DE2613877A1 - PROCESS FOR PRODUCING LOW POURPOINT LUBRICATING OIL - Google Patents

Description

K 5904 GEW : Λ. VAX'Δ

J 944 C (J / hg)

SHELL INTERNATIONAL RESEARCH MAATSCIIAPPIJ B.V. The Hague / Netherlands

"Process for Making Low Pour Point Lubricating Oil"

Claimed priority: April 2, 1975, France, No. 7510253

The invention relates to a method for producing lubricating oil with low pour puint.

ί »ί> is known to produce lubricating oils through a. ·, i '-.' stage hydrogenationb - .; hand-.umvj veal oiit asphaltier tt? n v / aoh.; hiH.i! j.> n ucliworen Hi neralölirak-tionen and subsequent »Ent-vach-seii herzu.itellen, The yield art iAiiriiie.roI with tu.neiu vcjrgegele-nen viscosity indux läij.st, however often ·, au wüiischen left.

kiB »/ urdo nun ubui / ranrheinl 'r' / üiui t ^> t, -j _t ·;> to lit ■, das .; di «.; / u V ' leadfe xVaiibfiut <*, in i>' chiui.:rol : · η four t Lulit-i jmi U'.ihl .ici! ti .. ". .i and dt * i> Katralyöütors in the two Hermit ;: l 1 na j.it; f: ui; ίι .tbhrm.t, as well as from the Verv / eiriun-j dea £ l.ü iijigcn <vbiaui.i ..m> .i.sr ur .t-Mi Hydrationiif-.rute Ln Λ st: there, othaltenen Zuiuuumeiuiet /.umj!. ■: ι jäpeisung far dia '/, tialtci Hy <lrierun.j '> s calls.

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ORIGINAL INSPECTED

The invention accordingly relates to a method for producing Low pour point lubricating oil characterized by: that in a first stage an essentially asphalt-free wax-containing mineral oil fraction is added in the presence of hydrogen Contciktiert a temperature of 390 to 450 C with a catalyst, of one or more metals and / or metal compounds of group VI and / or VIII of the periodic table on a carrier material the elements contains, in a second stage at least a portion of the liquid effluent from the first stage in the dert obtained composition in the presence of hydrogen at a temperature of 350 to 390 C with an acidic catalyst contacted, the one or more metals and / or metal compounds of group VI and one or on a carrier material contains several non-noble metals and / or metal compounds of Group VIII of the Periodic Table of the Elements, and optionally the drain from the second stage completely or partially dewaxed.

Suitable starting materials for the process according to the invention iiind high-boiling hydrocarbon mixtures such as heavy petroleum fractions as well as heavy fractions obtained by pyrolysis of coal, bituminous shale or tar sand, which in the context of the present Invention can be summarized under the term "essentially asphalt-free wax-containing mineral oil fraction". Particularly Petroleum fractions with at least some of their boiling point are advantageous is above the boiling range of lubricating oil. As an addition In the process according to the invention, a Deiitillut fraction is preferably used is used, which by vacuum distillation au a Rückstanclsöl- obtained by distillation at atmospheric pressure

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faction won v / ird. The boiling range of such a vacuum distillate is usually from 350 to 55 ° C. However, deasphalted petroleum residue fractions can also be used.

The inventive method is at elevated temperature and carried out at elevated pressure and in the presence of hydrogen or hydrogen-containing gas in the first and second stage. Pure hydrogen can be used, but this is not absolutely necessary. A gas with a hydrogen content of 70 volume percent or more is particularly suitable. In practice it is preferred to use one of a catalytic one Hydrogen-containing gas originating from a reforming plant, as this gas not only has a high hydrogen content, but also contains low-boiling hydrocarbons such as methane and a small amount of propane.

The pressure in the first and second treatment stages should not

2
below 50 kg / cm, as otherwise the life of the catalysts is reduced and there is a risk of an excessively high aromatic content in the end product, which has an adverse effect on the viscosity index

2 affects. On the other hand, a pressure of more than 250 kg / cm requires expensive equipment. Therefore, the pressure should be preferred

be between 100 and 200 kg / cm.

For the hourly space velocity. and the hydrogen / oil ratio very wide ranges can be selected. Preferably, however, the space velocity should be between 0.1 and 10 kg of oil per liter of catalyst per hour. One

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Air flow velocity of less than 0.1 kg of oil per liter Catalyst per hour makes the use of uneconomically large reactors necessary for a given degree of conversion, while with more than 10 kg of oil per liter of catalyst per hour, the degree of conversion remains very low. The hydrogen / oil ratio is preferably between 100 and 5000 liters under normal conditions (= liters at 1 bar and 0 C) per kilogram of oil. A very A low H / oil ratio has an unfavorable effect on the life of the catalytic converter, while a very high H / oil ratio leads to a considerable pressure loss in the catalyst beds, so that for the circulation of the hydrogen-rich Gas a high pressure is required.

Any heat-resistant material can be used as the catalyst carrier material in the first stage. They are suitable for this e.g. aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, zirconium oxide, thorium oxide, boron oxide and mixtures and compounds of these Metal oxides. Preferably, the catalyst support material consists essentially of the first and second treatment stages made of aluminum oxide. Mixtures of aluminum oxide and silicon oxide and in particular mixtures of aluminum oxide and boron oxide are also suitable.

Catalysts are particularly suitable for the first treatment stage, which contain one or more metals from the group nickel, cobalt, molybdenum and tungsten, in particular combinations of nickel or Cobalt on the one hand and molybdenum or tungsten on the other. A catalyst is particularly preferred for the first treatment stage,

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made of nickel and tungsten (or compounds of these metals, especially their oxides) on a carrier material made of aluminum and boron oxide.

Often there is also the presence of phosphorus and / or fluorine in the catalyst the first stage of the procedure is advantageous.

The metal content in the catalyst of the first process stage can be in a very wide range. Preferably the catalyst contains 10 to 30 parts by weight of a Group VI metal and 2 to 15 parts by weight of a. ¹ .; Metal of group VIII of the Periodic Table of the Elements per 100 parts by weight of catalyst.

Metals in oxidic form are special in fresh catalysts suitable.

The sequence from the first-.n stage can -mr Kntff-rnung unwanted £ Gi-.iV / iii'bindungen, z. IJ. SchwefelwaotjerKt-oil: ', ft i only treatment Uiifcei, v.'uri en -m'm .um (e.g. by adsorption of Ιΐ. ^ Ί in a wu; sri gaa Airtin.LooUiK ;, λ, Ii * a solution of IHi.; Wj rsip.U'C) 1, -unin). Vor-.mga v.'jilfjr ¹ . but the 'jtiüamte Abl.ml:mtjii : y. · dt; i "t ·. t cn Sturt · it-r - * wide ο tu tv; is supplied to' jt-i.

Dt'ucki ötün-ilijhf! K.iun Jt roiuutu /.- j-jeschwi r J L-11 eU un.i Uassot hL: j1. f · <> l-Viirhaltnis in .ijr ϊΛ / eitua iitufe £ * i 111 vor-jiiffUvftM η- fjl.oLi.Th η : .- d _s / if in the eriites: .tu ^, Di «Tsiaporatur»; oll jfidcK'ii '* i "i-hon> ^r >; · <ui i J!) 0 C lieg; - .; -Xh always lower; j «in than the '!'". I ρ-i ltui vn ler first Sta / ^,

Air; A catalyst adjusted to be acidic is to be used in the second stage. Below this were catalysts ν ei which, upon adsorption of dimethyl yellow (C..H -N = NC _C H -

basic ^{6 5 6 4}

N- (CH-) „) and other even weaker / indicators a color change result, indicating the presence of an acidic medium.

Suitable carriers for the acidified catalysts are e.g. compounds of silicon oxide and aluminum oxide, such as silicon oxide / aluminum oxide cracking catalysts, Compounds of silicon oxide and zirconium dioxide, compounds of boron trioxide and aluminum oxide, Compounds of boron trioxide and silicon oxide and compounds of aluminum oxide and halogen such as aluminum oxide and Fluorine, or aluminum oxide, silicon oxide and fluorine.

Those suitable or preferred for the catalyst in the second stage Metals (or metal compounds) used and their combinations are the same in type and amount as in the first stage. Particularly advantageous catalysts for use in the second stage are nickel and tungsten (or their compounds, e.g. nickel and tungsten oxides) on an aluminum oxide / boron oxide carrier material as well as fluorinated nickel and tungsten (or their compounds, e.g. nickel and tungsten oxides) on one iulium oxide / alumina carrier.

In many cases it can prove beneficial in the first one and second stage to use the same catalyst.

When the pour point of the liquid flow from the second stage »

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is still too high, one can outgrow the process as such. Preferably However, lower-boiling substances are removed before dewaxing, e.g. by distillation. Preferably be before dewaxing removes all compounds with a boiling point above 400 to 450 ° C.

Pas dewaxing may in any way performed v / ground, for example by adding a suitable liquid, such as cooling a mixture of methyl ethyl ketone and toluene, the resultant mixture to about -20 ⁰ C and then the solid wax is removed.

Preferably, however, the dewaxing is carried out by a catalytic route by the liquid to be dewaxed with a Contacted catalyst in the presence of hydrogen. Suitable catalysts include metals or compounds of Groups VI and VIII of the Periodic Table of the Elements on a support of crystalline mordenite. For example, are suitable for this Platinum, palladium and tungsten.

Prints from 40 to 120 kg / cm are suitable for dewaxing,

Temperatures from 300 to 400 ° C, in particular from 300 to 35O ° C, and room flow rates of 0.1 to 2 kg of oil per liter of catalyst per hour.

If desired, the catalytic dewaxing stage can proceed be topped to remove low-boiling components and / or with a suitable extraction agent, e.g. sulfur dioxide or SuIfolan, can be extracted in order to

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parts to remove.

The invention is explained in more detail using an example.

example

A waxy distillate with a boiling range of 430 to 550 C from Middle Eastern crude oil is used together with hydrogen at a

Pressure of 140 kg / cm, a space velocity of 0.8 kg of oil per liter of catalyst per hour and a hydrogen / oil ratio of 1750 Nl / kg over two successive catalyst beds directed.

The first reactor contains a catalyst of the following composition:
57.5% Al ₃ O ₃ - 6% B ₃ O ₃ - 30% WO ₃ - 6.5% NiO.

The catalyst in the second reactor has the following composition

57.5% Al ₂ O ₃ - 6% B ₃ O ₃ - 30% WO ₃ - 6.5% NiO.

In this case, the composition of the catalyst in the second reactor is accordingly the same as in the first reactor. The temperatures however, in the two reactors are different. Table I shows the yield of lubricating oil with a viscosity index of 95 as percent by weight based on the total weight of the liquid effluent from the second reactor, which is obtained by topping at 430 C and catalytic dewaxing. At the kata-

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26Ί3877

lytic dewaxing is the process (after topping at Ί30 C)

at a pressure of 60 kg / cni *, eirK >>; Raumströnuriqsjger.cbv.'j ndigkcit of 0.5 kg of oil per liter of catalyst per hour and at a temperature of 315 C over a catalyst of 10 percent by weight Tungsten (in oxide form) ... conducted on synthetic mordenite.

Similar experiments are carried out at different temperatures.

Table I.

Temperature in the 1st stage, ° C 402 401 3 97 395 Temperature in the 2nd stage, ° C 320 340 360 370 Lube oil yield, percent by weight 50 51 52 58.5

As Table I shows, the highest yields will be a lubricating oil

et vg with a viscosity index of 95 at a temperature of / 3 95 C in the first reactor and temperatures between 360 and 3 90 C in the second reactor. With decreasing temperature in the second reactor -jtin-ti-the yield decreases.

Claims (11)

26Ί3877 claims 1. Process for the production of low pour point lubricating oil, characterized in that in a first stage an essentially asphalt-free waxy Mineral oil fraction in the presence of hydrogen at a temperature of 3 90 to 450 C iait a catalyst contacted which on a carrier material one or more metals and / or metal compounds of group VI and / or VIII of the periodic table of Contains elements, in a second stage, at least part of the liquid effluent from the first stage in the composition obtained there contacted in the presence of hydrogen at a temperature of 350 to 3 90 C with an acidic catalyst, one or more metals and / or metal compounds of group VI and one or more on a carrier material Contains non-noble metals and / or metal compounds of Group VIII of the Periodic Table of the Elements, and optionally the Drainage from the second stage completely or partially dewaxed. 2. The method according to claim 1, characterized in that the Support material in the first and second stage consists essentially of aluminum oxide. 3. The method according to claim 1 or 2, characterized in that the carrier material in the first and aweit stage boron oxide contains. 6 0 9 8 4? / 0 B 3 β 4. The method according to claim 1 to 3, characterized in that df.-s the catalysts in the first and second stage contain nickel and tungsten compounds. 5. The method according to claim 1 to 4, characterized in that the catalysts in the first and second stage are the same. 6. The method according to claim 1 to 5, characterized in that the pressure in the first and second stages each 100 to 200 kg / cm. 7. The method according to claim 1 to 6, characterized in that the entire liquid flow from the first stage with the catalyst the second stage is contacted. 8. The method according to claim 1 to 7, characterized in that the dewaxing catalytically in the presence of hydrogen with a Mordenite is carried out. 9. The method according to claim 8, characterized in that the mordenite one or more non-noble metals of group VIII of Contains periodic table of the elements. 10. The method according to claim 9, characterized in that the Zeolite contains tungsten. 11. The method according to any one of claims 8 to 10, characterized in that that the catalytic dewaxing at one pressure R η q η / ■ -> / η · .. ->, e from 40 to 120 kg / cm, a temperature of 300 to 400 C and a space flow rate of 0.1 to 2 kg of oil per liter of catalyst is carried out per hour. 609842/0936