# US 4,399,057 A · Catalyst and support, their methods of preparation, and processes employing same

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- Number: US 4,399,057 A
- Document ID: US4399057A
- Status: Granted
- Kind: A
- Application number: 06/274,499
- Filed: 1981-06-17
- Granted: 1983-08-16
- Earliest claimed: 1981-06-17
- Assignees: Standard Oil Company (Indiana)
- Inventors: Albert L. Hensley, Jr.; Leonard M. Quick
- Web page: https://patentgrep.com/patent/US4399057A

## 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 23/28: Molybdenum
- 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}
- B01J 35/651: {50-500 nm}
- B01J 35/69: bimodal
- 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

Shaped catalyst which can be prepared by use of steam.

## Claims

### Claim 1

A method for preparing an improved catalyst support from a composite comprising two or more inorganic oxides, which method comprises forming said composite 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) and 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 catalyst support material having an average pore diameter of at least 18 nm (180 A) and a surface area below 200 m.sup.2 /gm.

### Claim 2 (depends on 1)

The method of claim 1, wherein said composite is a mixture of alumina and about 1 wt% to about 20 wt% silica, a mixture of alumina, about 1 wt% to about 20 wt% silica, and about 5 wt% to about 20 wt% oxides of phosphorus, a mixture of alumina and about 5 wt% to about 20 wt% oxides of phosphorus, a mixture of alumina and about 1 wt% to about 10 wt% boria, a mixture of alumina, about 1 wt% to about 10 wt% boria, and about 5 wt% to about 20 wt% oxides of phosphorus, or a mixture of alumina, about 1 wt% to about 20 wt% magnesia, and about 5 wt% to about 20 wt% oxides of phosphorus, said oxides of phosphorus being calculated as P.sub.2 O.sub.5 and said quantities being based upon the weight of said composite.

### Claim 3 (depends on 1)

The method of claim 1, wherein said temperature is within the range of about 704.degree. C. (1,300.degree. F.) to about 927.degree. C. (1,700.degree. F.).

### Claim 4 (depends on 1)

The method of claim 1, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 5 (depends on 2)

The method of claim 2 wherein said temperature is within the range of about 704.degree. C. (1,300.degree. F.) to about 927.degree. C. (1,700.degree. F.).

### Claim 6 (depends on 2)

The method of claim 2, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 7 (depends on 2)

The method of claim 2, wherein said composite is a mixture of alumina and about 1 wt% to about 20 wt% silica, based upon the weight of said composite.

### Claim 8 (depends on 3)

The method of claim 3, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 9 (depends on 5)

The method of claim 5, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 10 (depends on 7)

The method of claim 7, wherein said temperature is within the range of about 704.degree. C. (1,300.degree. F.) to about 927.degree. C. (1,700.degree. F.).

### Claim 11 (depends on 7)

The method of claim 7, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 12 (depends on 10)

The method of claim 10, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 13 (depends on 12)

The method of claim 12, wherein said composite comprises a mixture of alumina and about 1 wt% to about 7 wt% silica, based upon the weight of said composite.

### Claim 14

A method for preparing a catalytic composition, which method comprises forming a composite comprising two or more inorganic oxides 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 at least one hydrogenating metal.

### Claim 15 (depends on 14)

The method of claim 14, wherein said composite is a mixture of alumina and about 1 wt% to about 20 wt% silica, a mixture of alumina, about 1 wt% to about 20 wt% silica, and about 5 wt% to about 20 wt% oxides of phosphorus, a mixture of alumina and about 5 wt% to about 20 wt% oxides of phosphorus, a mixture of alumina and about 1 wt% to about 10 wt% boria, a mixture of alumina, about 1 wt% to about 10 wt% boria, and about 5 wt% to about 20 wt% oxides of phosphorus, or a mixture of alumina, about 1 wt% to about 20 wt% magnesia, and about 5 wt% to about 20 wt% oxides of phosphorus, said oxides of phosphorus being calculated as P.sub.2 O.sub.5 and said quantities being based upon the weight of said composite.

### Claim 16 (depends on 14)

The method of claim 14, wherein said temperature is within the range of about 704.degree. C. (1,300.degree. F.) to about 927.degree. C. (1,700.degree. F.).

### Claim 17 (depends on 14)

The method of claim 14, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 18 (depends on 14)

The method of claim 14, 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 19 (depends on 15)

The method of claim 15, wherein said temperature is within the range of about 704.degree. C. (1,300.degree. F.) to about 927.degree. C. (1,700.degree. F.).

### Claim 20 (depends on 15)

The method of claim 15, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 21 (depends on 15)

The method of claim 15, wherein said composite comprises a mixture of alumina and about 1 wt% to about 20 wt% silica, based upon the weight of said composite.

### Claim 22 (depends on 15)

The method of claim 15, 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 23 (depends on 16)

The method of claim 16, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 24 (depends on 19)

The method of claim 19, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 25 (depends on 21)

The method of claim 21, wherein said temperature is within the range of about 704.degree. C. (1,300.degree. F.) to about 927.degree. C. (1,700.degree. F.).

### Claim 26 (depends on 21)

The method of claim 21, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 27 (depends on 23)

The method of claim 23, wherein said at least one hydrogenating metal is molybdenum and is present in an amount within the range of about 0.5 wt% to about 20 wt%, calculated as MoO.sub.3 and based upon the weight of said catalytic composition.

### Claim 28 (depends on 24)

The method of claim 24, 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 29 (depends on 25)

The method of claim 25, wherein said steam is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 30 (depends on 28)

The method of claim 28, wherein said at least one hydrogenating metal is molybdenum and is present in an amount within the range of about 0.5 wt% to about 20 wt%, calculated as MoO.sub.3 and based upon the weight of said catalytic composition.

### Claim 31 (depends on 29)

The method of claim 29, 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 32 (depends on 31)

The method of claim 31, wherein said composite comprises a mixture of alumina and about 1 wt% to about 7 wt% silica, based upon the weight of said composite.

### Claim 33

A catalyst support which comprises two or more inorganic oxides and which is prepared by forming a composite comprising said two or more inorganic oxides 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) and 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 catalyst support material having an average pore diameter of at least 18 nm (180 A) and a surface area below 200 m.sup.2 /gm.

### Claim 34 (depends on 33)

The catalyst support of claim 33, wherein said composite is a mixture of alumina and about 1 wt% to about 20 wt% silica, a mixture of alumina, about 1 wt% to about 20 wt% silica, and about 5 wt% to about 20 wt% oxides of phosphorus, a mixture of alumina and about 5 wt% to about 20 wt% oxides of phosphorus, a mixture of alumina and about 1 wt% to about 10 wt% boria, a mixture of alumina, about 1 wt% to about 10 wt% boria, and about 5 wt% to about 20 wt% oxides of phosphorus, or a mixture of alumina, about 1 wt% to about 20 wt% magnesia, and about 5 wt% to about 20 wt% oxides of phosphorus, said oxides of phosphorus being calculated as P.sub.2 O.sub.5 and said quantities being based upon the weight of said composite.

### Claim 35 (depends on 34)

The catalyst support of claim 34, wherein said steam that is used in its preparation is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 36 (depends on 34)

The catalyst support of claim 34, wherein said temperature that is used in its preparation is within the range of about 704.degree. C. (1,300.degree. F.) to about 927.degree. C. (1,700.degree. F.).

### Claim 37 (depends on 34)

The catalyst support of claim 34, wherein said composite comprises a mixture of alumina and about 1 wt% to about 20 wt% silica, based upon the weight of said composite.

### Claim 38 (depends on 36)

The catalyst support of claim 36, wherein said steam that is used in its preparation is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 39 (depends on 37)

The catalyst support of claim 37, wherein said temperature that is used in its preparation is within the range of about 704.degree. C. (1,300.degree. F.) to about 927.degree. C. (1,700.degree. F.).

### Claim 40 (depends on 37)

The catalyst support of claim 37, wherein said steam that is used in its preparation is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 41 (depends on 40)

The catalyst support of claim 40, wherein said temperature that is used in its preparation is within the range of about 704.degree. C. (1,300.degree. F.) to about 927.degree. C. (1,700.degree. F.).

### Claim 42 (depends on 41)

The catalyst support of claim 41, wherein said composite is a mixture of alumina and about 1 wt% to about 7 wt% silica, based upon the weight of said composite.

### Claim 43

A catalyst which comprises a hydrogenating component comprising at least one hydrogenating metal and a large-pore, high-surface area support comprising two or more inorganic oxides, 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 said two or more inorganic oxides 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 44 (depends on 43)

The catalyst of claim 43, wherein said composite is a mixture of alumina and about 1 wt% to about 20 wt% silica, a mixture of alumina, about 1 wt% to about 20 wt% silica, and about 5 wt% to about 20 wt% oxides of phosphorus, a mixture of alumina and about 5 wt% to about 20 wt% oxides of phosphorus, a mixture of alumina and about 1 wt% to about 10 wt% boria, a mixture of alumina, about 1 wt% to about 10 wt% boria, and about 5 wt% to about 20 wt% oxides of phosphorus, or a mixture of alumina, about 1 wt% to about 20 wt% magnesia, and about 5 wt% to about 20 wt% oxides of phosphorus, said oxides of phosphorus being calculated as P.sub.2 O.sub.5 and said quantities being based upon the weight of said composite.

### Claim 45 (depends on 43)

The catalyst of claim 43, 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 46 (depends on 44)

The catalyst of claim 44, 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 47 (depends on 44)

The catalyst of claim 44, wherein said composite comprises a mixture of alumina and about 1 wt% to about 20 wt% silica, based upon the weight of said composite.

### Claim 48 (depends on 47)

The catalyst of claim 47, 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 49 (depends on 48)

The catalyst of claim 48, wherein the temperature that is used in its preparation is within the range of about 704.degree. C. (1,300.degree. F.) to about 927.degree. C. (1,700.degree. F.) and the steam that is used in its preparation is employed at a pressure within the range of about 30 kPa (4.4 psia) to about 274 kPa (25 psig).

### Claim 50 (depends on 49)

The catalyst of claim 49, wherein said at least one hydrogenating metal is molybdenum and is present within the range of about 0.5 wt% to about 20 wt%, calculated as MoO.sub.3 and based upon the weight of the catalyst.

### Claim 51

A method for preparing a catalyst support from a composite comprising two or more inorganic oxides, which method comprises forming the composite comprising two or more inorganic oxides into a shaped catalyst support material having a selected shape, a bimodal distribution of pore sizes, and a total pore volume that is at least 0.8 cc/gm and 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 catalyst support material having an average pore diameter of at least 18 nm (180 A) and a surface area below 200 m.sup.2 /gm.

### Claim 52

A catalyst support comprising two or more inorganic oxides and having a selected shape, a total pore volume that is at least 0.8 cc/gm, and a bimodal distribution of pore sizes, said catalyst support having been prepared by forming a composite comprising said two or more inorganic oxides into a shaped catalyst support material having said selected shape, said total pore volume, and said bimodal distribution of pore sizes and 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 catalyst support material having an average pore diameter of at least 18 nm (180 A) and a surface area below 200 m.sup.2 /gm.