US3142634A - Preparation of multi-grade lubricating oil - Google Patents

Description

H. R. IRELAND ETAL FUJI/RE Liquid Recycle VISCOSITY INDEX OF 650 F DEWAXED OIL Single Po\ 7 55 so as vlscosnv 0F 650 F" oewaxeo OIL ssu AT 210F.

/m/en/0rs Henry R //e/0/7d M/thae/ T 5/77/75/0' ag-Hm Affomey United States Patent Ofifice 3,142,634 Patented July 28, 1964- 3,142,634 PREPARATEQN OF MULTl-GRADE LUBRECATING GIL Henry R. Ireland, West Deptford Township, Gloucester County, and Michael T. Smilski, Mantua Township, Gloucester County, N.J., assignors to Socony Mobil Oil Company, Inc., a corporation of New York Filed Dec. 14, 1961, Ser. No. 159,339 Claims. (Cl. 208-95) This invention relates to a method for preparing multigrade lubricating oils. More particularly, this invention relates to the method of preparing multi-grade lubricating oils by hydrocracking particular deasphalted petroleum residuums at relatively low pressures.

Various methods are known to improve lubricating oils by hydrogen treatment at relatively low pressures. For instance, US. Patents 2,554,282, 2,787,582, and 2,904,505 describe procedures which hydrotreat various petroleum lubricating oil fractions under mild reaction conditions but avoid any substantial hydrocracking of these fractions. The hydrotreating procedures, however, have not been employed to prepare multi-grade oils. On the other hand, however, the preparation of multi-grade' lubricating oils by the catalytic treatment with hydrogen of deasphalted petroleum residuums to obtain combined hydrogenation and ring scission is described in US. 2,960,458. The disadvantage of this procedure relates to the fact that excessively high pressures ranging from 3600 to 4000 p.s.i.g. are necessarily employed. These high pressures are required to obtain a sufi'icient conversion of the petroleum fraction and provide suitable life of the catalyst to make the process commercially feasible. The use of higher pressures not only increases the cost of the production of multi-grade lubricating oils but requires expensive high pressure equipment. It would be, therefore, desirable to use relatively low pressures in the catalytic hydrocracking method of producing multi-grade lubricating oils in relatively high yields and at the same time avoid frequent regeneration or replacement which may be required of the catalyst utilized therein.

It is an object of this invention to provide a commercially attractive procedure for preparing multi-grade lubricating oils in relatively high yields by hydrocracking certain deasphalted petroleum fractions at relatively low reaction pressures. It is a further object to provide a procedure for preparing multi-grade lubricating oils utilizing relatively low catalytic hydrocracking reaction pressures wherein the life of the catalyst is not undesirably short. These and other objects will become apparent to those skilled in the art by the consideration of the following disclosure and appended claims.

Accordingly, a process for producing a multi-grade lubricating oil has been discovered wherein a charge stock of deasphalted residuum having a viscosity index in the range from about 60 to about 100 and a viscosity at 210 F. in the range from about 60 to about 250 S.S.U. is contacted with a recycle hydrocracked hydrocarbon stock boiling in the range from about 400 F. to about 700 F. which can be obtained by hydrocracking said charge stock, in which the volumetric ratio of said recycle stock to said charge stock ranges from about 0.111 respectively, to about 10:1, respectively, or higher. The combination of the deasphalted residuum and recycle stock is passed over a catalyst having hydrogenation and cracking properties in the presence of hydrogen at a temperature in the range from about 700 F. to about 870 F., at pressures in the range from about 800 to about 2400 p.s.i.g. and a liquid hourly space velocity from about 0.2 to about 2.0. This hydrocracking reaction requires a hydrogen consumption of at least about 750 standard cubic feet (s.c.f.) per barrel of charge stock. The product of the hydrocracking procedure boiling above about 600 F. can be dewaxed, if necessary, and distilled to provide components which directly, or upon blending with each other, meet the S.A.E. specifications for a multi-grade lubricating oil and have a viscosity index of 115 or above.

The starting charge stock which is used in the process of this invention can be any residuum boiling in excess of 600 F. obtained by distillation of a petroleum crude which after deasphalting with known low boiling deasphalting hydrocarbons such as propane provides a charge stock oil having a viscosity index in the range from about 60 to 100, preferably in the range from about to and viscosity at 210 F. of about 70 to about 200 S.S.U. These residuums can be obtained by distillation from various petroleum crudes such as Kuwait, North African, Mid-Continent, Gulf Coastal, West Texas, Tia Juana, and the like. Using a charge stock which has a viscosity index below about 60 and a viscosity at 210 F. below about 60 will generally not provide acceptable yields of multi-grade oils.

The reaction conditions necessary to produce multigrade lubricating oils of this invention require temperatures in the range from about 700 F. to about 870 F., preferably in the range from about 725 to about 850 F. The pressures which are employed include those ranging from about 800 pounds per square inch to about 2400 pounds per square inch, the liquid hourly space velocity which can be used ranges from about 0.1 to about 2.0, preferably in the range from about 0.2 to about 1.0. Utilizing the conditions described above, will provide conversions of the starting charge stock (i.e., 100-material boiling above 650 F., expressed as volume percent of charge), in the range from about 30 to about 60 volume percent and minimum yields of desirable lubricating oil fractions of about 30 volume percent, generally in range from about 40 to 60 volume percent, based on the deasphalted charge stock.

In hydrocracking operations, utilization of pressures in the range used for hydrotreating operations significantly increase the catalyst aging rate wherein frequent regeneration of the catalyst is necessary or early replacement of the catalyst is a requirement. YVhen frequent regeneration of the catalyst is required, the production of the desired products is seriously curtailed while early replacement of the catalyst is extremely costly. To avoid these problems, high pressures are desirable in hydrocracking operations to obtain acceptable yields of the desired product and to prevent accumulation of various poisons such as the deposit of carbonaceous materials and the like on the catalyst and prevent a significant decrease of catalytic activity or permanent catalyst damage. In a hydrotreating operation, the principal reaction is hydrogenation while generally avoiding any type of cracking reaction and the production of substantial catalytic poisons. In using hydrotreating pressures, the problem of catalyst aging is not as acute as in a hydrocracking operation and low pressures can be used and are desirable.

By the process of this invention, relatively low hydrocracking pressures can be utilized for the production of multi-grade lubricating oils in high yields by combining a hydrocracked hydrocarbon fraction boiling in the range from about 400 to about 700 F. with a deasphalted residuum charge stock in the hydrocracking zone. This hydrocracked hydrocarbon fraction can be obtained from the hydrocracked product of this process or other processes and combined with the deasphalted residuum charge stock in a volumetric ratio of 0.1:1 to about 10:1 or higher, preferably in the range from 1:1 to 5 :1. The use of the recycle hydrocracked fraction, herein, significantly decreases the catalyst aging rate by a factor of at least 2 at pressures below about 2400 p.s.i.g. Utilizing the recycle operation of this invention would provide hydrocracking operations to remain on stream approximately two times as long as the nonrecycle hydrocracking operation before regeneration is required. Thus, significantly extending life of the catalyst in a relatively low pressure hydrocracking process provides a commercially feasible and economically attractive method for producing multi-grade oils.

The catalyst employed in the process of this invention can include any type of catalyst having hydrogenation and cracking properties. Such catalyst are known in the art, for instance, these hydrocracking catalysts can include oxides and sulfides of any metal of Group VI left hand column of the Periodic System or mixture thereof, such as chromium, sulfide, molybdenum sulfide, tungsten sulfide and the like; oxides and sulfides of Group VIII of the Periodic Table or mixtures thereof such as the sufides of iron, cobalt, nickel, palladium, platinum, rhodium, osmium, iridum; mixtures of the above oxides and sulfides of the metals of Group VI left hand column and Group VIII such as a mixture of nickel sulfide and tungsten sulfide; cobalt sulfide and molybdenum sulfide, nickel sulfide and molybdenum sulfide and the like. These metals can be deposited on absorbent carriers such as alumina, silica-alumina, silica-zirconia, among others. Preferred catalysts include those comprising at least one of the metals having atomic numbers 44, 45, 46, 76, 77 and 78 deposited on a composite-like oxide of at least 2 of the metals of Group IIA, IIB, IVA, and NB of the Periodic arrangement of the elements particularly Where such composite has an activity index in excess of 25. Additional preferred catalysts include a sulfided or unsulfided 1 to 8 weight percent cobalt oxide and 3 to 20 Weight percent molybdenum trioxide on a silicaalumina or silica-zirconia base containing silica in amounts from about 5 to about 95 Weight percent.

The preferable type of hydrogen which may be used herein is, of course, pure hydrogen. However, hydrogen of a low purity such as a recycle hydrogen from a reforming operation can be used. If recycle hydrogen is used, it is preferable to remove the various contaminants therefrom by conventional purification procedures. The hydrogen can be circulated in this process at a ratio in the range from about 2000 to about 15,000 standard cubic feet (s.c.f.) per barrel of deasphalted residuum charge. It is essential, however, in obtaining multi-grade lubricating oils that the hydrogen consumption exceed 750 s.c.f. per barrel of deasphalted residuum charge. Hydrogen consumption will depend on the type of residuum charged, reaction conditions used, the types of catalyst use, among other factors. In most instances, however, the hydrogen consumption will generally range from about 900 to about 1500 s.c.f. per barrel of deasphalted residuum charge.

The products from the hydrocracking operation are then distilled, preferably by vacuum distillation, to separate the desired lubricating oil fractions from the low boiling reaction products such as, gases, gasoline, fuel oil and the like. These lubricating oils which boil above about 600 F. may contain some wax products. Removal of wax, if present, can be accomplished by any treatment conventionally used for dewaxing oils to provide an oil having a pour point below about F. Lower pour points can be obtained, if desired. The lubricating oil obtained can be used without blending various components if the requirements of multi-grade oils are met. If it is desirable to meet various specifications, the dewaxed lubricating oils can be distilled and blended accordingly. A modification Which can be used relates to the distillation of the hydrocracked lubricating oil into various oil components followed by the dewaxing procedure and blending the resulting components to obtain the desired multi-grade lubricating oil. Typical of a satisfactory dewaxing process is the method wherein the oil is dissolved in a solvent, such as propane; methyl ethyl ketone and toluene; and the like, cooling and filter- VISCOSITY VALUES OF MULTI-GRADE LUBRICATING OILS Viscosities, Saybolt Universal Seconds Oil designation At 0 F. At 210 F.

Maximum Minimum Maximum 4. 000 45 less than 58 12, 000 45 less than 58 12, 000 58 less than 70 12.000 70 less than 48. 000 58 less than 70 48, 000 70 less than 85 The above-described multi-grade lubricating oils, in general, require a viscosity index in excess of about 115.

The multi-grade lubricating oils produced by the process of this invention have a viscosity index in excess of about and can range as high as depending on the reaction conditions and initial charge stocks used. The advantage of the lubricating oils, produced herein, relates to the fact that a viscosity index improver additive is generally not required; however, if higher viscosity indices are desired, minimum amounts of viscosity index improvers can be added. Additional oil additives such as pour depressants, antioxidants, corrosion inhibitors, detergents, and the like can be added, if desired, to the multi-grade oils obtained herein to provide further improvements and requirements.

The hydrocracking process of this invention can be carried out in any equipment suitable for catalytic hydrocracking operations. The process may be operated batchwise. It is preferable, however, and generally more feasible to operate continuously. Accordingly, the process can be adapted to operations using a fixed bed of catalyst. Also, the process can be operated using a moving bed of catalyst wherein the hydrocarbon flow can be concurrent or countercurrent to the catalyst flow. A fluid type of operation may also be employed.

The following examples will serve to illustrate the process of the invention without limiting the same:

Example 1 A Kuwait-Barco propane deasphalted raflinate was used as the residuum charge stock to be hydrocracked. The charge stock had the following properties.

The catalyst utilized in the hydrocracking operations was prepared in the following manner:

A silica-zirconia support containing approximately 11 percent by weight ZrO was prepared by reacting 320 cc. of aqueous zirconium sulfate solution containing 0.05 g. ZrO /cc., 27 cc. of 50 percent by weight sulfuric acid, 1476 cc. of water and 700 cc. dilute N-Brand sodium silicate. The resulting silica-zirconia hydrosol set to a firm hydrogel in 30-50 seconds having a 6.3-6.8 pH. This gel was aged for 24 hours in water at room temperature, and then for 48 hours at 200 F. in /2 percent aqueous sulfuric acid solution reducing the pH of the hydrogel to 2.6. The hydrogel was thereafter base-exchanged with a 2 weight percent aqueous ammonium chloride solution free of chloride ion, water washed and dried for 16 hours at 280 F. in air and then calcined for 13 hours at 1000 F. in air. The silica-zirconia gel base so obtained was characterized by a pore volume of 0.54 cc./g.; an apparent density of 0.63 g./cc.; a surface area of 597 mP/g. and a weight composition of 0.01 percent Na, 0.01 percent 50;, 11.1 percent ZrO and remainder SiO Hydrocracking catalyst was prepared by first vacuum spray impregnating the above silica-zirconia gel with 10 percent M as a water solution of ammonium molybdate [(NH4)3MO70244H20], drying at 220 for hours and calcining 3 hours at 1000 F. in air. The resulting composite was then impregnated with 3 percent CoO as a water-solution of cobalt nitrate dried at 230 F. for 3 hours and calcined 10 hours at 1000 F. in air. The resulting catalyst was sulfided with a 50 percent H 50 percent H S mixture employing 2 volumes per volume of catalyst per minute for 5 hours at 800 F.

Example 2 Using the deasphalted residuum charge stock and catalyst described in Example 1, a single pass and recycle hydrocracking operation are conducted over a 7 day period utilizing the following conditions:

Operation Single Pass Recycle Recycle hydrocracked stock (400-700 F.),

volume per volume of fresh feed 0 1. 1 Pressure, ponds per square inch gauge- 2,000 2, 000 Temperature, F. (average) 770 728 Liquid hourly space velocity of charge stoc 0.5 0.5 Hydrogen circulation, standard cubic feet per barrel of charge stock 10, 000 10,000 Catalyst aging rate, F. per day appg tlg 5 to 0.1

Conversions (loo-products boiling above 650 F, expressed as volume percent) 48-52 48-52 [Inspection of various fractions of hydrocracked product boiling above 650 F. and dweaxed to a pour point of 20 The data described in the above example is graphically illustrated in the accompanying figure wherein the fractions having the same viscosity of dewaxed oil boiling in excess of 650 F. obtained from a single pass operation and a recycle operation using similar reaction conditions is plotted versus the viscosity index of the oil. The accompanying figure demonstrates the production of 'superior multi-grade oils of the recycle operation over the single pass operation. The recycle operation not only provides superior multi-grade lubricating oils but extends the life of the catalyst utilized by a factor of at least 5 over the single pass operation at the pressures utilized. The use of the recycle operation permits longer on-time stream operation in the production of lubricating oils and requires fewer regenerations than the single pass operation over the useful life of the catalyst. Similar improvements in using the recycle operation of this invention which are demonstrated in this example are also realized when pressures of about 2400 pounds per square inch gauge are utilized.

To demonstrate the comparative data of extremely low pressures in the hydrocracking operations, of single pass versus recycle operations, the deasphalted residuum and catalyst described in Example 1 are used under the following conditions:

[Inspection of 50 8.8.110. 210 F. oil of hydrocracked pgoldalct boiling above 650 and dewaxcd to a pour point of 20 Single Recycle pass Viscosity Index 114 123 118 Viscosity:

S.S.U. 0 F. (extrapolated) 12, 500 9,500 11, 500 S.S.U. F 231 205 216 Meets requirements of a 10W/2O multi-grade oil no yes yes The data of the above example demonstrates again the significant improvement of the catalyst aging rates of the recycle operation over the single pass operation. At a pressureof 1000 pounds per square inch gauge the catalyst aging rate of the single pass operation is about 2 times greater than for the recycle operation. Furthermore, in the separation of an oil having a viscosity of 210 F. of 50 S.S.U., the product obtained by the single pass operation does not meet the S.A.E. requirements of a 10W/ 20 multi-grade oil. It should be noted, however, that in the recycle operation at pressures as low as 800 pounds per square inch, the catalyst aging rate is slightly lower than the single pass operation at higher pressures yet provides an oil which meets the S.A.E. specifications of a 10W/ 20 multi-grade lubricating oil.

In the above Examples 2 and 3, the recycle operation requires a hydrogen consumption in excess of about 750 standard cubic feet (s.c.f.) of hydrogen per barrel of charge stock to provide the multi-grade lubricating oils. The hydrocracked cycle stock boiling in the range from about 4 00 to about 700 P. which can be used in the recycle operation of this invention is obtainable from the same hydrocracking operation which is preferable or from a completely different hydrocracking operation utilizing a petroleum charge stock.

It should be understood that this invention includes all changes and modifications of the examples of the invention herein chosen for purposes of disclosure Which do not constitute departures from the spirit and scope of the invention.

What is claimed is:

1. A method for producing multi-grade lubricating oils by hydrocracking at relatively low pressures which comprises contacting a deasphalted residuum charge stock having a viscosity index from about 60 to about 100 and a viscosity at 210 F. from about 60 to about 250 S.S.U. with a hydrocracked cycle hydrocarbon stock boiling in the range from about 400 F. to about 700 F. in a volumetric ratio of said cycle stock to said deasphalted residuum charge stock from about 0.1:1, respectively, to about 10:1, respectively, with hydrogen in the presence of a hydrocracking catalyst at a temperature in the range from about 700 F. to about 870 F., at pressures in the range from about 800 to about 2400 p.s.i.g., at a liquid hourly space velocity from about 0.2 to about 2.0 and a hydrogen consumption in excess of about 750 s.c.f. per barrel of deasphalted residuum charge stock, and separating from the hydrocracked product a multi-grade lubricating oil having a maximum and minimum viscosity limits of the S.A.E. specifications and a viscosity index in excess of about 115.

2. A method for producing multi-grade lubricating oils by hydrocracking at relatively low pressures which comprises contacting a deasphalted residuum charge stock having a viscosity index from about 60 to about 100 and a viscosity at 210 F. from about 60 to about 250 S.S.U. with a hydrocracked cycle hydrocarbon stock boiling in the range from about 400 F. to about 1700 F. in a volumetric ratio of said cycle stock to said deasphalted residuum charge stock from about 0.1:1, respectively, to about 10:1, respectively, with hydrogen in the presence of a hydrocracking catalyst at a temperature in the range from about 700 F. to about 870 F., at pressures in the range from about 800 to about 2400 p.s.i.g., at a liquid hourly space velocity from about 0.2 to about 2.0 and a hydrogen consumption in excess of about 750 s.c.f. per barrel of deasphalted residuum charg stock, dewaxing the hydrocracked product boiling above 600 F. to a pour point below about 20 F. and separating components of said dewaxed product to obtain a multi-grade lubricating oil having a maximum and minimum viscosity limits of the S.A.E. specifications and a viscosity index in excess of about 115.

3. A method for producing multi-grade lubricating oils by hydrocracking at relatively low pressures which comprises contacting a deasphalting residuum charge stock having a viscosity index from about 60 to about 100 and a viscosity at 210 F. from about 60 to about 250 S.S.U. with a hydrocracked cycle hydrocarbon stock boiling in the range from about 400 F. to about 700 F. in a volumetric ratio of said cycle stock to said deasphalted residuum charge stock from about 1:1, respectively, to about 5:1, respectively, with hydrogen in the presence of a hydrocracking catalyst at a temperature in the range from about 700 F. to about 870 F., at pressures in the range from about 800 to about 2400 p.s.i.g., at a liquid hourly space velocity from about 0.2 to about 2.0 and a hydrogen consumption in excess of about 750 s.c.f. per barrel of deasphalted residuum charge stock, dewaxing the hydrocracked product boiling above 600 F. to a pour point below about 20 F. and separating components of said dewaxed product to obtain a multi-grade lubricating oil having a maximum and minimum viscosity limits of the S.A.E. specifications and a viscosity index in excess of about 115.

4. A method for producing multi-grade lubricating oils by hydrocracking at relatively low pressures which comprises contacting a deasphalted residuum charge stock having a viscosity index from about 60 to about 100 and a viscosity at 210 F. from about 60 to about 250 S.S.U. with a hydrocracked cycle hydrocarbon stock boiling in the range from about 400 F. to about 700 F. in a volumetric ratio of said cycle stock to said deasphalted residuum charge stock from about 0.1:1, respectively, to about 10:1, respectively, with hydrogen in the presence of a hydrocracking catalyst at a temperature in the range from about 700 F. to about 870 F., at pressures in the range from about 800 to about 2400 p.s.i.g., at a liquid hourly space velocity from about 0.2 to about 2.0 and a hydrogen consumption in excess of about 750 s.c.f. per barrel of deasphalted residuum charge stock, dewaxing the hydrocrackecl product boiling above 600 F. to a pour point below about 20 F. and separating fractions which upon blending have a maximum and minimum viscosity limits of the S.A.E. specifications and a viscosity index in excess of about 115.

5. A method for producing multi-grade lubricating oils by hydrocracking at relatively low pressures which comprises contacting a deasphalted residuum charge having a viscosity index from about 75 to about and a viscosity at 210 F. from about 70 to about 200 S.S.U. with a hydrocracked cycle hydrocarbon stock boiling in the range from about 400 F. to about 700 F. in a volumetric ratio of said cycle stock to said deasphalted residuum charge stock from about 0.1:1, respectively, to about 10:1, respectively, with hydrogen in the presence of a hydrocracking catalyst at a temperature in the range from about 7 00 F. to about 870 F., at pressures in the range from about 800 to about 2400 p.s.i.g., at a liquid hourly space velocity from about 0.2 to about 2.0 and a hydrogen consumption in excess of about 750 s.c.f. per barrel of deasphalted residuum charge stock, dewaxing the hydrocracked product boiling above 600 F. to a pour point below about 20 F. and separating components of said dewaxed product to obtain a multi-grade lubricating oil having a maximum and minimum viscosity limits of the S.A.E. specifications and a viscosity index in excess of about 115.

6. A method for producing multi-grade lubricating oils by hydrocracking at relatively low pressures which comprises contacting a deasphalted residuum charge stock having a viscosity index from about 75 to about 100 and a viscosity at 210 F. from about 70 to about 200 S.S.U. with a hydrocracked cycle hydrocarbon stock boiling in the range from about 400 F. to about 700 F. in a volumetric ratio of said cycle stock to said deasphalted residuum charge stock from about 1:1, respectively, to about 5:1, respectively, with hydrogen. in the presence of a hydrocracking catalyst at a temperature in the range from about 700 F. to about 870 F., at pressures in the range from about 800 to about 2400 p.s.i.g., at a liquid hourly space velocity from about 0.2 to about 2.0 and a hydrogen consumption in excess of about 750 s.c.f. per barrel of deasphalted residuum charge stock, dewaxing the hydrocracked product boiling above 600 F. to a pour point below about 20 F. and separating components of said dewaxed product to obtain a multi-grade lubricating oil having a maximum and minimum viscosity limits of the S.A.E. specifications and a viscosity index in excess of about 115.

7. A method for producing multi-grade lubricating oils by hydrocracking at relatively low pressures which comprises contacting a deasphalted residuum charge stock having a viscosity index from about 75 to about 100 and a viscosity at 210 F. from about 70 to about 200 S.S.U. with a hydrocracked cycle hydrocarbon stock boiling in the range from about 400 F. to about 700 F. in a volumetric ratio of said cycle stock to said deasphalted residuum charge stock from about 0.1:1, respectively, to about 10:1, respectively, with hydrogen in the presence of a hydrocracking catalyst at a temperature in the range from about 700 F. to about 870 F., at pressures in the range from about 800 to about 2400 p.s.i.g., at a liquid hourly space velocity from about 0.2 to about 2.0 and a hydrogen consumption in excess of about 750 s.c.f. per barrel of deasphalted residuum charge stock, dewaxing the hydrocracked product boiling above 600 F. to a pour point below about 20 F., and separating fractions which upon blending have a maximum and minimum viscosity limits of the S.A.E. specifications and a viscosity index in excess of about 115.

8. A method for producing multi-grade lubricating oils by hydrocracking at relatively low pressures which comprises contacting a deasphalted residuum charge stock having a viscosity index from about 75 to about 100 and a viscosity at 210 F. from about 70 to about 200 S.S.U. with a hydrocracked cycle hydrocarbon stock boiling in the range from about 400 F. to about 700 F. in a volumetric ratio of said cycle stock to said deasphalted residuum charge stock from about 0.1:1, respectively, to about 10:1, respectively, with hydrogen in the presence of catalyst which comprises a sulfided mixture of cobalt oxide and molybdenum trioxide on a silica-Zirconia base at a temperature in the range from about 700 F. to about 870 F., at pressures in the range from about 800 to about 2400 p.s.i.g., at a liquid hourly space velocity from about 0.2 to about 2.0 and a hydrogen consumption in excess of about 750 s.c.f. per barrel of deasphalted residuum charge stock, dewaxing the hydrocracked product boiling above 600 F. to a pour point below about 20 F. and separating components of said dewaxed product to obtain a multi-grade lubricating oil having a maximum and minimum viscosity limits of the S.A.E. specifications and a viscosity index in excess of about 115.

9. A method for producing multi-grade lubricating oils by hydrocracking at relatively low pressures which comprises contacting a deasphalted residuum charge stock having a viscosity index from about 75 to about 100 and a viscosity at 210 F. from about 70 to about 200 S.S.U. with a hydrocracked cycle hydrocarbon stock boiling in the range from about 400 F. to about 700 F. in a volumetric ratio of said cycle stock to said deasphalted residuum charge stock from about 1:1, respectively, to about 5:1, respectively, with hydrogen in the presence of catalyst which comprises a sulfided mixture of cobalt oxide and molybdenum trioxide on a silica-zirconia base at a temperature in the range from about 700 F. to about 870 F., at pressures in the range from about 800 to about 2400 p.s.i.g., at a liquid hourly space velocity 10 I from about 0.2 to about 2.0 and a hydrogen consumption in excess of about 750 s.c.f. per barrel of deasphalted residuum charge stock, dewaxing the hydrocracked product boiling above 600 F. to a pour point below about 20 F. and separating components of said dewaxed product to obtain a multi-grade lubricating oil having a maximum and minimum viscosity limits of the S.A.E. specifications and a viscosity index in excess of about 115.

10. A method for producing multi-grade lubricating oils by hydrocracking at relatively low pressures which comprises contacting a deasphalted residuum charge stock having a viscosity index from about to about and a viscosity at 210 F. from about 70 to about 200 S.S.U. with a hydrocracked cycle hydrocarbon stock boiling in the range from about 400 F. to about 700 F. in a volumetric ratio of said cycle stock to said deasphalted residuum charge stock from about 0.1:1, respectively, to about 10:1, respectively, with hydrogen in the presence of catalyst which comprises a sulfided mixture of cobalt oxide and molybdenum trioxide on a silica-zirconia base at a temperature in the range from about 700 F. to about 870 F., at pressures in the range from about 800 to about 2400 p.s.i.g., at a liquid hourly space velocity from about 0.2 to about 2.0 and a hydrogen consumption in excess of about 750 s.c.f. per barrel of deasphalted residuum charge stock, dewaxing the hydrocracked product boiling above 600 F. to a pour point below about 20 F., and separating fractions which upon blending have a maximum and minimum viscosity limits of the S.A.E. specifications and a viscosity index in excess of about 115.

References Cited in the file of this patent UNITED STATES PATENTS 1,951,792 Harding Mar. 20, 1934 2,904,505 Cole Sept. 15, 1959 2,960,458 Beuther et a1. Nov. 15, 1960 2,967,146 Manley Jan. 3, 1961 3,011,974 Henke et a1. Dec. 5, 1961 3,046,218 Henke et a1. July 24, 1962 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. a, 142,634 July 28, 1964 Henry R. Ireland et a1.

, It is hereby certified that error appears in the above numbered patent feqiiring correction and that the said Letters Patent should read as corrected below. I

Column 3 line 50 for "use" read used column 5 llxample 2 first table under the heading "-=Operacion" third line thereof for "ponds" read -pounds same table -underthe heading "Recycle" first line thereoi for "l. 1" read 121 under same heading "Recycle", third line t..hereof,, a for ""728" read 782 column 7 line 30, for 1700 F0 read "(00 F. column 8 line 16 after "charge" insert stock Signed and sealed this lst day of December 1964. (SEAL) Attest:

ERNEST w s'wwER EDWARD J; BRENNER enlisting Officer Commissioner of Patents

Claims (1)

1. 2. A METHOD FOR PRODUCING MULTI-GRADE LUBRICATING OILS BY HYDROCRACKING AT RELATIVELY LOW PRESSURES WHICH COMPRISES CONTACTING A DEASPHALTED RESIDUM CHARGE STOCK HAVING A VISCOSITY INDEX FROM ABOUT 60 TO ABOUT 100 AND A VISCOSITY AT 210*F. FROM ABOUT 60 TO ABOUT 250 S.S.U. WITH A HYDROCRACKED CYCLE HYDROCARBON STOCK BOILING IN THE RANGE FROM ABOUT 400*F. TO ABOUT 1700*F. IN A VOLUMETRIC RATIO OF SAID CYCLE STOCK TO SAID DEASPHALTED RESIDUUM CHARGE STOCK FROM ABOUT 0.1:1, RESPECTIVELY TO ABOUT 10:1, RESPECTIVELY, WITH HYDROGEN IN THE PRESENCE OF A HYDROCRACKING CATALYST AT A TEMPERATURE IN THE RANGE FROM ABOUT 700*F. TO ABOUT 870*F. AT PRESSURES IN THE RANGE FROM ABOUT 800 TO ABOUT 2400 P.S.I.G., AT A LIQUID HOURLY SPACE VELOCITY FROM ABOUT 0.2 TO ABOUT 2.0 AND A HYDROGEN CONSUMPTION IN EXCESS OF ABOUT 750 S.C.F. PER BARREL OF DEASPHALTED RESIDUUM CHARGE STOCK, DEWAXING THE HYDRCRACKED PRODUCT BOILING ABOVE 600*F. TO A POUR POINT BELOW ABOUT 20*F. AND SEPARATING COMPO-

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