus produced over a contact material consisting of zinc oxide, manganese oxide or iron oxide (preferably zinc oxide) under conditions as stated above.

Svovelsyrebehandlingen kan utføres på vanlig måte ved eller under romtempera-tur. Man hør ikke la temperaturen av olje-og syreblandingen stige til over 40° C. En hensiktsmessig konsentrasjon av svovelsyre er 90—98 vektprosent. The sulfuric acid treatment can be carried out in the usual way at or below room temperature. Do not allow the temperature of the oil and acid mixture to rise above 40° C. An appropriate concentration of sulfuric acid is 90-98 percent by weight.

Olje- og syreblandingen som er igjen etter svovelsyrebehandlingstrinnet, kan hensiktsmessig adskilles elektrostatisk. The oil and acid mixture remaining after the sulfuric acid treatment step can conveniently be separated electrostatically.

Etter elektrostatisk adskillelse fra syren, vaskes hydrocarbonoljen fortrinnsvis med vandig alkali, f. eks. natriumhydroxyd for å fjerne gjenværende svovelsyre, adskilles elektrostatisk fra alkaliet og vaskes til slutt med vann. After electrostatic separation from the acid, the hydrocarbon oil is preferably washed with aqueous alkali, e.g. sodium hydroxide to remove residual sulfuric acid, is electrostatically separated from the alkali and finally washed with water.

Den adskilte syre kan føres tilbake til karet hvor hydrocarbonoljen og syren blandes. I det annet trinn av fremgangsmåten er temperaturen fortrinnsvis fra 380—400° C, er trykket er fortrinnsvis -mellom 4 og 20 atmosfærer. Særlig egnedé<1->hydroavsvov-lingskatalysatorer er palladium, platina eller koboltmolybdat, på en bærer av aluminiumoxyd. Såkalte koboltmolybdatkata-lysatorer er velkjente og omfatter bxydene av kobolt og molybden, enten som slike eller i kombinert form. The separated acid can be returned to the vessel where the hydrocarbon oil and the acid are mixed. In the second step of the method, the temperature is preferably from 380-400° C, the pressure is preferably between 4 and 20 atmospheres. Particularly suitable hydrodesulphurisation catalysts are palladium, platinum or cobalt molybdate, on an aluminum oxide support. So-called cobalt molybdate catalysts are well known and comprise the oxides of cobalt and molybdenum, either as such or in combined form.

Ethvert egnet materiale som er i stand til å absorbere hydrogensulfid kan anvendes i tredje trinn av prosessen. Det absor-berende materiale omfatter imidlertid fortrinnsvis zinkoxyd, manganoxyd eller jernoxyd (zinkoxyd foretrekkes). Disse stoffer har'den fordel at de absorberer hydrogensulfid effektivt fra den varme hydrogen-damp, som derfor ikke må avkjøles først. Any suitable material capable of absorbing hydrogen sulphide can be used in the third stage of the process. However, the absorbent material preferably comprises zinc oxide, manganese oxide or iron oxide (zinc oxide is preferred). These substances have the advantage that they absorb hydrogen sulphide efficiently from the hot hydrogen vapour, which therefore does not have to be cooled first.

Behandlingen med et kontaktmateriale bestående av zinkoxyd, manganoxyd eller jernoxyd, som kan utgjøre minst én del av første trinn av prosessen, og det annet og tredje trinn av prosessen kan hensiktsmessig utføres i én operasjon ved å føre hydrocarbondampen blandet med hydrogen gjennom 'en «sandwich» bestående av et lag hydroavsvovliirgs-katalysator anbragt mellom to lag som hvert består av zinkoxyd, manganoxyd eller jernoxyd. The treatment with a contact material consisting of zinc oxide, manganese oxide or iron oxide, which can form at least one part of the first stage of the process, and the second and third stages of the process can conveniently be carried out in one operation by passing the hydrocarbon vapor mixed with hydrogen through a "sandwich" » consisting of a layer of hydrodesulphurisation catalyst placed between two layers each consisting of zinc oxide, manganese oxide or iron oxide.

Fremgangsmåten i henhold til foreliggende oppfinnelse er særlig egnet til avsvovling av «straight run» naftha; med dette menes en blanding av paraffiniske, naftheniske og aromatiske hydrocarboner som man får ved fraksjonert destillasjon av petroleum og som har et kokeområde på ca. 10 til ca. 200° C. Fremgangsmåten er ikke egnet for avsvovling av hydrocarboner som inneholder vesentlige mengder av ethylen- eller acetylen-umettede forbindelser, som f. eks. hydrocarboner oppnådd fra en termisk krackningsprosess. The method according to the present invention is particularly suitable for desulphurisation of "straight run" naphtha; by this is meant a mixture of paraffinic, naphthenic and aromatic hydrocarbons which is obtained by fractional distillation of petroleum and which has a boiling range of approx. 10 to approx. 200° C. The method is not suitable for the desulphurisation of hydrocarbons which contain significant amounts of ethylene- or acetylene-unsaturated compounds, such as e.g. hydrocarbons obtained from a thermal cracking process.

Når en «straight run» naftha avsvovles i henhold til foreliggende oppfinnelse, blandes nafthaen i annet trinn av prosessen med hydrogen, fortrinnsvis i et 1 : 1 molforhold. When a "straight run" naphtha is desulphurised according to the present invention, the naphtha is mixed in the second stage of the process with hydrogen, preferably in a 1:1 molar ratio.

Det er funnet at for å nedsette svovelinnholdet av «straight run» naftha fra 500—2000 d.p.m. til 2—5 d.p.m. eller mindre, som er meget ønskelig hvis nafthaen skal anvendes i en dampomformningspro-sess til fremstilling av methanol-synthese-gass, er det viktig at mesteparten av svovelet fjernes før hydroavsvovlingstrinnet. Ved fremgangsmåten i henhold til foreliggende oppfinnelse fjernes meget mer enn 70 % av svovelet i første trinn av prosessen. I det annet trinn, som det foretrekkes å inkludere i det første trinn av prosessen, fjerner laget av zinkoxyd, eller en likeverdig forbindelse, i alt vesentlig alle de gjenværende mengder av de typer svovelinneholdende forurensninger som dette materiale er i stand til å fjerne, dvs. mercapta-ner, sulfider og disulfider. Det antas at disse forurensninger enten absorberes som slike eller hydrogeneres til hydrogensulfid, som deretter absorberes. Den gjenværende mengde av svovel er meget liten. Hydrogen-avsvovlingskatalysatoren katalyserer hy-drogeneringen av organiske svovelforbindelser, som f. eks. thiofener og thiofaner, til hydrogensulfid, som absorberes av det en-delige lag av zinkoxyd eller en likeverdig forbindelse. Forholdet mellom hydrogen og hydrogensulfid i kontakt med hydroavsvovlings-katalysatoren er meget høyt. Det er således umulig for noen påviselig mengde av organiske svovelforbindelser å eksistere i likevekt med hydrogen og hydrogensulfi-det som er dannet ved hydroavsvovlings-reaksjonen, og man kan oppnå en meget høy grad av svovelfjerning. It has been found that to reduce the sulfur content of "straight run" naphtha from 500-2000 d.p.m. to 2-5 d.p.m. or less, which is highly desirable if the naphtha is to be used in a steam reforming process for the production of methanol synthesis gas, it is important that most of the sulfur is removed before the hydrodesulfurization step. In the method according to the present invention, much more than 70% of the sulfur is removed in the first stage of the process. In the second step, which is preferably included in the first step of the process, the layer of zinc oxide, or an equivalent compound, removes substantially all of the remaining amounts of the types of sulfur-containing contaminants that this material is capable of removing, i.e. .mercaptans, sulfides and disulfides. It is assumed that these pollutants are either absorbed as such or hydrogenated to hydrogen sulphide, which is then absorbed. The remaining amount of sulfur is very small. The hydrogen desulphurisation catalyst catalyses the hydrogenation of organic sulfur compounds, such as e.g. thiophenes and thiophanes, to hydrogen sulphide, which is absorbed by the monolayer of zinc oxide or an equivalent compound. The ratio between hydrogen and hydrogen sulphide in contact with the hydrodesulphurisation catalyst is very high. It is thus impossible for any detectable amount of organic sulfur compounds to exist in equilibrium with hydrogen and the hydrogen sulphide formed by the hydrodesulphurisation reaction, and a very high degree of sulfur removal can be achieved.

Blandingen av varm, avsvovlet naftha-damp og hydrogen, som frembringes ved len foretrukne metode etter den foreliggende oppfinnelse, kan blandes med damp Dg anvendes som matningsmateriale ved en iampomformningsprosess for fremstilling av methanolsynthesegass. Dette er selvføl-gelig bare én anvendelse av oppfinnelsen, som finner en rekke vide anvendelsesområ-der i industrielle prosesser hvor hydrocarbonoljer må avsvovles i stor utstrekning. The mixture of hot, desulphurised naphtha steam and hydrogen, which is produced by the preferred method according to the present invention, can be mixed with steam Dg used as feed material in a reforming process for the production of methanol synthesis gas. This is of course only one application of the invention, which finds a number of wide areas of application in industrial processes where hydrocarbon oils must be desulphurised to a large extent.

De følgende eksempler er illustrerende for fremgangsmåten etter foreliggende oppfinnelse. The following examples are illustrative of the method according to the present invention.

Eksempel 1: Example 1:

En «straight run» naftha (fra Vene-zuela) med egenvekt 0,746 og kokeområde 103—164° C, inneholdende 250 d.p.m. svovel ble ført gjennom et lag av zinkoxyd ved 400° C med en væske-volumhastighet pr. time («liquid hourly space velocity») på 0,75. Svovelinnholdet av produktet var 56 d.p.m. Dette delvis rensede materiale blandet med et ekvimolekylært volum hydrogen ble deretter ført gjennom en katalysator bestående av 0,3 % platina på aluminiumoxyd ved 385° C, og deretter gjennom et lag av zinkoxyd i form av 3 mm kuler ved 385—390° C. Væske-volumhastigheter pr. time gjennom disse lag var henholdsvis 1.1 og 0.75. Svovelinnholdet av produktet var mindre enn 1 d.p.m. A "straight run" naphtha (from Venezuela) with specific gravity 0.746 and boiling range 103-164° C, containing 250 d.p.m. sulfur was passed through a layer of zinc oxide at 400° C with a liquid-volume rate per hour ("liquid hourly space velocity") of 0.75. The sulfur content of the product was 56 d.p.m. This partially purified material mixed with an equimolecular volume of hydrogen was then passed through a catalyst consisting of 0.3% platinum on aluminum oxide at 385° C, and then through a layer of zinc oxide in the form of 3 mm balls at 385-390° C. Liquid volume rates per hour through these layers were respectively 1.1 and 0.75. The sulfur content of the product was less than 1 d.p.m.

Eksempel 2: Example 2:

En «straight run» naftha med egenvekt 0,72 og kokeområde 55 til 166° C, inneholdende 357 d.p.m. med svovel, ble behandlet med 2 vektprosent 98 % svovelsyre i en vibrerende plateblander, og svovelinnholdet ble derved nedsatt til 46 d.p.m. Dette delvis rensede materiale ble deretter fordampet og ført sammen med et ekvimolekylært volum hydrogen gjennom lag av koboltmolybdat på aluminium og kuler av zinkoxyd under de følgende betingelser: Temperatur 380° C A "straight run" naphtha with specific gravity 0.72 and boiling range 55 to 166° C, containing 357 d.p.m. with sulphur, was treated with 2% by weight of 98% sulfuric acid in a vibrating plate mixer, and the sulfur content was thereby reduced to 46 d.p.m. This partially purified material was then evaporated and passed with an equimolecular volume of hydrogen through layers of cobalt molybdate on aluminum and spheres of zinc oxide under the following conditions: Temperature 380° C

Trykk 3,06 atmosfærer Væske-volumhastighet pr. time over koboltmolybdat-katalysator 0,9 Væske-volumhastighet pr. time over zinkoxydkuler 1,2 Pressure 3.06 atmospheres Liquid-volume rate per hour over cobalt molybdate catalyst 0.9 Liquid volume rate per hour over zinc oxide balls 1.2

Svovelinnholdet av produktet etter at dette eksperiment var utført i 7 dager, var 1—3 d.p.m. The sulfur content of the product after this experiment was carried out for 7 days was 1-3 d.p.m.

Eksempel 3: Example 3:

En «straight run» naftha (fra Kuwait) med egenvekt 0,725 og kokeområde 55— 166° C, inneholdende 250 d.p.m. svovel, ble behandlet med 2 vektprosent 96 % svovelsyre i en skovltypeblander, vasket med 10 % kaustisk soda og endelig vasket med vann. Denne behandling nedsatte svovel innholdet til 20 d.p.m. Nafthan ble deretter fordampet, blandet med et ekvimolekylært volum hydrogen og for-oppvarmet til 400° C ved et totalt trykk på 16 atmosfærer. Blandingen av naftha og hydrogen ble deretter ført suksessivt gjennom et lag av zinkoxyd-kuler, et lag koboltmolybdat-pel-lets og til slutt et annet lag av zinkoxyd-kuler. Væske-volumhastigheter pr. time gjennom disse lag var henholdsvis 2,4, 1,0 og 2,4. Det totale svovelinnhold i nafthaen var etter denne behandling 3—5 d.p.m. A "straight run" naphtha (from Kuwait) with specific gravity 0.725 and boiling range 55— 166° C, containing 250 d.p.m. sulphur, was treated with 2% by weight 96% sulfuric acid in a paddle type mixer, washed with 10% caustic soda and finally washed with water. This treatment reduced sulphur the content to 20 d.p.m. Naphthane was then evaporated, mixed with an equimolecular volume of hydrogen and preheated to 400°C at a total pressure of 16 atmospheres. The mixture of naphtha and hydrogen was then passed successively through a layer of zinc oxide pellets, a layer of cobalt molybdate pellets and finally another layer of zinc oxide pellets. Liquid volume rates per hour through these layers were respectively 2.4, 1.0 and 2.4. The total sulfur content in the naphtha after this treatment was 3-5 d.p.m.

Claims (4)

1. Fremgangsmåte til avsvovling av en hydrocarbonolje som i alt vesentlig ikke inneholder ethylen- eller acetylen-umette-te forbindelser, som f. eks. en «straight run» naftha, karakterisert ved at fremgangsmåten omfatter følgende tre trinn, 1) å behandle hydrocarbonoljen med svovelsyre, fortrinnsvis 90—98 vektprosent, ved romteperatur, idet syren deretter fjernes, f. eks. ved elektrostatisk atskillelse, og/ eller fordampe oljen og deretter føre damp-ene over et kontaktmateriale valgt fra gruppen bestående av zinkoxyd, manganoxyd og jernoxyd ved en temperatur mellom 350 og 450° C og ved et trykk mellom 1 og 50 atmosfærer, hvorved minst 70 %1. Process for desulphurisation of a hydrocarbon oil which essentially does not contain ethylene or acetylene-unsaturated compounds, such as e.g. a "straight run" naphtha, characterized in that the method comprises the following three steps, 1) treating the hydrocarbon oil with sulfuric acid, preferably 90-98 percent by weight, at room temperature, the acid then being removed, e.g. by electrostatic separation, and/or vaporizing the oil and then passing the vapors over a contact material selected from the group consisting of zinc oxide, manganese oxide and iron oxide at a temperature between 350 and 450° C and at a pressure between 1 and 50 atmospheres, whereby at least 70 % av svovelinnholdet i hydrocarbonoljen fjernes, 2) å føre det fordampete hydrocarbon sammen med hydrogen, f. eks. i molforhold ca. 1:1, ved en temperatur mellom 350 og 450° C, spesielt mellom 380 og 400° C, og ved et trykk mellom 1 og 50 atmosfærer, fortrinnsvis mellom 4 og 20 atmosfærer, over en hydroavsvovlings-katalysator, og 3) å bringe produktet fra det andre trinn i kontakt med et hydrogensulfidabsorber-ende materiale. of the sulfur content in the hydrocarbon oil is removed, 2) passing the evaporated hydrocarbon together with hydrogen, e.g. in molar ratio approx. 1:1, at a temperature between 350 and 450° C, especially between 380 and 400° C, and at a pressure between 1 and 50 atmospheres, preferably between 4 and 20 atmospheres, over a hydrodesulfurization catalyst, and 3) bringing the product from the second step in contact with a hydrogen sulphide absorbing material. 2. Fremgangsmåte i henhold til på-stand 1, karakterisert ved at det anvendes en hydroavsvovlings-katalysator som består av palladium, platina eller koboltmolybdat på en bærer av aluminiumoxyd. 2. Method according to claim 1, characterized in that a hydrodesulphurisation catalyst consisting of palladium, platinum or cobalt molybdate is used on a support of aluminum oxide. 3. Fremgangsmtåe i henhold til en av de foregående påstander, karakterisert ved at det som hydrogensulfid - absorberende materiale i tredje trinn av fremgangsmåten anvendes zinkoxyd, manganoxyd eller jernoxyd. 3. Method according to one of the preceding claims, characterized in that zinc oxide, manganese oxide or iron oxide is used as hydrogen sulphide absorbing material in the third step of the method. 4. Fremgangsmåte i henhold til en av de foregående påstander, karakterisert ved at behandlingen med kontakt-materialet bestående av zinkoxyd, manganoxyd eller jernoxyd, som kan utgjøre i det minste én del av det første trinn i prosessen, og også det andre og det tredje I trinn av prosessen, utføres i én operasjon ved å føre hydrocarbondampen blandet med hydrogen gjennom en «sandwich» bestående av et lag av hydroavsvovlingskata-lysator anbrakt mellom to lag, som hvert består av zinkoxyd, manganoxyd eller jernoxyd.4. Method according to one of the preceding claims, characterized in that the treatment with the contact material consisting of zinc oxide, manganese oxide or iron oxide, which can form at least one part of the first step in the process, and also the second and the third In steps of the process, performed in one operation by passing the hydrocarbon vapor mixed with hydrogen through a "sandwich" consisting of a layer of hydrodesulfurization catalyst placed between two layers, each of which consists of zinc oxide, manganese oxide or iron oxide.
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