# US 4,395,328 A · Catalyst and support, their methods of preparation, and processes employing same

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- Number: US 4,395,328 A
- Document ID: US4395328A
- Status: Granted
- Kind: A
- Application number: 06/274,553
- Filed: 1981-06-17
- Granted: 1983-07-26
- Earliest claimed: 1981-06-17
- Assignees: Standard Oil Company (Indiana)
- Inventors: Albert L. Hensley, Jr.; Leonard M. Quick
- Web page: https://patentgrep.com/patent/US4395328A

## CPC

- B01J 37/10: in the presence of water, e.g. steam
- B01J 21/02: Boron or aluminium; Oxides or hydroxides thereof
- B01J 21/12: Silica and alumina
- B01J 27/16: containing oxygen {, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr}
- B01J 35/60: characterised by their surface properties or porosity
- B01J 35/615: {100-500 m2/g}
- B01J 35/638: {more than 1.0 ml/g}
- B01J 35/647: {2-50 nm}
- C10G 2300/107: Atmospheric residues having a boiling point of at least about 538 °C
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES

## Abstract

A catalyst support is prepared from a composite comprising alumina and one or more oxides of phosphorous by forming the composite into a shaped support material having at least 0.8 cc/gm of its pore volume in pores having diameters of 0 nm (0 A) to 120 nm (1,200 A) and at least 0.1 cc/gm of its pore volume in pores having diameters of 120 nm (1,200 A) to 5,000 nm (50,000 A) and heating said shaped support material in the presence of steam at sufficient elevated temperature, steam pressure, and time period to increase the average pore diameter of said shaped support in the absence of any appreciable reduction in pore volume. A catalyst is prepared by impregnating the steam-treated support with at least one hydrogenating metal. The catalyst can be used suitably in hydrocarbon conversion processes, such as a process for the hydrodemetallization of a hydrocarbon stream containing asphaltenes and a substantial amount of metals.

## Claims

### Claim 1

A process for the conversion of a hydrocarbon stream, which process comprises contacting said stream under suitable conditions and in the presence of hydrogen with a catalyst comprising a hydrogenating component comprising at least one hydrogenating metal and a large-pore, high-surface area support comprising an alumina and one or more oxides of phosphorus, said at least one hydrogenating metal being present in the elemental form, as the oxide, as the sulfide, or mixtures thereof, said catalyst having been prepared by forming a composite comprising alumina and one or more oxides of phosphorus into a shaped catalyst support material having a selected shape and at least 0.8 cc/gm of its pore volume in pores having diameters of 0 nm (0 A) to 120 nm (1,200 A) and at least 0.1 cc/gm of its pore volume in pores having diameters of 120 nm (1,200 A) to 5,000 nm (50,000 A), heating said shaped catalyst support material in the presence of steam at sufficient elevated temperature, steam pressure, and time period to increase the average pore diameter of said shaped catalyst support material in the absence of any appreciable reduction in pore volume so as to provide a steam-treated support material having an average pore diameter of at least 18 nm (180 A) and a surface area below 200 m.sup.2 /gm, and subsequently impregnating said steam-treated support material with said at least one hydrogenating metal.

### Claim 2 (depends on 1)

The process of claim 1, wherein said catalyst is present in one or more ebullating beds and said at least one hydrogenating metal is selected from the group consisting of vanadium, metals of Group VIB of the Periodic Table of Elements, and metals of Group VIII of the Periodic Table of Elements.

### Claim 3 (depends on 1)

The process of claim 1, wherein said catalyst is present in one or more fixed beds and said at least one hydrogenating metal is selected from the group consisting of vanadium, metals of Group VIB of the Periodic Table of Elements, and metals of Group VIII of the Periodic Table of Elements.

### Claim 4

A process for the hydrodemetallization of a hydrocarbon stream containing asphaltenes and a substantial amount of metals, which process comprises contacting said stream in the presence of hydrogen and under hydrodemetallization conditions with a catalyst comprising a hydrogenating component comprising at least one hydrogenating metal and a large-pore, high-surface area support comprising an alumina and one or more oxides of phosphorus, said at least one hydrogenating metal being present in the elemental form, as the oxide, as the sulfide, or mixtures thereof, said catalyst having been prepared by forming a composite comprising alumina and one or more oxides of phosphorus into a shaped catalyst support material having a selected shape and at least 0.8 cc/gm of its pore volume in pores having diameters of 0 nm (0 A) to 120 nm (1,200 A) and at least 0.1 cc/gm of its pore volume in pores having diameters of 120 nm (1,200 A) to 5,000 nm (50,000 A), heating said shaped catalyst support material in the presence of steam at sufficient elevated temperature, steam pressure, and time period to increase the average pore diameter of said shaped catalyst support material in the absence of any appreciable reduction in pore volume so as to provide a steam-treated support material having an average pore diameter of at least 18 nm (180 A) and a surface area below 200 m.sup.2 /gm, and subsequently impregnating said steam-treated support material with said at least one hydrogenating metal.

### Claim 5 (depends on 4)

The process of claim 4, wherein said operating conditions comprise an average catalyst bed temperature of about 371.degree. C. (700.degree. F.) to about 482.degree. C. (900.degree. 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 m.sup.3 /m.sup.3 (1,000 SCFB) to about 1,780 m.sup.3 /m.sup.3 (10,000 SCFB), and a LHSV of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst.

### Claim 6 (depends on 4)

The process of claim 4, wherein said catalyst is present in one or more ebullating beds and said at least one hydrogenating metal is selected from the group consisting of vanadium, metals of Group VIB of the Periodic Table of Elements, and metals of Group VIII of the Periodic Table of Elements.

### Claim 7 (depends on 4)

The process of claim 4, wherein said catalyst is present in one or more fixed beds and said at least one hydrogenating metal is selected from the group consisting of vanadium, metals of Group VIB of the Periodic Table of Elements, and metals of Group VIII of the Periodic Table of Elements.

### Claim 8 (depends on 4)

The process of claim 4, wherein said at least one hydrogenating metal is selected from the group consisting of vanadium, metals of Group VIB of the Periodic Table of Elements, and metals of Group VIII of the Periodic Table of Elements.

### Claim 9 (depends on 6)

The process of claim 6, wherein said operating conditions comprise an average catalyst bed temperature of about 371.degree. C. (700.degree. F.) to about 482.degree. C. (900.degree. 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 m.sup.3 /m.sup.3 (1,000 SCFB) to about 1,780 m.sup.3 /m.sup.3 (10,000 SCFB), and a LHSV of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst.

### Claim 10 (depends on 7)

The process of claim 7, wherein said hydrogenating component comprises molybdenum and said molybdenum is present in an amount within the range of about 0.5 wt% to about 20 wt%, calculated as molybdenum trioxide and based upon the total catalyst weight.

### Claim 11 (depends on 7)

The process of claim 7, wherein said operating conditions comprise an average catalyst bed temperature of about 371.degree. C. (700.degree. F.) to about 482.degree. C. (900.degree. 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 m.sup.3 /m.sup.3 (1,000 SCFB) to about 1,780 m.sup.3 /m.sup.3 (10,000 SCFB), and a LHSV of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst.

### Claim 12 (depends on 8)

The process of claim 8, wherein said operating conditions comprise an average catalyst bed temperature of about 371.degree. C. (700.degree. F.) to about 482.degree. C. (900.degree. 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 m.sup.3 /m.sup.3 (1,000 SCFB) to about 1,780 m.sup.3 /m.sup.3 (10,000 SCFB), and a LHSV of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst.

### Claim 13 (depends on 10)

The process of claim 10, wherein said operating conditions comprise an average catalyst bed temperature of about 371.degree. C. (700.degree. F.) to about 482.degree. C. (900.degree. 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 m.sup.3 /m.sup.3 (1,000 SCFB) to about 1,780 m.sup.3 /m.sup.3 (10,000 SCFB), and a LHSV of about 0.2 to about 2.5 volumes of hydrocarbon per hour per volume of catalyst.