DE2043849A1 - Process for the production of lubricating oil - Google Patents

Description

^{PATENT ACCOUNTS} 20A 3849

Dipl.-Ing. EI D E N EI E R Dipl.-Chem. Dr. R U F F Dipl.-Ing. J. B EI E R

7 STUTTGART 1 Neckarstrasse 5O Telephone 22 7O51

September 3, 1970 R / Fi

Applicant: Atlantic Richfield Company

717 Fifth Avenue New York, N, Y. 10022 United States

A 12 694

Process for the production of lubricating oil

The invention relates to a process for the production of mineral lubricating oils of high quality from starting materials used in previous industrial processes for Manufacture of such products are not normally used · In addition to mineral lubricating oil distillates and relatively high quality deasphalted residues can contain materials with high percentages of sulfur, nitrogen and carbon residues, such as acidic oils and stronger contaminated deasphalted oils, can be used as starting materials. In addition, there are a large number of Products possible. Lubricating oils with viscosity indices up to approx. 150 or more (ASTM designation: D-2270) with partial

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wise or even complete aromatic saturation are possible. The process is also more economical than previous methods of producing high viscosity index oils, including solvent treatment, dewaxing and refining oils are prepared by hydrocracking the mineral oil material while it is in contact with a catalyst containing nickel and tungsten or molybdenum along with boron oxide on an alumina support. The materials obtained by hydrocracking with lubricating oil viscosity are then hydrogenated over a hydrogenation catalyst, producing a high viscosity index oil. Thus, in one embodiment of the invention, a mineral lubricating oil with a high viscosity index is produced, by treating, for example, a deasphalted residue or a crude heavy lubricating oil distillate in a two-step process. The starting material becomes treated first by catalytic hydrocracking and then by catalytic hydrogenation and can be fractionated and dewaxed to produce a refined product will. Catalysts such as nickel tungstate on boron oxide-aluminum oxide or nickel molybdate on aluminum oxide are used in the two stages. The catalysts are preferably used in sulfurized form.

Many of the refining techniques used today for Production of high quality mineral lubricating oils with high viscosity indices have certain undesirable effects Properties. The production of refined oils with a viscosity index of 95 by known fractionation »·

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and solvent extraction processes from vacuum distillates or deasphalted residues and the subsequent dewaxing and refining with acid, clay or oxygen for example, normally gives a yield of about 50 to 65 volume percent. With the invention, however, yields of about 60 to 80 percent by volume of oils can be achieved a viscosity index of 95 on a dewaxed basis and yields of about 40 volume percent or more oils with viscosity indices of approx. 120 and more on a dewaxed basis.

The treated by the method of the invention, lubricating oils have a lubricating oil viscosity at about 100 ⁰ C (210 ⁰ F.) and are mainly materials of which at least 'about 90 percent by weight of a boiling point above about 315 ° C (600 ⁰ F .) to have; the starting material is preferably a residue of which at least about 90 percent by weight have a boiling point above about 54O ° C (1000 ⁰ F). The starting materials are usually oils with a viscosity index of at least about 50, for example about 50 to 80 or even about 70 to 80, and can be obtained from paraffinic or crude oils on a mixed basis. The full- or multigrade oil of lubricating oil viscosity obtained by the process of the invention has a viscosity index in the range of at least about 90 to about 150 or more, with the viscosity index of the product being at least about 20, preferably at least about 30 higher Both the hydrocarbon feedstock and the lubricating oil viscosity product from the hydrogenation reaction have a substantial boiling range, e.g., a range of at least about 55 ° C (100 ° F.), often at least about 110 ° C (approx. 200 ⁰ F.). The hydrocarbon

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material preferably has a specific dispersion (ASTM designation: D-1218) in the range from approx. 105 to 165, whereas the specific dispersion of the product with Schmler oil viscosity preferably in the range from about 100 to 110. The method of the invention is particularly suitable for the treatment of starting materials with a specific dispersion in the range from approx. 135 to 165, these Materials are the more heavily contaminated with larger amounts of aromatics, which are often just fractionated and have undergone deasphaiting. So this process can make these economically cheaper materials for the production of high quality lubricating oils with high yields »

The hydrocracking of the material, to which also the ring opening and usually a desulphurisation and removal of nitrogen is part of being in contact with a catalyst carried out, the nickel and molybdenum and / or tungsten contains, which together with boron oxide on a catalytic active alumina base are kept. The metals of the catalyst can be in the form of free metals or in the form of Compounds may be present as oxides and sulfides, the sulfide form being preferred. Examples of such mixtures or compounds are nickel molybdate or tungstate (or Thiomolybdate or thio tungstate). These catalytic components, together with boron oxide, are catalytically active Alumina deposited form applied The catalyst is composed of small, catalytic effective amounts of nickel, tungsten and / or molybdenum and boron oxide on the aluminum base * Nickel can often

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20438A9

ca «make up 1 to 40 percent by weight of the catalyst, preferably about 2 to 10 percent, the total amount of tungsten and molybdenum approx. 5 to 30 percent by weight, preferably approximately 10 to 20 percent of the metal oxide based catalyst makes up «The boron oxide is preferably in an amount of about« 2 to 10 percent by weight, based based on the total weight of the catalyst, while the alumina is the main constituent of the catalyst, e.g. the essential remainder the composition

The catalyst composition used in the hydrocracking stage of the invention can be prepared by adding the nickel, tungsten, molybdenum and boron oxide components to the aluminum oxide by various methods known in the art, for example by impregnation, precipitation and coprecipitation using suitable compounds of metals and boron. For example, aluminum oxide particles can contain boron oxide or a material which, when heated, yields boron oxide, with aqueous ammonia solutions containing nickel and tungsten and / or molybdenum or other aqueous solutions Solutions of water-soluble components of nickel and tungsten and / or molybdenum are mixed so that the metal components are absorbed on the base material will. The other possibility is to place the promoting materials on the boron oxide-containing alumina base material by suitable reaction of an aqueous slurry of the water-insoluble salts of the promoting To precipitate the carrier containing metals. The boron oxide-containing ingredients can either be before or after mixing with the nickel and tungsten and / or

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Molybdenum components can be formed into macro-size * The catalyst can be dried and calcined, e.g. at temperatures from approx. 42S to approx. 650 ° C (approx. 800 to 1200 ⁰ F.) or slightly above * Before the catalyst is preferably sulphurised at an elevated temperature during use »

The hydrocracking stage is carried out under conditions which are intended to selectively crack the starting material, so that the breaking of the aromatic and naphthenic rings is promoted rather than the breaking of chains into constituents of lower ?! Molecular weight "These conditions include eiaie T siperatur of approx · 28S to about" 470 ° C (about 725 to 875? F.), Preferably about 400 to 455 ° fca "75obis 850 ^o F») · Zu.den wsiteren reaction conditions Often includes a hydrogen partial pressure in the range of about 70 to 35C atu (100 to 5000 psig _c ), preferably about 105 to 210 at (1500 to 3000 psig). In the manufacture of oils with a VI of 95 according to the invention Cracking can take place to such an extent that about 5 to 10 percent by volume of the product from the hydrocracking stage is a material with a boiling point below about 315 ° C (about 600 ° F) About 30 to 40 volume percent of the product from the hydrocracking stage consists of these materials. The amount of free hydrogen used in hydrocracking can generally be about 178nm ³ to 890nm ³ 1000 to 5000 SCF / barrel}, preferably about 267nm ³ to 534ot ³ ClSOO to 3000 SCF / barrel) per m of hydrocarbon Ai isgangssaateri »! The weight-space-velocity sigkait per hour (WHEV), the

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Units of weight of raw material, which per hour in entered the reaction aone per unit weight of catalyst are often in the range of approx »0.3 to 3, preferably about 0.5 to 2 »The reactor effluent from the 1st or hydrocracking stage can be relaxed» üBi to prevent hydrogen sulfide and ammonia come to the hydrogenation stage, but this is especially not necessary if base metal hydrogenation catalyst a * lysers in the hydrogenation stage can be used. if if desired, any light hydrocarbons can also be removed from the feedstock for the hydrogenation step will·

SehtPJLeröl from the hydrocracking stage is subjected to a hydrogenation, in which lubricating oil ₉ preferably the substantially over the full range lubricating oil, from the hydrocracking stage in the presence of hydrogen with a solid hydrogenation catalyst at a temperature of approx. 285 to approx. 440 ⁰ C cca "550th to 825 ° F), preferably about 315 to 425 ° C (about 600 to SOO ⁰ is P.), into contact ge""preferably, the applied in the second stage temperature is at least about .28 ° C (50 ° P.) Less than the temperature of the first stage for optimal decolorization and saturation. The other reaction conditions often include pressures of about 70 to 350 atmospheres (1000 to 5000 psig), preferably about 105 to 210 atmospheres (1500 to 3000 psig) »space velocities (CWHSV) of about 0.3 to 5, preferably approx. 0.5 to 3, and a ratio of molar hydrogen to starting material of approx. 9Onm ³ to 625nra ³ C500 to 3500 SCF / barrel) hydrogen per m ³ hydrocarbon »starting material _s preferably approx.267nm ³ to 445nm ³ C100 to 2500 SCF / barrel) hydrogen per m ³ hydrocarbon base material

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The solid catalyst used in the hydrogenation is preferably a hydrogenation catalyst resistant to sulfur made of base metal, such as is commonly used in the hydrogenation of black petroleum oils will. Examples of suitable catalytic constituents are tin, vanadium, elements of group VIB of the periodic Systems such as chromium, molybdenum and tungsten, and metals of the iron group such as iron, cobalt and nickel. These metals are present in small, catalytically effective amounts, for example in amounts of about 2 to 30 percent by weight of the catalyst and can be in elemental form or as compounds such as the oxides or sulfides, the sulfide form being the preferred · mixtures of these materials or compounds of two or more oxides or sulfides can be used. Mixtures or compounds of the iron group metal oxides or sulfides with the oxides or sulfides of group VIB are, for example, very satisfactory catalysts. Examples of such mixtures or compounds are nickel molybdate tungstate or chromate (or thiomolybdate thiotungstate or thiochromate) or mixtures of nickel or Cobalt oxides with molybdenum, tungsten or chromium oxides. As is known in the art and as are the specific examples show below, these catalytic ingredients are generally in a suitable carrier of a refractory oxide applied form, e.g. on a predominantly calcined or activated aluminum oxide To prevent improper cracking, the catalyst base and other ingredients have only one little or no hydrocarbon cracking activity. Usually no more than approx. 5 percent by volume,

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preferably no more than about 2 percent by volume of the starting material is cracked in the second or hydrogenation stage to materials having a boiling point below about 315 ° C (60Q ⁰ F ₀ ). Commonly used catalysts contain approx. 1 to 10 percent by weight of a metal from the iron group and approx. 5 to 25% of a metal from group VIB (calculated as oxide) ο It is advantageous to use nickel molybdate or cobalt molybdate on an aluminum oxide support as the catalyst. Such preferred catalysts can be prepared by the process described in US Pat. No. 2,938,002.

Other suitable hydrogenation catalysts which can be used in the process of the invention include those of the platinum group metals. Such catalysts often have a small, catalytically effective amount, about 0.05 to 2, preferably about 0.1 to 1 percent by weight of a metal or more metals of the platinum group on a solid support, in particular an active alumina. Suitable platinum group metals include platinum, palladium, rhodium and ruthenium, with platinum preferred wi _r d.

Both those in the hydrocracking and those in the hydrogenation stage Catalysts used in the process of the invention are preferably in the reaction zone as Fixed Bed Arranged «Such fixed bed catalysts are usually macro-sized particles, e.g. Diameter from about 0.4mm to 6.4mm (1/64 inch to 1/4 inch), preferably about 1.6mm to 3.2mm (1/16 inch to 1/8 inch) and with a length of about 0.4mm to 25mm

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(1/64 inch to 1 inch) or more, preferably about 3.2mm to 12.7mm (about 1/8 to 1/2 inch). These catalysts can be produced by extrusion, tabletting or other suitable processes *

The hydrogenation creates an additional aromatic saturation, color improvement and stability against oxidation and corrosion. Additional color enhancement can be achieved by subjecting the effluent from the hydrogenation to treatment with ultraviolet light. This treatment has been found to lighten the color of the darker oils considerably, a surprising result since normally such a treatment has the opposite effect and can be fed to a steam scraper to remove excess, lightly hydrogenated constituents. »The oil can then be fractionated and the lubricating oil fractions can be dewaxed This dewaxing stage can be carried out, for example, by pressing or by dewaxing with a solvent using methyl ethyl ketone and toluene as solvents-S- The dewaxing can also be carried out before the initial hydrocracking stage, but it is preferably done after the hydrogenation is complete Oils with a VI of 95 are nothing unusual, and refined base oils with yiskosity indices of 120 and more can be used in economic yields, for example. In the range of

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get approx 40 percent by volume and more *

The following example illustrates the method of the invention.

Deasphalted petroleum residue was added to an isothermal reactor unit with a nickel-wolf catalyst ramat on boron oxide-aluminum oxide in the first or Hydrocracking stage and a nickel-colybdate catalyst on alumina fed in the second or hydrogenation stage «The catalysts were macro-size and were pre-sulphurized »The starting material used had the following characteristics

VI CD-2270) (dewaxed base) 76 Density, ⁰ API 23.1 Flash point, ⁰ C (° .F.) 290 (555) Viscosity, SUS / 99 ⁰ C (21O ⁰ Fo) 154.4 Pour point, ⁰ C ( ⁰ F.) 49 (120+) ASTM color dark Carbon residue (contamination), Weight percent 1.58 10% boiling point> 538 ° C > ClOOO ⁰ F ₀ )

Table 1 counts operating conditions and investigations of dewaxed oil for operations with nominal VI of 100 and 130 on «

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Table 1 100 VI 1
1 445 (2500) 130 VI Operating conditions 176 (775)
(700) 176 (2500) Pressure, atü (pslg),
(1st and 2nd stage) 413
370 Oil inspection {dewaxed base) »0
; s 435 (815)
370 (700) Temperature (1 "level)
(1st stage), ⁰ C (Jp.)
(2nd stage), ⁰ C ( ⁰ P.) (2500) 1.0
1.5 WHSV (1st stage)
(2nd stage) 445 (2500) H ₅ rate, nm ³ / m ³ (SCP / bbl)
(ί, and 2o level) Second stage product

Yield, volume percent 61 density, ⁰ API 28.7

Flash point, ⁰ C ( ⁰ P ..) 207 (405) Viscosity, SUS / 37.8 ° C (100 ⁰ P ₀ ) 605.8 Viscosity, SUS / 99 ° C {210 ⁰ Po) VI (D-2270)

Pour point, ⁰ C (° F _C )
ASTM color

Carbon residue
(Pollution)

Specific dispersion

70.17 100 -15 (+5) L2.0

0.026 102.4

50

33.2 (375) 180.9

47.27 128

-12 (+10) Ll,

0.004 101.5

The catalysts used in the successive stages have the following analysis:

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Tabel 2 Nickel; Weight
percent 5.35 NiMo on
Alumina NiW on boron oxide
Alumina Weight tungsten oxide
percent 12.15 2 j 30 Molybdenum oxide, weight
percent Silica, weight
percent 0.29 15.60 Boron oxide, weight
percent 5.06 on

Volatile stock

parts at 649 ° C (1200 ^o F ") 3.98

(at 538 ° C) t 1000 ⁰ Fo)

Perceptible density, g / ml 0.75

0.86 0.765

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Claims (1)

A 12 694 - 14 - Expectations The process of producing a mineral hydrocarbon lubricating oil with a viscosity index of at least about 90 on a dewaxed basis, characterized in that, that a) a mineral Kohlenwasserstcfföl raw material of lubricating oil viscosity bsi about 100 ⁰ C <210 ° F *) _f from the at least about 90 percent by weight of a boiling point above about 315 ° C (about 600 ° F.) and a viscosity index vosi ca «. 50 to 80, with molecular hydrogen under hydrocracking conditions at a temperature of about 385 ° C to about 47O ° C (about 725 to 875 ° F _e ) in the presence of a catalyst with small catalytically effective amounts of nickel and tungsten and / or molybdenum and boron oxide is brought into contact on an active aluminum oxide carrier, and b) Hydrocarbon oil with lubricating oil viscosity from the first stage with molecular hydrogen under hydrogenation conditions at a temperature of about 290 to about «440 ⁰ C (about 550 to 825 ° F.) In the presence of a solid hydrogenation catalyst for the production of oil with "lubricating oil viscosity having a viscosity index which is at least about 90 and at least 20 higher than the viscosity index of the hydrocarbon oil starting material fed to the first stage. 2ο method according to claim 1, characterized in that the catalysts are used in sulfide form. 109811/1854 ν 20438 A 12 694 - 15 - 3 _β method according to claim 1 or 2, characterized in that (psig cao lOOObis 5000th) on the conditions for hydrocracking a Wasserstöff partial pressure of ca · 70 to 350 atm _f a Gewiclrb-hourly space velocity (WHSV) of about 0.3 to 3 and a ratio of molecular hydrogen to hydrocarbon content 3 3 raw material of approx. 180 Ms 890nm per m of raw material (approx. 1000 to 5000 SCF / barrel) include 4. The method according to any one of claims 1 to 3, characterized overall A indicates that the catalyst for hydrocracking about 2 to 10 weight percent nickel, about 10 to 20 tungsten or molybdenum, based on oxide, in particular tungsten "and about 2 to 10% of boron oxide contains « 5 «Method according to one of the preceding claims, characterized in that au UEN conditions for the hydrogenation a Wasserstöff partial pressure of about _o 70 to 350 atmospheres (about '1000 to 5000 psig *), a weight-Raumgeschwindtgkeit per hour (WHSV) from about 0.3 to 5 and a ratio of molecular hydrogen to carbon ■ 3 3 hydrogen starting material from approx. 90nm to 625nm per is starting material (approx. 500 to 3500 SCF / barrel) ^ belong. 6. The method according to any one of the preceding claims, characterized characterized in that the in the hydrogenation stage The catalyst used contains small catalytically effective amounts of nickel or cobalt and molybdenum on aluminum oxide « 109811/1854 A 12 694 - 16 - 7. The method according to any one of the preceding claims, characterized in that the product of the second stage is fractionated to separate oil with lubricating oil viscosity and the lubricating oil fraction is dewaxed. 8. The method according to any one of the preceding claims, characterized in that at least about 90 percent by weight of the starting material for the hydrocracking stage boils above about 54O ° C (1000 ° F.) And the hydrocracking at about 400 to 455 ° C (approx. 750 to 850 ° F.) An H ₂ partial pressure of about 105 to 210 atmospheres (about 1500 to 3000 psig.), A weight hourly space velocity (WHSV) of about 0.5 to 2 and a ratio of molecular Hydrogen to hydrocarbon feedstock of approx. 3 3 270 to 540nm per m of starting material (approx. 1500 to 3000 SCP / barrel). 9. The method according to any one of the preceding claims, in particular according to claim 8, characterized in that the hydrogenation treatment at a temperature of about 315 ° C to 43O ° C Cca. 600 to 800 ⁰ F.) a Hg partial pressure of approx. 105 to 210 atm. (Approx. 1500 to 3000 psig.) A weight space velocity (WHSV) of approx. 0.5 to 3 and a ratio of molecular hydrogen to hydrocarbon feedstock from about 270 to 3 3 450nm per m of starting material (approx. 1500 to 2500 SCF / barrel) is performed to determine the viscosity index of the feedstock fed to the hydrocracking stage by at least 30 units. 10981 1/1854