CA1133457A - Hydrodemetallization catalyst and process employing same - Google Patents

Abstract

ABSTRACT
A catalyst and hydrodemetallization process employing the catalyst are provided. The catalyst com-prises a small amount of a single active original hydrogenation metal selected from Group VIB or Group VIII
deposed on a large-pore, high-surface area support com-prising catalytically active alumina and one or more oxides of phosphorus, said phosphorus being present in an amount within the range of about 7 wt.% to about 11 wt.%, calculated as P2O5 and based upon the weight of said support, and said catalyst having a surface area that is greater than 120 m2/gm, a pore volume that is greater than 0.7 cc/gm, and an average pore diameter that is greater than 12.5 nm (125 .ANG.).

Description

~1~3~

Background of the Invention It is widely known that various organometallic com-pounds and asphaltenes are present in petroleum crude oils and other heavy hydrocarbon streams, such as petro-leum hydrocarbon residua, hydrocarbon streams derivedfrom tar sands, and hydrocarbon streams derived from coals. The most common metals found in such hydrocarbon streams are nickel, vanadium, and iron. Such metals are very harmful to various petroleum refining operations, such as hydrocracking, hydrodesulfurization, and cata-lytic cracking. The metals and asphaltenes cause in-terstitial plugging of the catalyst bed and reduced catalyst life. The various metal deposits on a catalyst tend to poison or deactivate the catalyst. Moreover, the asphaltenes tend to reduce the susceptibility of the hydrocarbons to desulfurization. If a catalyst, such as a desulfurization catalyst or a fluidized cracking cata-lyst, is exposed to a hydrocarbon fraction that contains metals and asphaltenes, the catalyst will become deacti-20 vated rapidly and will be subject to premature removalfrom the particular reactor and replacement by new cata-lyst.
There have been disclosed hydrogenation, hydrode-sulfurization, hydrodenitrogenation, and/or hydrode-metallization catalysts containing at least one metalfrom Group VI of the Periodic Table of Elements and at least one metal from Group VIII of the Periodic Table of Elements on a solid porous refractory inorganic oxide material. Christman, et al., United States Patent 3,814,683; Christman, et al., United States Patent 3,876,680; Jacobson, et al., United States Patent 3,114,701; and Conway, United States Patent 3,960,712.
In some cases, the catalysts may be large-pore, high-surface area catalysts. Christman, et al., United States Patent 3,730,879; Roselius, United States Patent 3,684,688; Bertolacini, et al., United States Patent 3,393,148; Wilson, United States Patent 3,898,155; and Christensen, et al., United States Patent 3,902,991.
Catalysts may have one or more metals from Group VI and 11;~34~7 Group VIII of the Periodic Table of Elements on a support, such as alum-ina. Kehl, et al., United States Patent 3,297,588; Rosinski, et al., United States Patent 3,712,861; Oleck, et al., United States Patent 3,891,541;
S and Oleck, et al., United States Patent 3,931,052.
Moreover, catalysts can contain one or more metals from Group VI and Group VIII on a support, such as alumina, and can have large pores and a high surface area.
Rosinski, et al., United States Patent 3,876,523;
10 Hamner, et al., United States Patent 3,928,176; Hamner, United States Patent 3,977,961; Arey, et al., United States Patent 3,985,684; Long, et al., United States Patent 3,989,645; Arey, et al., United States Patent 3,993,598; Long, et al., United States Patent 3,993,601;
Mattox, United States Patent 3,993,599; White, United States Patent 3,577,353; and Rosinski, et al., United States Patent 4,082,695.
In United States Patents 3,977,961; 3,985,684;
3,989,645; 3,993,598; 3,993,599; and 3,993,601, the patentees disclose two different catalyst compositions, each of which has a pore size distribution that is different than that of the other catalyst disclosed.
Either catalyst comprises a hydrogenation component comprising a Group VIB or Group VIII metal, or both, on a suitable porous refractory inorganic oxide support, preferably alumina. The inorganic oxide support suitably comprises alumina, silica, zirconia, magnesia, boria, phosphate, titania, ceria, thoria, and the like.
A support comprising a combination of alumina and a phosphate or a phosphorus oxide is not disclosed.
Either catalyst can contain from about 5 to about 50 wt.% Group VI metal and about l to about 12 wt.%, pre-ferably, about 4 to about 8 wt.% Group VIII metal.
On the other hand, Hamner, et al., in United States Patent 3,928,176, disclose the hydroconversion of heavy hydrocarbon streams in a two-catalyst process. Each of the two catalysts comprises a hyd~ogenation component of a Group VIB metal and/or a Group VIII metal on a support, such as alumina, silica, zirconia, magnesia, boria, ~. . . ~ .

.~ 11334 titania, ceria, and thoria. The preferred support for the first catalyst is alumina and is a large-pore sup-port. The same support materials can be employed in the second catalyst; however, they are in admixture with aluminum phosphate. The second catalyst is a small-pore catalyst and always includes an aluminum phosphate com-ponent, preferably in concentrations ranging from about 30% to about 100%. Hamner, et al., teach that the pre-ferred small-pore aluminum phosphate catalyst includes a o combination of properties comprising at least about 90%, and preferably at least about 99%, of its total pore volume of absolute diameter within the range of about 1.5 nm (15 Angstrom units IA] ) to about 10.0 nm (100 A), and less than about 5%, and preferably 2%, of its total pore volume of absolute diameter within the range of about 8.0 nm (80 A) to about 15.0 nm (150 A). The pore volume of this aluminum phosphate catalyst ranges from ; about 0.25 to about 0.75 cc/gm, and preferably from about 0.4 to about 0.8 cc/gm. The Hamner, et al. J
patent does not teach a catalyst having an average pore diameter that is greater than 12.5 nm (125 A) and con-taining a high-surface area support comprising cata-lytically active alumina and one or more oxides of phos-phorus, which is present in an amount that is greater than 6 wt.%, calculated as P2O5. Furthermore, it teaches a process which employs two catalysts, the second catalyst of which contains the aluminum phosphate.
In-a co-pending application SN 305,761 filed June 19, 1978 ; 30 (United States Serial No.`811,8351 Hopkins and Hensley disclose a catalyst consisting essentially of a small amount of a single hydrogenation metal deposed on a large-pore, high-surface area alumina, which hydro-genation metal is a Group VIB metal or a Group VIII
metal and is present in an amount within the range of about 0.5 wt.% to about 3 wt.%, based upon the total catalyst weight and calculated as the oxide, and a demetallization process employing that catalyst.

, : -11334~7 Anderson, et al,, in United States Patent 2,890,162, teach that suitable additives may be used to promote pore size distribution growth and/or for acting as active catalytic components of the finished contact agents. This patent discloses that various metals, mixtures of metals, metal compounds or mixtures of metal compounds, or of one or more metals and one or more metal compounds are suitable as such additives. They disclose that the materials may or may not be in chemical combination with the porous solid on the surface thereof. They list phosphates as one of the suitable metallic agents for such purposes. They provide that such promoters are present in an amount of about 0.1 wt.% to about 10 wt.%, preferably 0.5 wt.% to about 5 wt.%, although amounts greater than that may be employed if desired. They do not disclose a specific catalytic composition that contains more than 6 wt.%
phosphorus, calculated as P2O5. They teach that the catalysts of their invention are quite suitable for hydrocracking residua and other asphalt-containing materials to lower boiling distillates and oils. They do not suggest that such a catalyst would be suitable for the hydrodemetallization of heavy hydrocarbon streams.
Eberly, in United States Patent 4,003,828, teaches that increased catalytic activity for demetallization of metal-contaminated hydrocarbon feedstocks is realized for catalysts containing phosphorus oxides. Eberly dis-closes that the phosphorus oxide is present in an amount within the range of 1 to 6 wt.%, preferably 1.1 to 5.5 wt.%, expressed as P2O5 and based on the weight of alumina and phosphorus oxide (the support). Eberly does not consider a catalyst containing a support of alumina and one or more phosphorus oxides, wherein the phos-phorus is present in an amount that is greater than 6 wt.%, calculated as P2O5 and based upon the weight of the support.
Pine, in United States Patent 3,904,550, discloses the preparation of alumina-aluminum phosphate catalyst ~3 ~7 support materials by reacting an aluminum alkoxide with an aqueous solution containing phosphate ions and their use in hydrocarbon conversion processes, such as cata-lytic cracking, hydrocracking, hydrofining, and reform-ing. He teaches the combination of his alumina-aluminum phosphate support with 0 to 50 wt.%, usually 20 to 30 wt.%, of any of the Group VIB and Group VIII metals for use in the desulfurization and denitrogenation of light and heavy petroleum fractions. His alumina-aluminum phosphate support contains from 35 to 85 wt.% aluminum phosphate. He does not consider a catalyst for hydro-demetallization and does not restrict his catalyst to a small amount of hydrogenation metal.
Kehl, in United States Patent 4,080,311, discloses thermally stable composite precipitates containing aluminum phosphate and alumina and having a surface area of about 100 m2/gm to about 200 m2/gm and an average pore radius of 7.5 nm (75 A) to 15.0 nm ~150 A). He teaches that such thermally stable composite precipi-tates contain from 10 to 60 mole % alumina and from 40to 90 mole % aluminum phosphate. He indicates that the term "composite" is used to denote the new compositions which are not physical admixtures. He discloses that the alumina-aluminum phosphate composite precipitates are suitable for use in catalytic cracking or for use as catalyst supports in reactions such as hydrogenation wherein a hydrogenation metal or metals from Group VI
and/or Group VIII are deposited on the surface of the alumina-aluminum phosphate. He does not teach a cata-lyst wherein the phosphorus is present in an amount of at least 6 wt.%, calculated as P205, and only a small amount of a hydrogenation component is employed and such catalyst is used to hydrodemetallize a heavy hydrocarbon stream containing metals and asphaltenes.
In United Kingdom Patent Specification 1,514,671, the patentee discloses a process for desulfurizing various petroleum hydrocarbon fractions at low pressure with a catalyst comprising 0.5 to 7 wt.% cobalt and/or ~3;~4~7-- 6 --nickel, expressed as the oxide, 8 to 20 wt.% molybdenum, calculated as MoO3, and 2 to lO wt.% phosphorus, calcu-lated as P205, preferably on a carrier. This patent specification indicates that the phosphorus is not part of the catalyst carrier, does not consider the surface area, pore volume, and average pore diameter of the catalyst, and does not consider the hydrodemetallization of heavy hydrocarbon streams.
In United States Patent 3,232,887, Pessimisis dis-closes stabilized aqueous solutions that are useful in the impregnation of catalyst carriers and the method of making such solutions. He teaches the preparation of catalysts containing Group VI and Group VIII metals and phosphorus, which phosphorus is incorporated into the catalyst through the use of a phosphorus-containing acid stabilizer, and their use in desulfurizing hydrocarbon streams. He does not disclose catalysts that have pore volumes in excess of 0.7 cc/gm and he does not consider the demetallization of heavy hydrocarbons.
There has now been found and developed a catalyst that is suitable for the hydrodemetallization of hydro-carbon streams, which catalyst contains only a small amount of a hydrogenation component deposed on a large-pore, high-surface area support comprising catalytically active alumina and one or more oxides of phosphorus, the phosphorus being present in an amount that is greater than 6 wt.%, calculated as P205 and based upon the weight of the support.
Summary of the Invention Broadly, according to the present invention, there is provided a catalyst for the catalytic hydrodemetal-lization of a metal-containing hydrocarbon stream, which catalyst comprises a small amount of a hydrogenation component comprising at least one active original hydrogenation metal deposed on a large-pore, high-surface area support comprising catalytically active alumina and one or more oxides of phosphorus, said hydrogenation component being present in the elemental form, as oxides, as sulfides, or mixtures thereof, said 11334.j7 phosphorus being present in an amount that is greater than 6 wt.%, calculated as P2O5 and based upon the weight of said support, and said catalyst having a surface area that is greater than 120 m2/gm, a pore volume that is greater than 0.7 cc/gm, and an average pore diameter that is greater than 12.5 nm (125 A). The original hydrogenation metal or metals are selected from the group consisting of metals of Group VIB of the Periodic Table of Elements and metals of Group VIII of the Periodic Table of Elements.
There is also provided a process for the hydrode-metallization of a hydrocarbon feedstock containing asphaltenes and a substantial amount of metals, which process comprises contacting said feedstock in a reac-tion zone under suitable operating conditions and in thepresence of hydrogen with the above catalyst. Suitable operating conditions comprise a temperature of about 371C (700F) to about 482C (900F), a hydrogen partial pressure of about 3.45 MPa (500 psia) to about 20.7 MPa (3,000 psia), a total pressure of about 3.55 MPa (500 ps~g) to about 41.5 MPa (6,000 psig), a hydro-gen flow rate of about 178 m3/m3 (1,000 standard cubic feet of hydrogen per barrel of hydrocarbon [SCFB~) to about 1,780 m /m (10,000 SCFB), and a liquid hourly space velocity (LHSV) of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst.
Brief Description of the Accompanying Drawings Two figures accompany this document.
Figure l presents a simplified flow diagram of a preferred embodiment of the process of the present in-vention.
The accompanying Figure 2 presents the amount of demetallization of a Jobo II residuum provided by embodiments of the catalyst of the present invention and compares such demetallization to that provided by a prior art demetallization catalyst.

Detailed Description of the Invention The present invention includes a novel catalyst for the hydrodemetallization of hydrocarbon feedstocks con-taining asphaltenes and a substantial amount of metals and to a process for the removal of metals, which process employs the catalyst. Such catalyst and process should effectively demetallize various heavy hydrocarbon feedstocks.
Typical feedstocks that are treated satisfactorily by the catalyst and process of the present invention contain a substantial amount of components that boil appreciably above 538C (l,000F). They often contain metals in an amount that is greater than 500 parts per million (ppm) and asphaltenes in an amount that is as great as 25 wt.% asphaltenes. Examples of such feed-stocks are crude oils, topped crude oils, petroleum hydrocarbon residua, both atmospheric and vacuum residua, oils obtained from tar sands, residua derived from tar sand oil, and hydrocarbon streams derived from coal. Such hydrocarbon streams contain organometallic contaminants which create deleterious effects in various refining processes that employ catalysts in the con-version of the particular hydrocarbon stream being treated. The metallic contaminants that are found in such feedstocks include, but are not limited to, iron, vanadium, and nickel.
Iron may be present in the form of soluble organo-metallic compounds, such as are present frequently in various Western United States crude oils and residuum fractions. The presence of such iron porphyrin com-plexes and other iron organometallic complexes causes severe difficulties in the refining and utilization of heavy hydrocarbon fractions, even if the concentration of such complexes is relatively small. It is known that a cracking catalyst deteriorates rapidly and its selec-tivity changes when in the presence of an appreciable quantity of the organometallic iron compounds. An appreciable quantity of such organometallic iron com-pounds in feedstocks that are being hydrotreated or ~1~3457 g hydrocracked harmfully affects such processes. The cata-lyst becomes deactivated and plugging or increasing of the pressure drop in a fixed-bed reactor results from the deposition of iron compounds in the interstices be-tween catalyst particles.
Nickel-containing compounds and vanadium-containing compounds are present in practically all crude oils that are associated with the high Conradson carbon asphaltic and/or asphaltenic portion of the crude. Of course, such metals are concentrated in the residual bottoms, when a crude is topped to remove those fractions that boil below about 232C (450F) to 316C (600F). If such residuum is treated by additional processes, the presence of such metals adversely affects the catalyst in such processes. It should be pointed out that nickel-containing compounds deleteriously affect cracking catalysts to a greater extent than do iron-containing compounds. If an oil containing such metals is used as a fuel, the metals will cause poor fuel oil performance in industrial furnaces, since they corrode the metal surfaces of the furnaces.
While metallic contaminants, such as vanadium, nickel, and iron, can be present in various hydrocarbon streams in rather small amounts, they are often found in concentrations in excess of 40 to 50 ppm by weight. Of course, other metals may also be present in a particular hydrocarbon stream. Such metals may exist as the oxides or sulfides of the particular metal, or they may be present as a soluble salt of the particular metal, or they may be present as high molecular weight organo-metallic compounds, including metal naphthenates and metal porphyrins, and derivatives thereof.
Broadly, according to the present invention, there is provided a catalyst for the catalytic hydrodemetal-lization of a metal-containing hydrocarbon stream, which catalyst comprises a small amount of a hydrogenation component comprising at least one active original hydro-genation metal deposed on a large-pore, high-surface area support comprising catalytically active alumina and 3~L;7 one or more oxides of phosphorus, said hydrogenation com-ponent being present in the elemental form, as oxides, as sulfides, or mixtures thereof, said phosphorus being present in an amount that is greater than 6 wt.%, cal-culated as P2O5 and based upon the weight of saidsupport, and said catalyst having a surface area that is greater than 120 m2/gm, a pore volume that is greater than 0.7 cc/gm, and an average pore diameter that is greater than 12.5 nm (125 A). The term "at least one 0 active original hydrogenation metal" is used herein to refer to only the hydrogenation metal or metals that are incorporated into the catalyst during its preparation and does not include any metal that is deposited upon the catalyst during the use of the catalyst in any process.
The catalyst of the present invention comprises a small amount of a hydrogenation component and a large-pore, high-surface area support. The hydrogenation com-ponent of this novel catalyst comprises at least one active original hydrogenation metal, which metal can be present as the element, as oxides thereof, as sulfides thereof, or mixtures thereof. Preferably, the hydro-genation component consists essentially of only a single original metal. The metal is typically selected from either Group VIB of the Periodic Table of Elements or Group VIII of the Periodic Table of Elements. The Periodic Table of Elements referred to herein is found on page 628 of WEBSTER'S SEVENTH NEW COLLEGIATE
DICTIONARY, G. & C. Merriam Company, Springfield, Massachusetts, U.S.A. (1965). A preferred metal from Group VIB is molybdenum, while a preferred metal from Group VIII is nickel or iron.
Therefore, according to the present invention, there is provided a catalyst for the catalytic hydro-demetallization of a metal-containing hydrocarbon stream, which catalyst comprises a small amount of a hydrogenation component comprising a metal of Group VIB
of the Periodic Table of Elements, a metal of Group VIII
- of the Periodic Table of Elements, or both deposed on a '- 113~4i-7 large-pore, high-surface area support comprising cata-lytically active alumina and one or more oxides of phosphorus, said hydrogenation component being present in the elemental form, as oxides, as sulfides, or mixtures thereof, said phosphorus being present in an amount that is greater than 6 wt.%, calculated as P2O5 and based upon the weight of said support, and said catalyst having a surface area that is greater than 120 m /gm, a pore volume that is greater than 0.7 cc/gm, and an average pore diameter that is greater than 12.5 nm (125 A).
The hydrogenation component will be present in the catalyst in an amount within the range of about 0.5 wt.%
to about 3 wt.%, based upon the total catalyst weight and calculated as the oxide of the respective metal.
Preferably, the hydrogenation component should be present in an amount of about 1 wt.% to about 2 wt.%, based upon the total catalyst weight and calculated as the oxide of that particular metal. If more than one metal makes up the hydrogenation component, the total amount of hydrogenation metals falls within the ranges listed above in this paragraph.
The support of the catalyst of the present inven-tion is a large-pore, high-surface area material which comprises a catalytically active alumina and one or more oxides of phosphorus. The phosphorus is present in an amount that is greater than 6 wt.%, calculated as P2O5 and based upon the weight of the support. Suitably, the phosphorus is present in an amount within the range of about 7 wt.% to about 11 wt.%, calculated as P205 and based upon the weight of said support. The support has a surface area that is greater than 120 m2/gm, a pore volume that is greater than 0.7 cc/gm, and an average pore diameter that is greater than 12.5 nm (125 A).
Such support is characterized by a surface area ranging from about 120 m2/gm to about 400 m2/gm, a pore volume within the range of about 0.7 cc/gm to about 1.5 cc/gm, and an average pore diameter of about 12.5 nm (125 A) to about 35.0 nm (350 A).

11~34~7 It is not understood at this time how the phos-phorus exists in the catalytic support material or the finished catalytic composite. It may be present as aluminum phosphate, or as a combination of aluminum phosphate in admixture with alumina, or it may be present as one or more oxides of phosphorus, or as an oxide and/or other compound of phosphorus. In any event, the term "one or more oxides of phosphorus" is used in this specification and the associated claims to designate any one of the above situations.
The catalyst of the present invention may be pre-pared by the typical commercially available method of impregnating an appropriate support with a solution containing a heat-decomposable compound of the metal to be placed on the catalyst, drying, and calcining the impregnated material. The drying may be conducted in air at a temperature within the range of ambient tem-perature to about 204C (400F) for a period of 1 to 70 hours. Typically, the calcination can be carried out at a temperature of about 427C (800F) to about 649C (1,200F) for a period of from 0.5 to 8 hours.
Water is a typical solvent for the impregnation solu-tion. The support may have been calcined prior to the impregnation.
Only a small amount of the hydrogenation component (metal or metals) is incorporated into the catalyst.
The impregnation of only a small amount of the hydro-genation metal or metals does not appreciably affect the physical properties of the support. Hence, the catalyst of the present invention has a surface area of 120 m2/gm to about 400 m /gm, a pore volume of 0.7 cc/gm to about 1.5 cc/gm, and an average pore diameter of 12.5 nm (125 A) to about 35.0 nm (350 A).
The catalyst may be employed in the form of a fixed-bed or an ebullated bed of particles. In the case of afixed-bed, the particulate material should have a parti-cle size of at least 0.8 mm (l/32 inch).
An advantage of the catalyst of the present inven-- tion is its low cost and cheap method of preparation.

11~34~7 The large-pore, high-surface area support is commer-cially available. Such support is relatively inexpen-sive and can be impregnated with a small amount of hydrogenation metal or metals without appreciable change in the surface properties of the support material. The resulting catalyst possesses high capacity for metals removal from the feedstock being treated.
According to the invention, there is provided a process for the hydrodemetallization of a hydrocarbon o feedstock containing asphaltenes and a substantial amount of metals, which process comprises contacting said feedstock in a reaction zone under suitable operating conditions and in the presence of hydrogen with the catalyst described hereinabove. The term "substantial amount of metals" as used herein refers to any amount that is 3 ppm or greater and could be as large as 1,000 ppm or more.
The catalyst and process of the present invention are particularly useful for the hydrodemetallization of a heavy hydrocarbon stream. They can be employed suit-ably to hydrodemetallize crude oils, topped crude oils, petroleum hydrocarbon residua, both atmospheric resids and vacuum resids, oils obtained from tar sands, residua derived from tar sand oil, and hydrocarbon streams de-rived from coal.
Suitable operating conditions for this hydrode-metallization process comprise an average catalyst bed temperature of about 371C (700F) to about 482C (900F), a total pressure of about 3.55 MPa (500 psig) to ahout 41.5 MPa (6,000 psig), a hydrogen partial pressure of about 3.45 MPa (500 psia) to about 20.7 MPa (3,000 psia), a hydrogen flow rate or hydrogen addition rate of about 178 m3/m3 (1,000 SCFB) to about 1,780 m3/m3 (10,000 SCFB), lgas volumes are measured at 15.6C and 101.3 kPa] and a LHSV of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst. Preferably, the operat-ing conditions comprise an average catalyst bed tempera-ture of about 388C (730F) to about 432C (810F), a total pressure of about 8.4 MPa (1,200 psig) to about 11~34~i7 20.8 MPa (3,000 psig), a hydrogen partial pressure of about 8.3 MPa (1,200 psia) to about 13.8 MPa (2,000 psia), a hydrogen flow rate or hydrogen addition rate of about 712 m3/m3 (4,000 SCFB) to about 1,424 m3/m3 (8,000 SCFB), and a LHSV of about 0.4 to about 2.0 volumes of hydrocarbon per hour per volume of catalyst.
A preferred embodiment of the process of the present invention is presented in the accompanying Figure 1, which is a simplified flow diagram and does not show o various pieces of auxiliary equipment, such as pumps, compressors, heat exchangers, and valves. Since one having ordinary skill in the art would recognize easily the need for and location of such auxiliary equipment, its omission is appropriate and facilitates the simpli-fication of the figure. This process scheme is pre-sented for the purpose of illustration only and is not intended to limit the scope of the present invention.
Referring to Figure 1, a Jobo II 204C+ (400F+) residual oil, containing about 3.7 wt.% sulfur, about 0.6 wt.% nitrogen, and about 543 ppm of nickel plus vanadium, is withdrawn from source 10 through line 11 into pump 12, whereby it is pumped through line 13. A
hydrogen-containing recycle gas stream, discussed hereinafter, is passed from line 14 into line 13 to be mixed with the hydrocarbon feed stream to form a mixed hydrogen-hydrocarbon stream. The mixed hydrogen-hydro-carbon stream is then passed from line 13 into furnace 15, where it is heated to a temperature within the range of about 399C (750F) to about 421C (790F) The heated stream is then passed through line 16 into reaction zone 17.
Reaction zone 17 comprises one or more reactors, each of which contains one or more fixed beds of cata-lyst. The catalyst comprises a hydrogenation component consisting essentially of about 1 wt.% molybdenum, cal-culated as MoO3 and based upon the total catalyst weight, deposed on a support comprising alumina and oxides of phosphorus, the amount of phosphorus being about 7.8 wt.% phosphorus, calculated as P2O5. The catalyst ' 113~4~-J,7 possessed a surface area of 227 m2/gm, a pore volume of 1.03 cc/gm, and an average pore diameter of 18.1 nm (l81 A).
The operating conditions employed in reaction zone 17 comprise a total pressure of about 11.8 MPa (1,700 psig) to about 13.2 MPa (1,900 psig), a hydrogen partial pressure of about 11.0 MPa (1,600 psia) to about 12.8 MPa (1,850 psia), an average catalyst bed temperature within the range of about 399C (750F) to about 421C
(790F); an LHSV within the range of about 0.9 volume of hydrocarbon per hour per volume of catalyst to about 1.1 volumes of hydrocarbon per hour per volume of catalyst;
and a hydrogen recycle rate within the range of about 1,120 m3/m3 (6,300 SCFB) to about 1,230 m3/m3 (6,900 SCFB).
The effluent from reaction zone 17 is passed through line 18 into a second reaction zone 19 contain-ing a suitable resid desulfurization catalyst. Such a catalyst is a catalyst comprising about 2.5 wt.% CoO and 10 wt.% MoO3 on a large-pore, high-surface area alumina having a surface area of 350 m /gm and an average pore diameter of 11.2 nm (112 A). Operating conditions employed in reaction zone 19 include an average catalyst bed temperature of 371C (700F) to about 416C (780F);
an LHSV within the range of about 0.4 volume of hydro-carbon per hour per volume of catalyst to about 1.5 volumes of hydrocarbon per hour per volume of catalyst;
a pressure of about 11.7 MPa (1,685 psig) to about 13.2 MPa (1,900 psig); and a hydrogen recycle rate of about 1,120 m3/m3 (6,300 SCFB) to about 1,230 m3/m3 (6,900 SCFB). The effluent from reaction zone 19 is passed through line 20 into high-temperature, high-pressure, gas-liquid separator 21, which is operated at reactor pressure and temperature. In separator 21, the hydro-gen-containing gas is separated from the rest of the effluent. The hydrogen-containing gas is passed from separator 21 through line 22. It is cooled and sent into light-hydrocarbon separator 23, wherein the con-densed light hydrocarbons are separated from the 11339~7 hydrogen-containing gas and withdrawn via line 24. The hydrogen-containing gas is removed by way of line 25 and passed into scrubber 26, wherein the hydrogen sulfide is removed or scrubbed from the gas. The hydrogen sulfide is removed from the system by way of line 27. The scrubbed hydrogen-containing gas is then passed through line 14, where it can be joined by make-up hydrogen, if necessary, via line 28. The hydrogen-containing gas stream is then added to the hydrocarbon feed stream in o line 13, as described hereinabove.
The liquid portion of the effluent is passed from the high-temperature, high-pressure, gas-liquid sepa-rator 21 by way of line 29 to high-temperature flash drum 30. In flash drum 30, the pressure is reduced to atmospheric pressure and the temperature of the material is within the range of about 371C (700F) to about 427C (800F). In flash drum 30, the light hydrocarbons containing not only the naphtha but those distillates boiling up to a temperature of about 288C (550F) to 3]6C (600F), such as fuel oil, is flashed from the rest of the product and is removed from the system by way of line 31. Such light hydrocarbons, can be sepa-rated into their various components and sent to storage or to other processing units.
The heavier material that is separated from the light hydrocarbons, that is, material that boils at a temperature above about 316C (600F), present in an amount of about 60 wt.% to about 90 wt.% based upon the hydrocarbon feed, is removed from flash drum 30 hy way of line 32 for use as feeds to other processes. Such Iiquid material contains about 0.2 wt.% to about 1.0 wt.% sulfur, about 2.0 wt.% to about 4.0 wt.% asphal-tenes, and about 20 ppm to about 60 ppm nickel plus vanadium .
This liquid effluent is passed via line 33 to furnace 34, or other suitable heating means, to be heated to a temperature as high as 427C (800F).
The heated stream from furnace 34 is passed by way of line 35 into vacuum tower 36, where vacuum gas oil .

11~34~7 (VGO) is separated from a low-sulfur residual fuel. The VGO is passed from vacuum tower 36 by way of line 37 to storage or to a conventional catalytic cracking unit (not shown). The low-sulfur residual fuel is passed from vacuum tower 36 by way of line 38 to storage or to other processing units where it can be used as a source of energy.
Alternatively, the material boiling above 316C
(600F) that is removed from flash drum 30 through line 0 32 can be sent by way of line 39 to a resid catalytic cracking unit (not shown~.
Alternatively, the effluent from reaction zone 17 can be sent through line 18a directly to high-tempera-ture, high-pressure separator 21, and the demetallized liquid effluent from high-temperature, high-pressure separator 21 can be sent to storage or to other process-ing units.
The following examples are presented to facilitate a better understanding of the present invention. They are presented for the purpose of illustration only and are not intended to limit the scope of the present in-vention.
Example I
An embodiment of the hydrodemetallization catalyst of ~he present invention was prepared. In this elllbodi-ment, the support material was a large-pore, high-sur-face area material made up of catalytically active alumina and oxides of phosphorus. This catalyst is identified hereinafter as Catalyst A. The support contained a substantial amount of phosphorus, speci-fically, 7.8 wt.%, calculated as P2O5, and was obtained from the Nalco Chemical Company. It had a surface area oL 288 m2/gm, an average pore diameter of 15.9 nm (159 A), and a pore volume of 1.15 cc/gm. Its pore size distribution, as measured from nitrogen desorption isotherms, was as shown in Table I.

113~4~i7 TABLE I
PORE SIZE DISTRIBUTION OF SUPPORT
OF CATALYST A
Pore Diameter Range % of Total Pore Volume ___ O
5 _ nm A
4.0 - 5.0 40 - 50 1.9 5.0 - 10.0 50 - 100 17.8 10.0 - 15.0 100 - 150 18.9 l5.0 - 20.0 150 - 200 16.9 10 20.0 - 30.0200 - 300 13.0 30.0+ 300+ 31.3 The catalyst was prepared by first grinding the support material to a 14/20-mesh material, that is, a material that would pass through a 14-mesh screen (U.S.
Sieve Series), but would be retained on a 20-mesh xcreen, and then impregnating the ground support particles with a solution of ammonium molybdate. This solution had been prepared by dissolving 120 gm of ammonium molybdate in 250 ml concentrated ammonia and diluting with distilled water to make about 500 ml of stock solution. A l-ml portion of the stock solution contained the equivalent of 0.20 gm of MoO3. A 1.6-ml portion of the stock solution was diluted to 55 ml and added to 32.8 gm (99 cc) of the support material. The chosen amount of solution just wetted all the support material. The impregnated support was then dried in static air at ambient temperature overnight and calcined in static air at a temperature of 538C (1,000F) for a period of 2 hours.
The finished catalyst, hereinafter identified as Catalyst A, was found to have a surface area of 242 m /gm, a pore volume of 1.14 cc/gm, and an average pore diameter of 18.8 nm (188 A). It contained 1.23 wt.%
MoO3, based upon the total catalyst weight.
Example II
Catalyst A was tested in a small-scale pilot plant for its ability to remove metals from a Jobo II 204C+
(400F+) residual oil. The properties of this feedstock are presented hereinafter in Table II.

11334~7 TABLE II
PROPERTIES OF FEEDSTOCK
Gravity, ~API 9.4 % Carbon 84.66 % Hydrogen 10.38 % Sulfur 3.70 % Nitrogen 0.62 % Oxygen 0.64 100 . 00 Metals, ppm Vanadium 461 Nickel 100 Iron 11.1 % Oils 41.8(a) % Resins 50.3 % Asphaltenes 7.9 /O Total 100.0 (a) Normalized.
This small-scale pilot plant had automatic controls for pressure, flow of reactants, and temperature. The reactor was fabricated from a l/2-inch schedule 80 stain-less steel pipe having an inside diameter of 0.55 inch(1.40 cm). It contained a 1/8-inch coaxial thermowell for a traveling thermocouple. Temperature in the reactor was measured by this traveling thermocouple.
The reactor was heated by an electrically-heated steel block. Near isothermal conditions were achieved by 3 electrical heaters separately controlled by Eurotherm*
temperature controllers.
A 60-cc portion of catalyst, ground to pass through a 14-mesh screen (U.S. Sieve Series~, but to be retained 35 on a 20-mesh screen, i.e., a 14/20-mesh material, was charged to the reactor. The catalyst particles were supported in the reactor on 3 7/8-inch (9.8 cm) layer of 8/12-mesh corundum chips, which layer in turn was sup-ported by a 4-inch (10.2 cm) layer of 1/8-inch corundum *Trademark ,, ~3;~4~37 balls. The catalyst bed was 16 3/4 inches (42.5 cm) in length. A layer of about 8 inches (20.3 cm) of 1/8-inch (0.32 cm) corundum balls was placed above the catalyst bed. Once-through hydrogen was employed and the reac-tants were passed up-flow through the catalyst bed. A
hydrocarbon feed rate of about 61 cc/hr was employed.
The catalyst was calcined in still air at a tem-perature of about 538C (1,000F) for 1 hour prior to the test. It did not receive any other pretreatment o prior to its use to convert the hydrocarbon feedstock.
The results obtained from this test, Test No. 1, are summarized in Table III hereinbelow. The test was conducted at a pressure of 12.51 MPa (1,800 psig) and a LHSV of 1.02 volumes of hydrocarbon per hour per volume of catalyst.

11334~-j7 TABLE III
RESULTS FROM TEST NO. 1 AND CATALYST A
Temp.~_ 3 3 Product Analyses Day F C SCFB m /m Ppm V(a) ppm Ni(a) ppm Fe 6 785 4185090 907 47 32 3.0 l0 12 785 4185410 964 67 38 15 22 -- _ 5190 924 91,96 42,42 24 785 4185190 924 103 42 2.2 20 32 784 4186890 1227 125,12945,43 25 42 806 430 -_ __ 120 42 48 807 4314990 889 168 50 1.7 49 (run terminated) (a) V, Ni analysis through day 18 by atomic absorption;
day 20 and later by XRF.

~1334~7 TABLE I I I ( CONTINUED ) Product Analyses Gravity, ~2 % S % C % H API h Oils % Resins 3 2.09 85.36 10.9517.4 40.8 39.1 4 2.14 16.5 6 16.3 8 15.9 10 10 15.9 12 85.55 10.9416.3 41.0 38.7 14 15.3 16 16.1 18 16.1 85.40 10.9015.8 39.1 40.0 22 15.5 24 2.32 15.7 26 85.60 10.9715.5 39.2 39.8 28 15.3 20 3o2.42 15.3 32 2.45,2.33 15.0 34 2.36 85.59 10.94 -- 42.9 38.9 36 2.15 16.5 38 2.22 16.1 25 4o2.23 16.5 42 2.04 85.70 10.9817.0 46.1 33.4 44 2.12 16.7 46 2.13 16.8 48 2.14 85.49 10.9516.7 43.1 27.3 4'~7 TABLE III (CONTINUED) Product Analyses % Removal % Asphaltenes V Ni V+Ni 3 2.4 89 64 84 12 3. S 85 62 81 3.6 80 60 77 22 80,79 58 76,75 24 7~ 58 74 26 3.8 77 58 74 34 3.8 71 54 68 42 3.2 74 58 71 48 4.2 64 S0 61 ~334~7 Example III
A second embodiment of the hydrodemetallization cata-lyst of the present invention was prepared. This catalyst, identified hereinafter as Catalyst B, was prepared by impregnating a portion of the same support material that was employed in the preparation of Catalyst A, described hereinbefore in Example I.
The catalyst was prepared by impregnating the sup-port with an aqueous solution of nickel nitrate, which lo had been prepared by dissolving 202 gm of nickel nitrate in distilled water and diluting with distilled water to make about 500 ml of stock solution. A 3.4-ml portion of the stock solution was then diluted to 52 ml and added to 33.9 gm (99 cc) of the support material. This solu-tion just wet the support material. There was no excesssolution. The impregnated material was dried overnight in static air at ambient temperature and then calcined in static air for 2 hours at a temperature of 538C
(1,000F). The completed catalyst, identified herein-after as Catalyst B, was found to have a surface area of 243 m2/gm, a pore volume of 0.99 cc/gm, and an average pore diameter of 16.2 nm (162 A). It contained 1.01 wt.% nickel, calculated as NiO and based upon the weight of the catalyst.
Example IV
Catalyst B was tested for its ability to remove metals from the Jobo II 204C+ (400F+) residual oil that is described in Example II hereinabove. The test was conducted in the same small-scale pilot plant that was employed in the test of Example II.
A 61-cc portion of Catalyst B was loaded into the reactor in the same manner as was Catalyst A. The cata-lyst was calcined in still air at a temperature of about 538C (1,000F) for 1 hour prior to the test. The test was conducted at a pressure of 12.38 MPa (1,780 psig) to 12.51 MPa (1,800 psig) and a LHSV of 1 volume of hydro-carbon per hour per volume of catalyst. The reactants were passed up through the catalyst bed.

1~334~ ,7 The results of this test, identified hereinafter as Test No. 2, are presented in Table IV hereinbelow.
TABLE IV
RESULTS FROM TEST NO. 2 AND CATALYST B
5Temp~, Gas Rate, Product_Analyses ~y F C SCFB m ~m ppm V ppm Ni ~m Fe

2 784 4184960 884 46 41 1.1 16 783 4174430 789 80 41 0.9 783 4173300 588 119 44 1.0 46 -- -- 4910 875 183 52 1.3 TABLE IV (CONTINUED) Product Analyses Gravity, ~ % S % C % H API % Oils % Resins 2 2.66 15.3 4 2.51 85.62 10.93 15.5 41.8 39.5 6 2.45 15.7 8 2.36 15.4 2.36 15.5 o 12 2.40 14 2.40 15.4 16 2.36 15.5 18 2.38 15.9 2.38 15.7 15 22 2.39 15.7 24 2.38 85.75 10.96 - - 43.2 39.5 26 2.37 --28 2.39 --2.40 --20 32 2.39 34 2.42 - -36 2.42 15.5 38 2.50 15.1 2.47 15.0 25 42 2.51 14.8 44 2.52 14.7 46 2.45 15.1 48 2.48 85.57 10.93 14.7 40.2 40.7 il33~7 TABLE IV (CONTINUED) Product Analyses % Removal ~y /0 Asphaltenes V Ni V+Ni s 4 3.5 89 59 83 o 14 84 59 79 5 24 4.1 79 57 75 48 5.1 57 47 56 . 30 ~334S7 As can be seen from the data obtained from Test No. 1 and Test No. 2, significant amounts of nickel and vanadium were removed from the Jobo II feedstock, the sulfur level was somewhat reduced, and some resins and asphaltenes 5 were eliminated, whether either Catalyst A or Catalyst B
was employed. Each of these catalysts was found to take up an amount of metals that was greater than 100% of the original catalyst weight. This is shown hereinbelow in Table V. These metal-retention data were calculated from o the data obtained from product analyses.
TABLE V
METALS RETENTION BY CATALYSTS A AND B
Test No. 1 2 Catalyst A B
15 Days on Metals, Metals, Stream wt.%(l) wt.%(l) 2 6.5

3 10.0

4 13.4 12.9 8 26.8 25.5 12 39.5 37.9 16 52.0 50.0 64.2 61.7 24 76.1 73.2 25 28 87.3 84.3 32 98.1 95.1 36 108.8 105.5 119.5 115.3 44 130.3 124.6 30 48 129.0(2) 49 142.4(2~

(1) wt.% of original catalyst weight.
(2) end of test.

Example V
Another embodiment of the catalyst of the present invention was prepared. This catalyst, identified herein-after as Catalyst C, was prepared to contain about 1 wt.%

5 molybdenum trioxide. Again, the catalyst support material was a portion of the material that is described herein-above in Example I.
The catalyst was prepared by impregnating the sup-port with an aqueous solution of ammonium molybdate that 10 had been prepared by diluting 2.7 ml of the solution described in Example I above to 80 ml with distilled water. The above solution was added to 54.2 gm of the support material. This solution just wet the support material. The impregnated material was dried in static air at ambient temperature over the weekend (Friday night to Monday morning). It was then calcined in static air for 1 1/2 hours at a temperature of 566C
(1,050F). The completed catalyst, identified herein-after as Catalyst C, was found to have a surface area of 20 227 m /gm, a pore volume of 1.03 cc/gm, and an average pore diameter of 18.1 nm (181 A). It contained 1.39 wt.% molybdenum, calculated as MoO3 and based upon the weight of the catalyst.
Example VI
Catalyst C was tested for its ability to hydrode-metallize the Jobo II 204C+ (400F+) residual oil de-scribed hereinbefore in Example II. The test was conducted in a bench-scale test unit having automatic controls for pressure, flow of reactants, and tempera-30 ture. The reactor was made from 3/8-inch inside diameter stainless-steel, heavy-walled tubing. A
1/8-inch (0.32 cm) outside diameter thermowell extended up through the center of the reactor. The reactor was heated by an electrically-heated steel block. The 35 hydrocarbon feedstock was fed to the unit by means of a Ruska*pump, a positive-displacement pump. The 14/20-mesh catalyst material was supported on 8/10-mesh ~LU~ W particles. A 14.4 cc-portion of catalyst was employed in the test. This amount of catalyst provided *Trad~k a catalyst bed length of about 9 inches (23 cm). A 2-inch (5 cm) layer of 8/10-mesh AL~M particles was placed over the catalyst. The catalyst that was employed was located in the annular space between the thermowell and the internal wall of the 3/8-inch-inside-diameter reactor.
Effluent from the reaction zone was collected in a liquid product receiver, while the gas that was formed was passed through the product receiver to a pressure lo control valve and then through a wet test meter to an appropriate vent. Selected samples were obtained from the product receiver and were analyzed for pertinent information.
Catalyst C was loaded into the reactor immediately following its calcination. It did not receive any addi-tional pretreatment. The test was conducted at a pressure of 12.51 MPa (1,800 psig) and a LHSV of 1 volume of hydrocarbon per hour per volume of catalyst.
The reactants were passed down through the catalyst bed.
20 The results of the test, Test No. 3, are presented in Table VI hereinbelow.
TABLE VI
RESULTS FROM TEST NO. 3 AND CATALYST C
Product Analyses Days on TemP, Gas Rate~
Stream F C SCFB m /m ppm V pPm Ni % S % C

6 -- -- 6770 1206 72 39

7 780 416 6510 1160 2.17 86.13

8 780 416 6560 1169 79 39

9 780 416 6680 1190 Trademark s. - ~
~ '''`' .

~1334~7 TABLE VI (CONTINUED) Product Analyses __ Days on Gravity, Str.-eam_ /O H API /O Oils % Resins S 2 15.9 3 15.7 4 15.7 15.5 6 15.5 7 ~Ø97 15.5 42.9 37.6 8 14.7 9 15.3 1() 16. 3 ]1 15.5 TABLE VI (CONTINUED) Days on Product Analyses % Removal Str.eam% Asphaltenes _ Ni V+Ni 7 3.4 .' 9 ]0 82 60 78 1~.
Example VII
A catalyst having an alumina support was prepared.
This catalyst is hereinafter identified as Catalyst D.
The support material was a commercially available cata-lytical.ly active KSA light alumina obtained from Kaiser Chemicals, a division of the Kaiser Aluminum and Chemicals Corporation.
The catalyst was prepared by impregnating the support with an aqueous solution of ammonium molybdate, which solution had been prepared by diluting with distilled water 11.0 ml of the solution described in 3~ 7 Example I above to 250 ml. The above solution was added to 218.7 gm (500 cc) of the support material. This solu-tion just wet the support material. The impregnated material was calcined in static air at a temperature of 538C (1,000F) for 1 1/2 hours. The completed catalyst had a surface area of 186 m2/gm a pore volume of 0.90 cc/gm, and an average pore diameter of 19.5 nm (195 A). It contained 1.22 wt.% molybdenum, calculated as MoO3 and based upon the weight of the catalyst.
Example VIII
The Catalyst D was tested for its ability to hydro-demetallize the aforesaid Jobo II 204C+ (400F+) residual oil described hereinabove in Example II. The test, iden-tified as Test No. 4, was conducted in the same bench-scale test unit that was employed in Example VI. Apressure of 12.51 MPa (1,800 psig) was employed and the reactants were passed down through the catalyst bed.
The results of Test No. 4 are presented hereinbelow in Table VII.

11334~i7 TABLE VII
RESULTS FROM TEST NO. 4 AND CATALYST D
Product Analyses Days on Temp, LHSV Gas Rate, Stream F C Vo/Vc/Hr SCFB m /m ppm V ppm Ni 2 781 416 1.0 4810 857113,110 54,53 3 - - - - 1.0 4930 878 113 52 4 780 416 1.0 5140 91696,106 46,50 6 780 416 1.0 5050 900109,96 51,46 o 8 -- -- 1.0 4850 864 94 43 780 416 1.0 4680 834 91 41 12 780 416 1.0 4630 825 91 40 ; 14 780 416 1.0 4640 827 87 37 -- -- 1.0 5200 926 -- --16 -- -- 1.0 4700 837 91 37 18 780 416 1.0 4220 752 97 37 780 416 1.0 5040 898 97 36 . .
` . 22 - - -- 1.0 5090 907 102 37 24 -- - - 1.0 4980 887 106 37 26 781 416 1.0 4430 789 108 36 28 -- -- 1.0 4880 869 115 37 " 29 -- -- 1.0 4780 851 121 38 . 31 781 416 1.07 4930 878 124 41 : 32 - - - - 1.07 5000 891 121 38 33 789 421 1.07 5030 896 124 38 34 780 416 1.07 4580 816 147 44 780 416 1.07 4960 884 149 44 36 781 416 1.07 4230 753 154 45 34.-~7 TABLE VII (CONTINUED) Product Analyses Days on Gravity, Stream E~ % S % C % H API
2 1.7 2.23,2.19 85.43 11.00 15.6 3 2.35 15.7 4 2.32,2.35 15.5 6 2.40,2.35 85.56 11.00 16.1 8 2.26 15.1 o 10 2.20 16.3 12 2.16 16.5 14 0.8 2.05 85.63 11.08 16.9 1.1 16.7 16 2.06 16.8 15 18 2.09 16.8 2.03 16.8 22 2.02 16.7 24 2.01 85.79 11.16 17.0 26 1.97 17.0 20 28 1.97 16.9 29 0.9 1.99 85.59 11.18 16.7 31 2.02 17.0 32 1.94 18.2 33 1.89 17.8 25 34 2.17 16.9 2.18 16.7 36 1.6 2.19 85.43 11.07 16.7 11334~7 - 35 ~
TABLE VII (CONTINUED) Product Analyses Days on % % % % Removal Stream Oils Resins Asphaltenes V Ni V+Ni 2 45.4 40.7 3.7 75,76 46,47 70,71 4 79,77 54,50 75,72 6 37.1 42.1 3.5 76,79 49,54 71,75 14 42.9 40.1 3.3 81 63 78 __ _ _ __ 24 40.4 37.7 3.7 77 63 74 29 45.6 38.4 4.0 74 62 72 ; 25 35 68 56 66 36 43.4 38.5 4.6 67 55 65 \

4~7 The performances of Catalyst C and Catalyst D for removal of nickel and vanadium from the Jobo II 204C+
(400F+) residual oil are compared in the accompanying Figure 2. The performances of Catalyst A and B are shown also.
Referring to Figure 2, after 10 days on stream, Catalysts C and D performed on an equivalent basis.
However, prior to that, the Catalyst C, an embodiment of the catalyst of the present invention, provided superior

10 hydrodemetallization.
Example IX
An additional embodiment of the catalyst of the present invention was prepared. This embodiment is identified hereinafter as Catalyst E.
The support material for Catalyst E was first pre-pared. A 222-gram portion of A12(SO4)3.l8H2O was dis-solved in 500 ml of distilled water and 218 gm of Na2OA12O3.3H2O were dissolved in a second 500-ml portion of distilled water. These two solutions were combined.
20 The aluminum sulfate solution was added from a sepa-ratory funnel to the sodium aluminate solution over a period of 10 minutes while the sodium aluminate solution was stirred rapidly with a mechanical stirrer. The pH
of the resulting alumina slurry was adjusted to a value of 7 to 7.5 by means of dilute sulfuric acid. The mixture was then heated on a hot plate to 90C (194F) and held at that temperature with stirring for 30 minutes. Subsequently, the alumina slurry was filtered by means of a suction filter and the resulting cake was 30 slurried with 2 liters of hot distilled water. The resulting slurry was heated to 90C (194F) on a hot plate and kept at that temperature for 30 minutes with continuous stirring. The filtration-and-washing pro-cedure was repeated 2 more times. At the termination of the third washing, the alumina sol was diluted with 400 ml of distilled water to make the slurry contain 10-12%
solids. To the resulting slurry, 23.0 gm of 85% H3PO4 were added. The acid and slurry were thoroughly mixed.
- The mixture was dried under a heat lamp overnight. A

11334~7 portion of the dried material was calcined in static air for 2 hours at a temperature of 538C (1,000F).
The calcined material was subsequently formed as spherical particles having a diameter of about 1/25 of an inch (1.0 mm). It was then dried under a heat lamp overnight and calcined in static air for 6 hours at a temperature of 760C (1,400F).
A 42-gm portion of the support was impregnated with 60 ml of a solution that had been prepared by dissolving 0 .53 gm of ammonium molybdate in distilled water and adjusting the volume to 60 ml with distilled water. The impregnated material was dried under a heat lamp over-night and then calcined in static air for 2 hours at a temperature of 538C (1,000F).
Catalyst E was prepared to contain 1 wt.% molyb-denum trioxide, 9.9 wt.% P2O5, and 89.1 wt.% alumina.
It possessed the pore-size distribution presented in Table VIII hereinbelow. It had a surface area of 235 m2/gm, a pore volume of 0.91 cc/gm, and an average 20 pore diameter of 15.5 nm (155 A).
TABLE VIII
PORE SIZE DISTRIBUTION OF CATALYST E
Pore Diameter Ran~e % of Total Pore Volume nm A
252 - 5 20 - 50 4.2 5 - 10 50 - 100 38.0 10 - 15 100 - 150 22.7 15 - 20 150 - 200 8.4 20 - 30 200 - 300 8.3 0 30+ 300+ 18.4 ~3345~

ExamPle X
Catalyst E was tested for its ability to hydrode-metallize the Jobo II 204C+ (400F+) residual oil de-scribed hereinabove in Example II. The test, identified hereinafter as Test No. 5, was carried out in a bench-scale test unit similar to the one described in Example VI.
A 6.1-gm portion (14.2 cc) of Catalyst E, ground to pass through an 8-mesh screen (U.S. Sieve Series), but lo be retained on a 14-mesh screen, i.e., 8/14-mesh material, was charged to the reactor. The catalyst bed was about 7.5 inches (19.1 cm) in length and was sup-ported on 12 inches (30.5 cm) of 8/12-mesh ALUNDUM
chips. A 2-inch (5.1-cm) layer of 8/12-mesh iALUNDUM
15 particles was placed over the catalyst bed in the reactor.
Test No. 5 was conducted at a total pressure of 12.51 MPa (1,800 psig) and the reactants were passed down through the catalyst bed. The test results are 20 presented hereinafter in Table IX.

~1334.J7 TA~LE IX
RESULTS FROM TEST NO. 5 AND CATALYST E
Days on Temp., LHSV, Gravity, Sulfur, Stream F C Vo/Vc/Hr API %
1 781 416 1 16.3 1.78 2 781 416 1 16.1 2.12 3 781 416 1 15.2 2.40 4 781 416 1 15.3 2.47 778 414 1 15.3 2.47 6 778 414 1 14.9 2.44 7 778 414 1 15.3 2.44 8 778 414 1 14.9 2.44 9 778 414 1 15.1 2.5S
778 414 1 15.1 2.47 15 11 778 414 1 15.2 2.40 12 780 416 1 15.1 2.42 13 780 416 1 14.9 2.46 14 780 416 1 14.9 2.53 ~ 14.9 --20 16 780 416 0.5 __ 1.76 17 780 416 0.5 17.2 1.73 18 780 416 0.5 17.6 1.75 19 780 416 0.5 17.6 1.79 780 416 0.5 17.8 1.82 25 21 780 416 0.5 17.0 1.83 22 780 416 0.5 16.8 1.94 23 780 416 0.5 16.8 l.9S
24 780 416 0.25 19.7 1.49 780 416 0.25 19.9 1.37 30 26 780 416 0.25 19.7 1.38 27 780 416 1 14.3 2.64 28 780 416 1 14.7 2.56 11334~7 TABLE IX ( CONTINUED ) Days on V, Ni, % Removal Stream ppm ppm S V Nl V+Ni 1 36 29 51.9 92.2 71 88.4 2 56 38 42.7 87.5 62 83.2 3 70 42 35.1 84.8 58 80.0 4 72 41 33.2 84.4 59 79.9 73 41 33.2 84.2 59 79.7 6 73 41 34.0 84.2 59 79.7 o 7 75 41 34.0 83.7 59 79.3 8 79 42 34.0 82.9 58 78.4 9 80 42 31.1 82.6 58 78.3 84 43 33.2 81.8 57 77.4

11 85 42 35.1 81.6 58 77.4

12 88 43 34.6 80.9 57 76.6

13 92 44 33.5 80.0 56 75.8

14 94 43 31.6 79.6 57 75.6 - - - -16 18 23 52.4 96.1 77 92.7 17 22 22 53.2 95.2 78 92.2 18 20 24 52.6 95.7 76 92.2 19 21 24 51.6 95.5 76 92.0 22 25 50.8 95.2 75 91.6 21 19 25 50.6 95.8 75 92.2 22 22 28 47.6 95.2 72 91.1 23 24 29 47.4 94.8 71 90.6 24 3 10 59.7 99.4 90 97.7 1 9 63.0 99.8 91 98.2 26 1 9 62.7 99.8 91 98.2 27 107 50 28.6 76.8 50 72.0 28 110 49 30.8 76.1 51 71.7 ~3~4~ ~7 The data in Table IX demonstrate that Catalyst E, an embodiment of the catalyst of the present invention, is an excellent catalyst for the hydrodemetallization of a metal-containing hydrocarbon stream. The metals re-moval obtained with Catalyst E is depicted in Figure 2.It effectively removed the nickel and the vanadium from the Jobo II 204C+ (400F+) residual oil, which con-tained 7.9 wt.% asphaltenes, 3.7 wt.% sulfur, 461 ppm vanadium, and 100 ppm nickel.
0 Moreover, the process of the present invention, employing such a catalyst as Catalyst E, will effec-tively remove metals from a heavy hydrocarbon stream containing asphaltenes and a substantial amount of metals.

15 WHAT IS CLAIMED IS:

Claims (18)

1. A catalyst for the catalytic hydrodemetal-lization of a metal-containing hydrocarbon stream, which catalyst comprises a small amount of a hydro-genation component comprising a single active original hydrogenation metal selected from Group VIB or Group VIII of the Periodic Table of Elements deposed on a large-pore, high-surface area support comprising catalytically active alumina and one or more oxides of phosphorus, said hydrogenation component being present in the elemental form, as oxides, as sulfides, or mixtures thereof in an amount within the range of about 0.5 wt.% to about 3 wt.%, based upon the total catalyst weight and calculated as the oxide of the hydrogenation metal, said phosphorus being present in an amount within the range of about 7 wt.% to about 11 wt.%, calculated as P2O5 and based upon the weight of said support, and said catalyst having a surface area that is greater than 120 m2/gm, a pore volume that is greater than 0.7 cc/gm, and an average pore diameter that is greater than 12.5 nm (125 .ANG.).

2. The catalyst of Claim 1, wherein said hydro-genation component is present in an amount within the range of about 1 wt.% to about 2 wt.%, based upon the total catalyst weight and calculated as the oxide of the hydrogenation metal.

3. The catalyst of Claim 1, wherein said hydro-genation metal is a member of Group VIB of the Periodic Table of Elements.

4. The catalyst of Claim 1, wherein said hydro-genation metal is a member of Group VIII of the Periodic Table of Elements.

5. The catalyst of Claim 2, wherein said hydro-genation component comprises a metal of Group VIB
of the Periodic Table of Elements and said metal of Group VIB is molybdenum.

6. The catalyst of Claim 2, wherein said hydro-genation component comprises a metal of Group VIII
of the Periodic Table of Elements and said metal of Group VIII is nickel.

7. The catalyst of Claim 3, wherein said member of Group VIB is molybdenum.

8. The catalyst of Claim 4, wherein said member of Group VIII is nickel.

9. A process for the hydrodemetallization of a hydrocarbon feedstock containing asphaltenes and a substantial amount of metals, which process com-prises contacting said feedstock in a reaction zone under suitable operating conditions and in the presence of hydrogen with a catalyst which comprises a hydrogenation component comprising a single active original hydrogenation metal selected from Group VIB
or Group VIII of the Periodic Table of Elements deposed on a large-pore, high-surface area support comprising catalytically active alumina and one or more oxides of phosphorus, said hydrogenation com-ponent being present in the elemental form, as oxides, as sulfides, or mixtures thereof and in an amount within the range of about 0.5 wt.% to about 3 wt.%, based upon the total catalyst weight and calculated as the oxide of the hydrogenation metal, said phos-phorus being present in an amount within the range of about 7 wt.% to about 11 wt.%, calculated as P2O5 and based upon the weight of said support, and said catalyst having a surface area that is greater than 120 m2/gm, a pore volume that is greater than 0.7 cc/gm, and an average gore diameter that is greater than 12.5 nm (125 .ANG.).

10. The process of Claim 9, wherein said hydro-genation metal of said catalyst is a member of Group VIB of the Periodic Table of Elements.

11. The process of Claim 9, wherein said hydro-genation metal of said catalyst is a member of Group VIII of the Periodic Table of Elements.

12. The process of Claim 9, wherein said condi-tions comprise an average catalyst bed temperature of about 371°C (700°F) to about 482°C (900°F), a total pressure of about 3.55 MPa (500 psig) to about 41.5 MPa (6,000 psig), a hydrogen partial pressure of about 3.45 MPa (500 psia) to about 20.7 MPa (3,000 psia), a hydrogen flow rate or hydrogen addition rate of about 178 m3/m3 (1,000 SCFB) to about 1,780 m3/m3 (10,000 SCFB), and a LHSV of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst.

13. The process of Claim 10, wherein said condi-tions comprise an average catalyst bed temperature of about 371°C (700°F) to about 482°C (900°F), a total pressure of about 3.55 MPa (500 psig) to about 41.5 MPa (6,000 psig), a hydrogen partial pressure of about 3.45 MPa (500 psia) to about 20.7 MPa (3,000 psia), a hydrogen flow rate or hydrogen addition rate of about 178 m3/m3 (1,000 SCFB) to about 1,780 m3/m3 (10,000 SCFB), and a LHSV of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst.

14. The process of Claim 10, wherein said member of Group VIB is molybdenum.

15. The process of Claim 11, wherein said condi-tions comprise an average catalyst bed temperature of about 371°C (700°F) to about 482°C (900°F), a total pressure of about 3.55 MPa (500 psig) to about 41.5 MPa (6,000 psig), a hydrogen partial pressure of about 3.45 MPa (500 psia) to about 20.7 MPa (3,000 psia), a hydrogen flow rate or hydrogen addition rate of about 178 m3/m3 (1,000 SCFB) to about 1,780 m3/m3 (10,000 SCFB), and a LHSV of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst.

16. The process of Claim 11, wherein said member of Group VIII is nickel.

17. The process of Claim 14, wherein said condi-tions comprise an average catalyst bed temperature of about 371°C (700°F) to about 482°C (900°F), a total pressure of about 3.55 MPa (500 psig) to about 41.5 MPa (6,000 psig), a hydrogen partial pressure of about 3.45 MPa (500 psia) to about 20.7 MPa (3,000 psia), a hydrogen flow rate or hydrogen addition rate of about 178 m3/m3 (1,000 SCFB) to about 1,780 m3/m3 (10,000 SCFB), and a LHSV of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst.

18. The process of Claim 16, wherein said condi-tions comprise an average catalyst bed temperature of about 371°C (700°F) to about 482°C (900°F), a total pressure of about 3.55 MPa (500 psig) to about 41.5 MPa (6,000 psig), a hydrogen partial pressure of about 3.45 MPa (500 psia) to about 20.7 MPa (3,000 psia), a hydrogen flow rate or hydrogen addition rate of about 178 m3/m3 (1,000 SCFB) to about 1,780 m3/m3 (10,000 SCFB), and a LHSV of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst.