US3714032A

US3714032A - Process for treating a high-boiling petroleum hydrocarbon feedstock

Info

Publication number: US3714032A
Application number: US00092582A
Authority: US
Inventors: R Bertolacini; H Radford
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1970-11-25
Filing date: 1970-11-25
Publication date: 1973-01-30
Anticipated expiration: 1990-01-30

Abstract

The process comprises contacting the high-boiling petroleum hydrocarbon feedstock under hydrocarbon conversion conditions and in the presence of hydrogen with a catalyst comprising a member selected from the group consisting of (1) uranium and a second hydrogenation metal, (2) their oxides, (3) their sulfides, and (4) mixtures thereof supported on a porous refractory inorganic oxide having an average pore diameter of about 100 Angstroms to about 300 Angstroms and a surface area in excess of 200 square meters per gram. The preferred second hydrogenation metal is molybdenum and the preferred porous refractory inorganic oxide is alumina.

Description

tlited States Patent n91 ttertolacini et al.

[54] PROCESS FOR TREATING A HIGH- BOILING PETROLEUM HYDROCARBON FEEDSTOCK [75] Inventors: Ralph J. Bertolacini, Chesterton,

t Ind; Herschel D. Radford, Flossmoor, Ill. [73'] As'ig'iiei stiiiiafiioiicompan Chicago, Ill.

['22 Filed: Nov. 25; 1970 21 Appl. No; 92,582

{ man, 1973 Primary Examiner-James E. Poer Assistant Examiner-Werten F. W. Bellamy Attorney-Arthur G. Gilkes, William T. McClain and James L. Wilson [57] ABSTRACT The process comprises contacting the high-boiling petroleum hydrocarbon feedstock under hydrocarbon conversion conditions and in the presence of hydrogen with a catalyst comprising a member selected from the group consisting of (l) uranium and a second hydrogenation metal, (2) their oxides, (3) their sultides, and (4) mixtures thereof supported on a porous refractory inorganic oxide having an average pore diameter of about 100 Angstroms to about 300 Angstroms and a surface area in excess of 200 square meters per gram. The preferred second hydrogenation metal is molybdenum and the preferred porous refractory inorganic oxide is alumina. I

13 Claims, 3 Drawing Figures PATENTEDJM 30 I973 SHEET 2 BF 3 3,714,032

=o zo Us;

On- 09 on G 3 m I om 1 n nu o m V u 0 ow ..N m 1 0m 09 Pmmmmso ms sum 3 OF 3 3.714.032

Fig. 3

CORRELATION BETWEEN DESULFURIZATION 8 REDUCTION OF RAMSBOTTOM CARBON MATERIAL 6atalyst 0 80 Gata/yst A 3 Catalyst 8 z. E 10-- i a: a 3 Catalyst 0 w 2.

0 IO 20 3O 4O 5O 6O 7O 8O 90 REDUCTION OF RAMSBOTTOM CARBON MATERlAL,-Wf. Z

PROCESS FOR TREATING A HIGH-BOILING PETROLEUM HYDROCARBON FEEDSTOCK BAC KGROUND OF THE INVENTION and hydrocarbon residua. High-boiling distillates boil at temperatures above about 570F. and include the heavy gas oils and light lubricating oils. Hydrocarbon residua are made up of saturates, monoaromatics, polyaromatics, resins, and asphalt and are found to have molecular weights that areat least about 600 and may exceed 1,200. At this time, the complete composition of petroleum is unknown. There are many areas in the make up of petroleum hydrocarbon crudes where the molecular compositions of the compounds remain unknown. One of these areas is the area comprising the high-boiling residual fractions.

While there are may processes employing numerous refining techniques which are used by petroleum refiners to upgrade the various fractions obtained from crudes, such processes do not convert effectively the higher-boiling feedstocks and fractions into sufficient quantities of usable products, such as motor fuels and heating fuels. For the most part, attempts'to refine the higher-boilin g hydrocarbons, such as heavy gas oils and petroleum hydrocarbonresidua, have shown that the processing must be done at such high severities that it is unattractive. These refractory higher-boiling materials give relatively low yields of usable products. The ordinary refinery process will not convert them into economical quantities of products.

The process of the present invention is an improved process for treating effectively the refractory higherboiling gas oils and residual hydrocarbons to obtain more usable products.

SUMMARY OF THE INVENTION vBroadly, there is provided a process for treating a high-boiling petroleum hydrocarbon feedstock. This process comprises contacting said high-boiling petroleum hydrocarbon feedstock under hydrocarbon conver- "sion conditions and in the presence of hydrogen with a catalyst comprising a hydrogenation component and a porous refractory inorganic oxide having an'average pore diameter of about 100 Angstroms to about 300 Angstroms and a surface area that is in excess of 200 square meters per gram. The hydrogenation component comprises a member selected from the group consisting of (l) uranium and a second hydrogenation metal, (2) their oxides, (3) their sulfides, and (4) mixtures thereof. The uranium is present in an amount of about I to about l0 weight percent, calculated as U0 and based on the weight of the catalyst. A preferred second hydrogenation metal is molybdenum. Molybdenum may be present in an amount of about 5 to about 15 weight percent, calculated as M00 and based on the weight of the catalyst.

A preferred porous refractory inorganic oxide is a catalytically active alumina.

BRIEF DESCRIPTION OF THE DRAWINGS Three drawings accompany this application.

FIG. 1 is a highly-simplified schematic flow diagram of a preferred embodiment of the process of the present invention.

FIG. 2 presents a comparison of the desulfurization activities of two catalysts, when each is used to treat a resid containing 1.7 weight percent sulfur.

FIG. 3 presents a correlation between desulfurization and the reduction of Ramsbottom Carbon material that was prepared from data obtained with various catalysts.

DESCRIPTION AND PREFERRED EMBODIMENTS Hydrocarbon residual materials, for the most part, are by-products of processes which are primarily used to obtain other petroleum products. The residual fuel oils are such hydrocarbon residua. Such residual fuel oils have been used generally to supply heat.

The heavier or higher-boiling fractions of the various petroleum crudes will contain appreciable amounts of sulfur and nitrogen, as well as certain so-called heavy metals, such as nickel and vanadium. For example, a vacuum reduced crude may be found to contain as much as 100 ppm nickel. These heavy metals affect deleterio'usly the life of any catalyst over which the hydrocarbons containing such metals are being processed. In upgrading the heavier fractions of a petroleum crude, it is ultimately required that a portion of the nitrogen be removed from the heavy-gas-oil fraction and that a substantial amount of the heavy metals be removed from the fraction boiling above 600F., this latter material being sent usually to a catalytic cracker for an additional treatment. 7

There'has now been found a process for treating a heavy or high-boiling petroleum hydrocarbon feedstock. This process can be used to hydroprocess, desulfurize, denitrogenate, or even hydrocrack, the feedstock. Desulfurization occurs when sulfur is removed from the feedstock being treated. Denitrogenation occurs when the amount of nitrogen in the feedstock is reduced. Hydroprocessing comprises bringing the feedstock into contact with hydrogen over the catalyst of the process. Generally, during hydroprocessing, ap preciable amounts of desulfurization and denitrogenation occur, while some hydrocracking is obtained to yield usable hydrocarbon products. Hydrocracking comprises the destructive hydrogenation of a petroleum hydrocarbon feedstock which has a relatively high molecular weight to produce a lower-molecular weight hydrocarbon fraction. Hydrocracking is performed at elevated temperatures and pressures in the presence of a suitable catalyst and a hydrogen-containing gas. Hydrogen is consumed in the conversion of organic nitrogen to ammonia and sulfur to hydrogen sulfide, in the splitting of higher-molecular-weight compounds into lower-molecular-weight compounds, and in the saturation of olefins and other unsaturated compounds.

The process of the present invention can be used to upgrade high-boiling hydrocarbon fractions. It is particularly useful in converting those hydrocarbon feedstocks which are composed mainly of hydrocarbons boiling above 650F. An example of such a hydrocarbon feedstock is a Cyrus crude which contains 69.8 volume percent material boiling at a temperature of at least 650F.,'which has a gravity of 8.9 API and a sulfur content of 4.5 weight percent, and which contains 230 ppm vanadium and ppm nickel.

The heavy metals in these higher-boiling hydrocarbon feedstocks exist in compounds. During the hydroprocessing reactions, compounds which contain metals are decomposed and the metals are subsequently deposited on the catalyst and in the coke which has accumulated on the catalyst. The coke and metals may be removed by suitable regeneration techniques; or, if the appropriate conditions exist, the spent catalyst may be discarded advantageously.

The catalyst of the process of the present invention is a catalytic composition which comprises a hydrogenation component and a porous refractory inorganic oxide having an average pore diameter of about 100 Angstroms to about 300 Angstroms and a surface area that is in excess of 200 square meters per gram.

The hydrogenation component of the catalyst of the present invention is a member selected from the group consisting of (l) uranium and a second hydrogenation metal, (2) their oxides, (3) their sulfides, and (4) mixtures thereof. The second hydrogenation metal may be molybdenum, rhodium, or similar transition metals and metals of Group VIII of the Periodic Table of Elements. The preferred second hydrogenation metal is molybdenum. The uranium is present in an amount of about 1 weight percent to about 10 weight percent, calculated as U and based on the weight of the catalyst. When molybdenum is employed, the molybdenum is present in an amount within the range of about weight percent to about weight percent, calculated as M00 and based on the weight of the catalyst.

The porous refractory inorganic oxide that is employed as a support in the catalyst that is used in the process of the present invention should have an average pore diameter of about 100 Angstroms to about 300 Angstroms and a surface area that is in excess of 200 square meters per gram. Such a support may be a catalytically active alumina, such as gammaalumina and/or eta-alumina, silica-alumina, magnesium alumina, and halide-containing aluminas.

The preferred porous refractory inorganic oxide for use in the catalyst of the process of the present invention is a catalytically active alumina having a large average pore diameter. Examples of this alumina are Nalco 47l-A alumina, manufactured by the Nalco Chemical Company, and Aero 100 alumina, manufactured by the American Cyanamid Company. A typical sample of Nalco 47l-A alumina was found to have a surface of 348 square meters per gram, an average pore diameter of 1 l2 Angstroms, and a total pore volume of 0.65 cubic centimeters per gram. A typical sample of Cyanamid Aero 100 alumina was found to have a surface area of 238 square meters per gram, an average pore diameter of 138 Angstroms (calculated), and a total pore volume of 0.82 cubic centimeters per gram.

Furthermore, such refractory inorganic oxide may have dispersed therethrough and suspended therein one or more of various aluminosilicate materials. Such aluminosilicate material may be either naturally-occuring or synthetic aluminosilicates, such as faujasites, chabazite, mordenite, X-type, Y-type, decationized Y- type, hydrogen-form Y-type, ultrastable aluminosilicate material, and the like. These aluminosilicates must be large pore materials and must be crystalline. A large-pore aluminosilicate material is a material that has pores which are sufficiently large to permit the passage thereinto of benzene molecules and larger molecules, and the passage therefrom of reaction products. It is preferred to employ a large-pore aluminosilicate material that has an average pore diameter of at least 8 Angstroms.

All of the components of the catalytic composition that is employed in the process of the present invention are materials that are readily available and relatively inexpensive. Even the uranium metal is an inexpensive item, since uranium metals and salts are readily available, cheap by-products from the many uses of atomic energy. As an example, spent reactor cores from atomic power plants are cheap sources of uranium.

The catalyst employed in the process of the present invention is prepared by conventional methods of catalyst preparation. For example, the porous refractory inorganic oxide, in the form of finely-divided particles, can be impregnated with a solution containing both uranium and the second hydrogenation metal. A]- ternatively, the porous refractory inorganic oxide can be impregnated sequentially with two sources of the desired hydrogenation metals, the one solution comprising a solution of the uranium salt and the other solution comprising a solution of the second hydrogenation metal, e.g., molybdenum. After impregnation, the finely-divided particles of the catalyst may be pelleted or extruded into macro-particles having a selected size. As an alternate method of preparation, the selected refractory inorganic oxide is first pelleted or extruded into particles of a pre-determined size and the resulting macro-particles are impregnated with the appropriate hydrogenation-metal solution or solutions, followed by drying and calcining. In still another method of preparation, a solution or solutions of the appropriate hydrogenation metals are thoroughly blended with a gel of the selected refractory inorganic oxide. After thorough blending, the gel is dried and calcined under conventional drying and calcining conditions.

Broadly, the hydrocarbon conversion conditions that are employed in the process of the present invention comprise an average catalyst temperature of about 600F. to about 1,200F.; a hydrogen pressure of about 800 psig to about 3,500 psig; a liquid hourly space velocity (LHSV) of about 0.25 to about 5.0 volumes of hydrocarbon per hour per volume of catalyst; and a hydrogen addition rate, that is, the rate of hydrogen being introduced into the reactor, of about 3,000 standard cubic feet per barrel (SCFB) to about 40,000 SCFB. Preferably, the operation conditions comprise an average catalyst temperature of about 725F. to about 1,050F.; a hydrogen pressure of about 1,200 psig to about 2,500 psig; a LHSV of about 0.3 to about 1.0 volume of hydrocarbon per hour per volume of catalyst; and a hydrogen addition rate of about 5,000 SCFB to about 30,000 SCFB.

The process of the present invention can be used as an independent process for the treating of heavy or high-boiling petroleum hydrocarbon fraction. It may comprise a one-stage operation employing one or more reactors. in addition, the process of the present invention may be one of the stages in a multi-stage operation. For example, it could be the first stage of a multi-stage process, wherein it would be employed to desulfurize and possibly hydrocrack the heavy feedstock being treated. However, the process of the present invention could be employed as a second stage of a multi-stage process wherein a different process might be employed as the first stage to desulfurize a particular feedstock and the process of the present invention would then be used to treat the effluent from the first stage to convert the hydrocarbons therein to more usable products.

FIG. 1 represents a simplified flow diagram of a preferred embodiment of the process of the present invention. It does not include certain pieces of auxiliary equipment, such as heat exchangers, valves, pumps, compressors, and associated equipment, which would be required in various places along the flow path of the process in addition to the pump and compressor which are depicted in the drawing. This additional auxiliary equipment and its location in the process scheme would be recognized quickly by one having ordinary skill in the art. Consequently, this equipment is not shown in the figure.

In the embodiment represented in FIG. 1, a highboiling hydrocarbon fraction, which is composed mainly of hydrocarbons boiling above 650F. and which contains substantial amounts of sulfur, nickel, and vanadium, is passed from source through line 11 into pump 12, which pumps the hydrocarbon material through line 13. Hydrogen-containing recycle gas is introduced into line 13 by way of line 14 to be mixed with the hydrocarbons in line 13. Additional hydrocarbons may be added to the mixture in line 13 by way of line 15. The hydrocarbon stream in line 15 is that portion of the liquid product that is recycled to be converted further in the reactor section. The hydrogen-hydrocarbon mixture passes through line 13, furnace 16, and line 17 into the top of reactor section 18. Whilereactor section 18 is represented by only one reactor in FIG. 1, two or more reactors could make up this reactor section 18.

The catalyst that is employed in reactor section 18 is a catalyst which comprises 2.5 weight percent U0 and 10 weight percent M00 on a catalytically active alumina which has an average pore diameter of at least 100 Angstroms and a surface area that is in excess of 200 square meters per gram.

The operating conditions in reactor section 18 comprise an average catalyst temperature of about 600F. to about I,200F., a hydrogen pressure of about 800 psig to about 3,500 psig, a LHSV of about 0.25 to about 5 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 3,000 SCFB to-about 40,000 SCFB.

The effluent from reactor section 18 is removed therefrom through line 19 into cooler 20. The cooled reactor effluent is passed subsequently through'line 21 into gas-liquid separator 22 wherein hydrogen-containing gas is separated from the cooled liquid product.

The hydrogen-containing gas is removed from separator 22 by way of line 23. The gas in line 23 is compressed by compressor 25. The compressed gas is then recycled to reactor section l8'by passage through

lines

26, 14, and 13, furnace 16, and line 17. Make-up hydrogen may be added to the system from source 27 via line 28. The liquid product from separator 22 is removed therefrom by way of line 24 to be sent to conventional product recovery equipment from which usable hydrocarbon products are obtained. A portion of the high-boiling bottoms material from this liquid product may'be recycled to line 15 by which it is introduced into the hydrogen-hydrocarbon mixture that is to be sent to the reactor section.

The following examples are presented herein to facilitate the understanding of the present invention. The examples are presented for the purpose of illustration only and are not intended to limit the scope of the present invention.

EXAMPLE I A commercially prepared catalyst comprising cobalt and molybdenum oxides on a support of typical Nalco 47 l-A alumina was obtained from the Nalco Chemical Co. This catalyst contained 3.5 weight percent C00 and 12.9 weight percent M00 based on the weight of the catalyst. The alumina that was employed in this catalyst, which catalyst will be identified hereinafter as Catalyst A, was shown, typically, to have a pore volume of 0.6 cubic centimeters per gram, an average bulk density of 0.74 grams per cubic centimeter, and a surface area of 284 square meters per gram.

EXAMPLE II A catalyst comprising cobalt, molybdenum and fluorine on an alumina having a large average pore diameter was prepared. A 500-gram portion of 1 /32 inch extrudates, which comprised cobalt and molybdenum on Nalco 471-A alumina and which were prepared by the Nalco Chemical Co., was impregnated with 600 ml. of an aqueous solution containing 40 grams of ammonium fluoride. The impregnated sample was dried in air at a temperature of about 250F. and calcined in air for 4 hours at a temperature of 1,000F. Unless otherwise specified, the flow rate of air during any drying or calcining treatment was maintained at about 1.5 cubic feet per hour. The calcined material was found to contain 3.1 weight percent fluoride. The catalyst also contained about 3.5 weight percent C00 and about 12.9 weight percent M00 This catalyst is identified hereinafter as Catalyst B.

EXAMPLE III A catalyst comprising the oxides of nickel and tungsten on a Nalco 471-A alumina was prepared by impregnating a 83-gram portion of l/ 16-inch extrudates of the alumina with an aqueous solution. This solution was prepared by dissolving 11.7 grams of Ni(NO and 14.1 grams of (NHQ H W O X H O in 100 ml. of hot water (about 160F.). The impregnated material was dried in air at a temperature of about 250F. and calcined in air for about 4 hours at a temperature of about l,000F. The catalyst, which is identified hereinafter as Catalyst C, was prepared to contain 3 weight percent NiO and 13 weight percent W0 based on the weight of the catalyst.

EXAMPLE IV A catalyst of the process of the present invention was prepared. A -gram portion of Aero alumina, prepared by the American 'Cyanamid Co'. and comprising 1/ 16-inch extrudates, was impregnated with a solution containing uranyl nitrate. The solution was prepared by dissolving 5.0 grams of U0, (N0 611 0 in 80 ml. of hot water (about F.). The impregnated material was dried at 250F. for 1 hour in air and then impregnated with a solution containing molybdenum. This latter solution was prepared by dissolving 12.1

grams of (NH Mo-,O, 41-1 in 60 ml. of hot water (about 160F.). The material was then dried at a temperature of 250F. in air and calcined at a temperature of 1,000F. for 1 hour. The catalyst, which is identified hereinafter as Catalyst D, was prepared to contain 2.5 weight percent U0 and weight percent M00 based on the weight of the catalyst.

EXAMPLE V The above catalysts were tested individually in a micro-flow test unit. In this unit, a mixture of preheated oil and hydrogen was passed over a 30 cc sample of the catalyst being considered. The reactor had an internal diameter of five-eighths inch and was sufficiently long to contain a 7-inch catalyst bed, a ,a-inch layer of tabular alumina above the catalyst bed, and a 1-inch layer of tabular alumina below the catalyst bed. The off-gas was continually vented and the liquid product was collected in either a product receiver of a slop receiver. The reactor was heated by an electrical heating block and the various temperatures in the reactor were determined by a manually-operated co-axial thermocouple. The reactor was operated under essentially isothermal conditions. Prior to being charged into the reactor, each catalyst was ground to a 12-20-mesh material (U. S. Sieve series).

Catalyst A was tested in Test No. 1; Catalyst B, in Test No. 2; Catalyst C, in Test No. 3; and Catalyst D, in Test No. 4 and Test No. 5.

For a given test, the reactor was charged with 30 cc of the selected catalyst. The catalyst was pretreated for a period of 2 hours at a temperature of about 650F. with 2 standard cubic feet per hour (SCFH) of a gas mixture comprising 8 volume percent hydrogen sulfide in hydrogen.- The pressure employed during this sulfiding pretreatment was 300 psig. The sulfided catalyst was contacted subsequently with the appropriate hydrocarbon feedstock at a temperature of 650F. During the on-stream time, the hydrogen flow rate was maintained at about 3 SCFH. After hours on stream at a temperature of 650F., the reactor temperature was increased to the operating temperature of 790F. Appropriate 4-hour samples were obtained daily after the reactor temperature had been elevated to 790F. The operating hydrogen pressure was maintained at 1,650 psig. Each test was conducted at LHSV of 0.45 volume of hydrocarbon per hour per volume of catalyst, except Test No. 4, which was conducted at a LHSV of 0.56 volume of hydrocarbon per hour per volume of catalyst.

Two desulfurized Cyrus atmospheric resids were employed as the hydrocarbon feedstocks for these tests. The properties of these feedstocks are given in Table 1.

TABLE I FEEDSTOCK PROPERTIES FEEDSTOCK N0. 1 2 Gravity, AP1 21.5 18.5 Sulfur, Wt.% 0.68 1.67 Pentane lnsolubles, Wt.% 9.3 15.2 Ramsbottom Carbon, Wt.% 6.6 10.1 Hot Benzene lnsolubles, Wt.% 0.05 Hydrogen Content, Wt.% 11.9 Oldershaw Distillation 650 F., Wt.% 78.4 85.0

The data obtained from Test No. 1 and Test No. 2 are presented in Table 11. The data obtained from Test No. 3, Test No. 4. and Test No. 5 are given in Table 111. The temperature is the arithmetic average temperature, that is, the arithmetic average of seven values taken 1 inch apart within the catalyst bed. The conversion was obtained from the following equation:

TABLE I1 Conv}, Test Cat- Feed Time, Temp., Desulffi, Carbon, No. alyst No. hours lhsv F. Wt.% Wt.% Wt.% 1 A 2 26 0.45 789 7. 81.4 4.2 52 0.45 790 7.1 76.2 4.7 76 0.45 790 9.6 74.3 5.6 2 B 1 34 0.45 788 68 75.0 2.2 58 0.45 786 75.5 3.1 82 0.45 787 2.9 70.6 3.1 106 0.45 789 5.4 72.1 3.2 0.45 789 2 3.2 154 0.45 788 6.2 66.2 3.3 178 0.45 789 69.1 3.3 202 0.45 787 2 63.2 4.1 226 0.45 788 2.5 67.7 3.7 250 0.45 787 2.6 60.3 4.0 274 0.45 787 3.7 58.8 4.0 298 0.45 788 2 57.4 4.0 322 0.45 785 2 58.8 3.9

1 Conversion 2 Desulfurization 3 Ramsbottom Carbon 4 1,000 ppm of difluoroacetic acid was added to feed TABLE 111 Conv', Test Cat- Feed Time, Temp., Desulf', Carbon No. alyst No. hours lhsv "F. Wt.% Wt.% Wt.% 3 C 1 35 0.45 787 19.0 91.2 2.6 56 0.45 785 9.0 85.3 3.4 80 0.45 782 5.0 70.6 4.3 104 0.45 785 9.8 64.7 4.4 128 0.45 785 6.0 61 8 4.3 152 0.45 785 4.3 176 0.45 785 4.6 200 0.45 783 4.5 224 0.45 784 63.2 4.6 4 D 2 24 0.56 789 6.5 78.1 3.6 48 0.456 788 7.8 69.6 4.3 72 0.56 788 6.5 56.0 5.8

1 Conversion 2 Desulfurization 3 Ramsbottom Carbon FIGS. 2 and 3 provide comparisons of the performance of the preferred catalyst of the process of the present invention to the performances of other typical hydroprocessing catalysts when employed to convert the above desulfurized Cyrus atmospheric resids under similar test conditions. FIG. 2 compares the performances for desulfurization of a preferred catalyst of the process of the present invention, Catalyst D, and a typical hydroprocessing catalyst, Catalyst A. FIG. 3 correlates for four different catalysts the desulfurization activity of each to the reduction of Ramsbottom Carbon in the product obtained for each. One of these four catalysts, Catalyst D, is an embodiment of the preferred catalyst of the process of the present invention.

The data in FIG. 2 demonstrate that the catalyst of the process of the present invention provides desulfurization which is similar to the desulfurization obtained with the other hydroprocessing catalyst. Moreover, the data in FIG. 3 indicate that thecatalyst employed in the process of the present invention provides a reduction of Ramsbottom Carbon for a given level of desulfurization that is greater than those obtained with the other hydroprocessin'g catalysts. This would suggest that the process of the present invention, while providing comparable desu lfurization, operates with a smaller amount of coke being deposited upon the catalyst for a given rate of hydrocarbon flow than do processes employingthe other catalysts,

What is claimed is: p

1. A process for hydroprocessing a high-boiling petroleum hydrocarbon feedstock, which process comprises contacting said feedstock under hydrocarbon 1 conversion conditions and in the presence of hydrogen with a catalyst comprising a hydrogenation component and a porous refractory inorganic oxide having an average pore diameter of about 100 Anstroms to about 300 Angstroms and a surface area that is in excess of 200 square meters per gram, said hydrogenation component comprising a member selected from the group consisting of (l) uranium and a second hydrogenation metal, (2) their oxides, (3) their sulfides, and (4) mixtures thereof.

2. The process .of claim 1 wherein said second hydrogenationmetal of said catalyst is molybdenum.

3. The process of claim 1 wherein said hydrocarbon conversion conditions comprise an average catalyst temperature of about 600F. to about 1,200F., a hydrogen pressure of about 800 psig to about 3,500 psig, a liquid hourly space velocity of about 0.25: to about 5.0 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 3,000 standard cubic feet per barrel of hydrocarbon to about 40,000 standard cubic feetper barrel of hydrocarbon.

4. The process of claim 1 wherein said uranium of said catalyst is present in an amount of about 1 weight percent to about 10 weight percent, calculated as U0 and based on the weight of the catalyst.

5. The process of claim 2 wherein said molybdenum of said catalyst is present in an amount of about 5 weight percent to about 15 weight percent, calculated as M00 and based on the weight of the catalyst, and said uranium of said catalyst is present in an amount of about 1 weight percent to about 10 weight percent, calculated asZUO and based on the wei ht of th tal t.

6. The proc ess of claim 2 whereiil said higit boi ling petroleum hydrocarbon feedstock is composed mainly of hydrocarbons boiling above 650F.

7. The process of claim 2 wherein said hydrocarbon conversion conditions comprise an average catalyst temperature of about 600F. to about 1,200F., a hydrogen pressure of about 800 psig to about 3,500 psig, a liquid hourly space velocity of about 0.25 to about 5 .0 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 3,000 standard cubic feet per barrel of hydrocarbon to about 40,000 standard cubic feet per barrel of hydrocarbon.

8. The process of claim 4 wherein said hydrocarbon conversion conditions comprise an average catalyst temperature of about 600F. to about 1,200F., a hydrogen pressure of about 800 psig to about 3,500 psig, a liquid hourly space velocity of about 025m about 5 .0 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 3,000 standard cubic feet per barrel of hydrocarbon to about 40,000 standard cubic feet per barrel of hydrocarbon.

9. The process of claim 5 wherein said hydrocarbon conversion conditions comprise an average catalyst temperature of about 600F. to about 1,200F., a

hydrogen pressure of about 800 psig to about 3,500

psig, a liquid hourly space velocity of about 0.25 to about 5 .0 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 3,000 standard cubic feet per barrel of hydrocarbon to about 40,000 standard cubic feet per barrel of hydrocarbon. 10. The process of claim 5 wherein said hydrocarbon conversion" conditions comprise an average catalyst temperature. of about 725F. to about 1,050F., a hydrogen pressure of about 1,200 psig to about 2,500 psig, a liquid hourly space velocity of about 0.3 to about 1.0 volume of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 5,000 standard cubic feet per barrel of hydrocarbon to about 30,000 standard cubic feet per barrel of hydrocarbon.

11. The process of claim 5 wherein said high-boiling I petroleum hydrocarbon feedstock is composed mainly of hydrocarbons boiling above 650F. 12. The process of claim 11 wherein'said hydrocarbon conversion conditions comprise an average catalyst temperature of about 600F. to about 1,200F., a hydrogen pressure of about 800 psig to about 3,500 psig, a liquid hourly space velocity of about 0.25 to about 5.0 volumes of hydrocarbons per hour per volume of catalyst, and a hydrogen addition rate of about 3,000 standard cubic feet per barrel of hydrocarbon to about 40,000 standard cubic feet per barrel of hydrocarbon. I

13. The process of claim. 11 wherein saidhydrocarbon conversion conditions comprise an average catalyst temperature of about 725F. to about 1,050F., a hydrogen pressure of'about 1,200 psig to about 2,500 psig, a liquid hourly space velocity of about 0.3 to about 1.0 volume of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 5,000 standard cubic feet per barrel of hydrocarbon to about 30,000 standard cubic feet per barrel of hydrocarbon.

W105) UPUTED S'lATES PA'IEIIT OFFICE i v QERTJLEiCAiL-S 03? CTZC-N Patent NO. 3,71 32 Dated v Jnflary '3 1973- inventoflsy Ralph J. Bertolacini and Herschel o. Redford It is certified that error appears in the above-identified pat-221': and that said Letters Patent are hereby corrected as shown belch-r:

Column 1, line 20 wa should be -ma'.ny--.

Column 4, line "operation" should be --opera.ti ng-- "or" should be --or-'.

Column 7, line 20 Claim 1, line 7 I "Anstroms" should be --Angstroms--;

\ttest;

EDWARD M.PLETCHER,JR.- 1 R'ene' Tegtmeyer \t'testing Officer Acting Commissioner of Patents

Claims

1. A process for hydroprocessing a high-boiling petroleum hydrocarbon feedstock, which process comprises contacting said feedstock under hydrocarbon conversion conditions and in the presence of hydrogen with a catalyst comprising a hydrogenation component and a porous refractory inorganic oxide having an average pore diameter of about 100 Anstroms to about 300 Angstroms and a surface area that is in excess of 200 square meters per gram, said hydrogenation component comprisiNg a member selected from the group consisting of (1) uranium and a second hydrogenation metal, (2) their oxides, (3) their sulfides, and (4) mixtures thereof.

2. The process of claim 1 wherein said second hydrogenation metal of said catalyst is molybdenum.

3. The process of claim 1 wherein said hydrocarbon conversion conditions comprise an average catalyst temperature of about 600*F. to about 1,200*F., a hydrogen pressure of about 800 psig to about 3,500 psig, a liquid hourly space velocity of about 0.25 to about 5.0 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 3,000 standard cubic feet per barrel of hydrocarbon to about 40,000 standard cubic feet per barrel of hydrocarbon.

4. The process of claim 1 wherein said uranium of said catalyst is present in an amount of about 1 weight percent to about 10 weight percent, calculated as UO2 and based on the weight of the catalyst.

5. The process of claim 2 wherein said molybdenum of said catalyst is present in an amount of about 5 weight percent to about 15 weight percent, calculated as MoO3 and based on the weight of the catalyst, and said uranium of said catalyst is present in an amount of about 1 weight percent to about 10 weight percent, calculated as UO2 and based on the weight of the catalyst.

6. The process of claim 2 wherein said high-boiling petroleum hydrocarbon feedstock is composed mainly of hydrocarbons boiling above 650*F.

7. The process of claim 2 wherein said hydrocarbon conversion conditions comprise an average catalyst temperature of about 600*F. to about 1,200*F., a hydrogen pressure of about 800 psig to about 3,500 psig, a liquid hourly space velocity of about 0.25 to about 5.0 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 3,000 standard cubic feet per barrel of hydrocarbon to about 40,000 standard cubic feet per barrel of hydrocarbon.

8. The process of claim 4 wherein said hydrocarbon conversion conditions comprise an average catalyst temperature of about 600*F. to about 1,200*F., a hydrogen pressure of about 800 psig to about 3,500 psig, a liquid hourly space velocity of about 0.25 to about 5.0 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 3,000 standard cubic feet per barrel of hydrocarbon to about 40,000 standard cubic feet per barrel of hydrocarbon.

9. The process of claim 5 wherein said hydrocarbon conversion conditions comprise an average catalyst temperature of about 600*F. to about 1,200*F., a hydrogen pressure of about 800 psig to about 3,500 psig, a liquid hourly space velocity of about 0.25 to about 5.0 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 3,000 standard cubic feet per barrel of hydrocarbon to about 40,000 standard cubic feet per barrel of hydrocarbon.

10. The process of claim 5 wherein said hydrocarbon conversion conditions comprise an average catalyst temperature of about 725*F. to about 1,050*F., a hydrogen pressure of about 1,200 psig to about 2,500 psig, a liquid hourly space velocity of about 0.3 to about 1.0 volume of hydrocarbon per hour per volume of catalyst, and a hydrogen addition rate of about 5,000 standard cubic feet per barrel of hydrocarbon to about 30,000 standard cubic feet per barrel of hydrocarbon.

11. The process of claim 5 wherein said high-boiling petroleum hydrocarbon feedstock is composed mainly of hydrocarbons boiling above 650*F.

12. The process of claim 11 wherein said hydrocarbon conversion conditions comprise an average catalyst temperature of about 600*F. to about 1,200*F., a hydrogen pressure of about 800 psig to about 3,500 psig, a liquid hourly space velocity of about 0.25 to about 5.0 volumes of hydrocarbons per hour per volume of catalyst, and a hydrogen addition rate of about 3,000 standard cubic feet per barrel of hydrocarbon to about 40,000 standard cubic feet per barrel of hydrocarbon.