DE1545389A1 - Process for the hydrogenative cleavage of hydrocarbon oils - Google Patents

Description

DR. ELISABETH JUNQ AND DR. VOLKER V088IU8 PATENTANWÄLTE F ö H 0 0 ö ίί

• MÖNCHEN St. SIEQEStTMAtSEl * ■ TELEPHONE ΜΜ · 7 ■ TELEQRAM ADDRES: IN VENT / MONCHEN

P 7513 / Fi / kä December 27, 1966

SHiSLL IMTJBHMATlOIiAIB BESEAiiCH ^ AATSCHAPPU 1 - .. V. The Hague / Holland

"Process for the hydrogenative cleavage of hydrocarbon oils"

Priority: December 29, 1965 * V, St.A. Ancelde-Jfr .: 517 477

The invention relates to a process for hydrogenative cleavage of hydrocarbon oils at elevated temperature and elevated Pressure in the presence of hydrogen and in the presence of a catalyst composed of fluorine and at least one metal from the iron group the periodic system of the elements, intimately connected with an acidic carrier material consisting of at least one refractory oxide, whereby the intimate connection of metal and carrier material is achieved by treating the carrier » materials in hydrogel form. with an aqueous solution of one or several soluble salts dee metals or the metals achieved were »and where dae i? luor that present in hydrogel form Carrier material was incorporated, with subsequent laundry,

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Drying and calcination of the loaded hydrogel.

From the British patent hv. 992 820 a process for the hydrogenative cleavage of hydrocarbon oils is known, in which the oil is brought into contact with a catalyst in the presence of hydrogen at elevated temperature and increased fracture, the fluorine and at least one metal of the iron group of the periodic table of elements in intimate connection with an acidic carrier material consisting of at least one refractory oxide, wherein the intimate union of metal and carrier material was achieved by treating the carrier material in hydrogel form with a solution of the metal or metals, and where the fluorine to the in Hydro ^ elform was incorporated into the present carrier material.

It was now found that the activity of this catalyst in the hydrogenative cleavage of starting materials with a vernal tnismä8si & · low aromatic close hold by treating the Catalyst can be improved considerably at elevated temperature in a reducing atmosphere.

The subject of the .Erfindung- is thus a process for hydrogenating Cleavage of hydrocarbon oils at elevated temperature and elevated temperature Pressure in the presence of hydrogen and in the presence of a Catalyst composed of fluorine and at least one metal of the iron group of the periodic system of the elements, innit; attached to an acidic one consisting of at least one refractory oxide acting carrier material, there is the intimate connection of metal and carrier material by treating the carrier material

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in hydro & elform with an aqueous solution of one or more soluble salts of the metal or metals were obtained and,

the fluorine being incorporated into the carrier material present in the hydrogel form, followed by washing, drying and calcination of the loaded hydrogel, which is characterized in that a hydrocarbon oil with a content of less than 2Ciillimol aromatics per IOC g of oil is present a catalyst is cleaved, which was activated with hydrogen at a temperature of'40C to 65O ^{0 G.}

The activation _u catalyst is carried out by heat treatment at a temperature of 480 to 650 g, the applied over the hydrogenated in the cleavage Raaktionateiaperaturen'liegt. The improved properties of the catalyst activated in this way are particularly surprising since, in the hydrogenative cleavage of hydrocarbon oils, the catalyst is in any case exposed to the action of hydrogen at elevated temperatures before and during the process. Furthermore, the cause of the improvement obviously cannot be attributed solely to a teniperature effect, since the catalyst is calcined during its production. The Caleinierune is preferably carried out Xm range of 425 to 65O ⁰ C.

The catalyst to be used in the orfindun ^ SteLiaesen process is extremely effective in the hydrogenative cleavage of high-boiling oils, which are preferably in a range from 230 to 54O ⁰ C,

boiling, e.g. straight-run gas oils.

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BATH ORIGINAL

The hydrogenolysis is preferably carried out completely at a temperature of 260-400 ⁰ C, a Viasserstoffpartialdruck 52.5 to 140 atmospheres and a IAIT Flüssigrauageschwindigkeit of C l to 5 volumes of oil per hour per volume of catalyst.

To produce the catalyst, an iron group metal and fluorine can be incorporated into a silicon-containing refractory oxide, for example silicon dioxide-aluminum oxide, which is present in the hydrogel, and the silicon dioxide-aluminum oxide hydrogel can be produced in any known manner. A known method for the preparation of the hydrogel is that the pH is reduced _o a Natriunisilikatlösun by adding einsr l'iineralsäure, for example sulfuric acid, to a value of 9, whereupon aqueous, e Aluminiurisulf solution at adding one. The mixture is then neutralized with a base such as ammonium hydroxide. The hydrochloride thus formed is & el for removal of undesirable ions, such «B _e sodium or sulfate ions washed υ.B. with acidic wax, metal-free water or an ammonium nitrate solution. This process is commonly referred to as gelling in the acidic range.

A suitable hydrogel can also be produced by gelling in a basic range. For example, a

& aqueous sodium silicate solution with an aqueous Katriuai-

u> alurainate solution ß-emisciit. Then you add so much mineral acid,

^ that the pH of the mixture is brought to about 7. That there- ^ when silicon dioxide is formed ^ aluminum oxide ^ hydro oil is used for removal unwanted ions, e.g. Sodium ionone, in suitable

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Way washed. The drying component is added to the catalyst by treating the hydrogel with an aqueous solution of a compound of an iron group metal, in which iron group metal, among other things, is present as a cation. Suitable metallverbindimgen Eisengrupperi · Z = ₀ are for example metal salts such as a corresponding sulfate ₈ suffered rat or fluoride, wherein fluorides are preferred.

Fluorine can be incorporated into the hydrogel in any suitable manner, e.g. during the formation of the hydrogel or preferably by treatment with a fluorine-containing solution. ·: Together with the metal component. The hydrogel containing the metal components and fluorine is then washed to remove excess solution, expediently with water, and treated with air at a temperature of preferably 425 to 65O ⁰ C,

The catalyst preferably contains 0.1 to 15% by weight of the iron group metal and 0.1 to 5% by weight of fluorine, based on the weight of the catalyst. Particularly effective catalysts contain about 2 to 7% by weight of the iron group metal. Kickel results in a particularly active catalyst and is therefore preferred as a metal coraponent. In addition to the iron group metal, accelerators can be used, for example other transition metals, preferably metals from group VIbj, in particular tungsten and / or molybdenum. The added accelerator metal is advantageously used in an amount γόη 0 _B l bi »5 Gew"<= - $ i "

The carrier material of the catalyst preferably consists of v; .ie / .end made of silicon dioxide, the catalyst carrier has advantages «»

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adherent enough, 40 to 90 wt ₀ = ^ silicon dioxide, with the balance ie, 60 to 10 $ _s Aluminiu: iiüxyd _s Kagnesiur / ioxyd ₉ zirconium oxide, boron oxide and / or titanium oxide is, Bin Siliciuiadioxyd-Aluminiurnoxyd- carrier material having good cracking activity consists of about 70 to 90 ⁰ P silicon dioxide and about 30 to 10 ° ^C. aluminum oxide. Although silicon dioxide-aluminum oxide is a particularly preferred carrier material, other acidic, refractory oxide compounds are also suitable, e.g. silicon dioxide, magnesium oxide, silicon dioxide-aluminum oxide-zirconium or Siliciumdioxyd-Titanoxydo Acid reacting refractory oxides, such as füliciumdioxyd-aluminum oxide, are generally known as predominantly amorphous materials and are to be distinguished from the crystalline aluminum silicates, which are known to those skilled in the art as molecular sieves.

The erimuuritäSgeiaäss to be used iron & group metal fluorine = Aluminum oxide-silicon dioxide catalyst is made by treating

ο activated with hydrogen at a temperature of about 480 to 650 C _5, preferably 510 to 59 ° C ₉ "At higher temperatures the complex catalyst decomposes easily and forms metallic iron group metal crystallites" Therefore, higher temperatures are to be avoided9 so that the catalyst does not decompose too much "

_{For activation, the catalyst is expediently treated with H 2 for} 1/2 Ms 10, preferably for 2 to 5 hours. The activation treatment can be carried out under a standing hydrogen atmosphere or in flowing hydrogen at any suitable pressure ) .dliing can

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gases containing oxygen, a »B. the hydrogen from a reformer Plant, or mixtures of hydrogen and e.g. inert gas ver = · be turned. Heiner hydrogen is therefore not required. It is expedient to use dry hydrogen which advantageously less than about 0.5 moles · = ^ preferably contains less than about 0.1 mol- ^ water.

The catalyst may be alctiviert during its manufacture, or after it is introduced into the reaction system, with the abe _& frass that the activation treatment is carried out before the catalyst to be reacted with oils into contact

The activation of the catalyst to be used according to the invention differs significantly from the heat treatment to which conventional impregnated catalysts are subjected. Impregnated catalysts are made by treating a previously prepared and calcined support with an aqueous solution of the metal salt. When impregnated catalysts are dried, the metal salt remains finely divided on the surface of the catalyst. When calcining the catalyst at elevated temperatures, the metal salt is decomposed under BjJdUn ₁ -V small lie tall oxydkristalli th sitting on the surface of the catalyst. The metallic oxides of the 'iisen = gruppenr.ietalle be' easily reduced hydrogen at elevated temperature to metal ..Cs However sor ^ ^ fälti claae to achtenf it not applied to high temperature or metal on flauere V / o i s · λ \\ <; ι sintering is brought. Accordingly wo? Xp j boi eier JiS'lttk'vi.o ;; 'ion :> niprä / .ξηχerten catalysts Tempera =

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Doors at 4oC and "preferably applied at 34O ⁰ C This temperature doors are _f even observed when the metal is converted to the corresponding Sulfia.

A catalyst that has been archived with hydrogen at high temperature acti = _"s is Oexen particularly to cleavage by hydrogenation of oils with low Arömatengehalt suitable zBvon less than 200 and preferably less than 150 Mllimol aromatics in IOC g oil.

A range of aromatic oils have a relatively high carbon-hydrogen ratio after hydrogenation to remove nitrogen and other impurities under severe conditions and are fairly heat-resistant. _S The arbriiatenarnen oils _s eraässen in fiction, ^ process as the raw material used, however, have generally a carbon water "material ratio of less than 7 * 2 and preferably less than 7.0.

example 1

In hydrogenated, catalytically cracked gas oil with a behavior = nisiiiassifa ^ erin ^ erin ^ en aromatics ^ exialt v / is cracked in a hydrogenative manner over a catalyst which has been treated with hydrogen at high temperature. For comparison, the experiment is repeated using a catalyst which has not been treated with hydrogen at a high temperature. The »hydrogenated gas oil ¹ used as the starting material has the following properties:

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Density 883 kg / m ⁵ boiling range; "

Beginning of boiling, ⁰ G 277

Up to 371 ⁰ C passing _7ς

Shares, # π

Embroidery fabric ₅ TPM 26

Carbon / it container _{7 n}

Relationship '» ^u

Total taroruat content,
Killimol / lüO g Gl

Molecular weight 280

The hydrocracking catalyst used consists of 3.7 nickel and 2.4 wt .- ^ fluorine, which is supported on a silica-aluminum oxide support (about 20 wt .- ^ Al ₂ 0, 80 wt .- JS SiO ₂ ) by treating a Practically natriura-free silicon dioxide-aluminum oxide hydrogel with an aqueous solution containing Mokeluitrat and AEiiuOr.iumfluorid, bags. Drying and galvanizing with admission of air at 593 ⁰ C are applied.

The hydrogenating cleavage occurs at a pressure of 105 atino spheres, an hourly liquid space velocity of 0.67 volume units oil per hour per unit volume of catalyst and with. carried out a molar ratio of hydrogen to oil of 15: 1 ·

The first experiment uses a catalyst which has been treated with hydrogen for 2 hours at J2C C before use. When NaCN about 250 Ätunuen stable process conditions ha ceased, the VMi to maintain a Üiawandlung- 67 CJüY / _n ~ / u ^ Austjan ßriaterials in below 216 ⁰ C is boiling

e hone) erased temperature 353 ⁰ C. To a conversion & rad of 9 098 35/1217

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To obtain 67 wt .- ^ upright, to be increased, the nut Reaictionsteinperatur per day by 0.2 C ^0. In contrast, if a catalyst is used, · which was treated for 2 hours at 590 C and at 1 Wasserotoff Atisosphäre pressure so beträft the 'Required / £' to obtain a Umwandlun ^ sgraues of 67 wt «~ .Temperature after 250 hours only 346 ⁰ C. _In this case, the reaction temperature must be increased by 0.08 ° C per day. The USN 6 ⁰ C deeper required Keaktionstemperatur and the lower decrease in catalyst activity represents a marked improvement with respect to represent the activity and life of the catalyst.

For example, if you follow the procedure described above

until a reaction temperature of 400 C is reached, without renewing the catalyst or regenerating it, so can the catalyst activated with hydrogen at high temperature can be used for about 877 days, compared with the Catalyst not hydrotreated at high temperature has a life of only 494 days.

Comparison attempt

In this example, a hydrogenated, extracted gas oil is used with a relatively high aronate content, hydrogenating splits. The properties of the oil used as Auagan's material ainu below listed:

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Density 900

Boiling range:

Onset of boiling, ⁰ C 177

Final boiling point, ⁰ C 360

Nitrogen, bpm 26

Carbon / hydrogen ₇

Relationship ''

Total aromatic content, . tfillimol / 100 g of oil

225

The same procedural measures are used in the hydrogenative cleavage and conditions as in Example 1 applied. Analogously to Example 1, two catalysts are prepared.

Catalyst A contains 1.9% by weight of nickel and 3.1% by weight of fluorine on a silicon oxide-aluminum oxide (about 20% by weight of AlpOv, 80% by weight of _{SiO 2} as a small catalyst A is treated with hydrogen at a temperature of 320 ^° C. for 2 hours.

Catalyst ß, consisting of 1 ₈ 9 wt .- '/ Mckel and 2.8 fluorine on a silicon dioxide "- aluminum oxide ="! Rager (about 20 wt .-? S Al ₅ O ₃ , 80 wt .-% Si O ₂ ) is treated with hydrogen at 60O ^{0 C for 2 hours.}

The clotting & footed difference iia Pluorgehalü of the catalysts is negligible, as it remains on the catalyst properties without significant influence. In the hydrogenative cleavage of the aromatic gas oil described above, the required iteration temperature of 352 ° C. after 200 hours and a decrease are practically the same for both catalysts

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the catalyst activity s, which _{makes a temperature increase of 1 S} 5 ° C per day necessary for both catalysts.

Claims

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Claims (1)

Claims 1. Process sur hydrogenating cleavage of hydrocarbon oils at elevated temperature and elevated pressure in the presence of '/ hydrogen and in the presence of a catalyst consisting of fluorine and at least one: metal of the iron group of the periodic systeras of the elements, iniii ^ connected with one of at least a refractory oxide bestehenaen consists acid-acting support material, wherein the intimate connection of Ketall and substrate material by treating the TrägerLiaterials in Hydro & elforia Jait an aqueous Lösun _o vcn one or more soluble salts of the metal or »of the metals has been achieved, and wherein the fluoropolymer is the in uydrogelforio present carrier material was incorporated, with automatic washing, drying and calcination of the loaded hydrogel, characterized in that a .Kohlenwasserstofföl with a content of less than 20.0 Piillimol aromatics per 100 g of oil is split in the presence of a catalyst that with V / water a temperature from 480 to 650 ⁰ C was activated. 2 » Process according to claim I _1, characterized in that a hydrocarbon oil with a boiling range of 230 to 540 C is cleaved by hydrogenation. 5. The method according to claim 1 or 2, characterized ge kennaeichnet that the hydrogenating cleavage at P60 to 40O ⁰ G ₈ at a hydrogen partial pressure from 52.5 to 140 abs. Ο and a Plüssi ^ rfmiageöchwindigkeit of 0.1 bie 5 volumes of oil per Hour per unit volume of catalyst 90 98 3 5 / ^ 1.2-1.7, BAD ORiOINAL will lead 4ο method according to one of claims 1 to 3 »thereby marked; that a catalyst with a Content of 0.1 to 5 wt. = · ^ Fluorine is used. 5. The method according to any one of claims 1 Ms 4 »4 a d u r c h mark τ that uses a catalyst is 0.1 to 15 wt. <= # of at least one iron & group metal contains. 6c method according to one of claims 1 to 5 »thereby & e k e η η ζ ei chnet that a catalyst is used containing nickel. 7. The method according to one of the claims 1 or 6, thereby marked that a catalyst is used containing 0.1 to 5 wt .- ^ tungsten and / or molybdenum. 8. The method according to any one of claims 1 to 7 »d * through Marked that a catalyst is used is, the carrier 40 to 90 wt · - ^ Siliciuradioxyd and 60 to 10 wt .-? I aluminum, magnesium, zirconium, boron and / or titanium oxide contains. 9. The method according to any one of claims 1 to Θ, characterized in that a catalyst used vivd, the carrier of 70 to 90 0ew "-? <". Silicon dioxide and 30 to 10% by weight of aluminum oxide. 909835/1217 BATHROOM ORiGINAL 10β method according to Ansprücne 1 to 9 »characterized gekennze leans that a catalyst is used which was activated at 510-595 ⁰ C with hydrogen. 11. The method according to any one of claims 1 to 10, characterized in that a catalyst is used which has been treated with hydrogen for 50 minutes to 10 hours for activation. ^: 12. The method according to any one of claims 1 to 11, characterized marked that a catalyst is used with less than 0.5 ί · ίο1-56 water containing hydrogen has been activated » 13 · proceed «according to one of claims 1 to 12, thereby characterized as being a hydrocarbon oil is split hydratically, which is less than 150 millimoles Contains aromatics per 100 g of oil. 9 0 9835/1217 BATH ORIGINAL