Hydrotreatment of heavy hydrocarbon oils containing asphaltenes, and catalysts therefor

• US 4,444,655 A
• Filed: 09/30/1982
• Issued: 04/24/1984
• Est. Priority Date: 02/19/1980
• Status: Expired due to Term

• Current Assignee: Chiyoda Chemical Engineering & Construction Company Limited (Mitsubishi Corporation)
• Original Assignee: Chiyoda Chemical Engineering & Construction Company Limited (Mitsubishi Corporation)
• Inventors: Asaoka, Sachio, Ono, Takeo, Shiroto, Yoshimi, Nakamura, Munekazu
• Primary Examiner(s): Gantz, Delbert E.
• Assistant Examiner(s): Prezlock, Cynthia A.
• Application Number:
  US06/428,796
• Time in Patent Office: 572 Days
• Field of Search: 208/210, 208/216 PP, 208/251 H, 208/97, 208/111
• US Class Current: 208/210
• CPC Class Codes: B01J 23/85 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 23/8872 Alkali or alkaline earth metals
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 35/66 Pore distribution
• CPC Class Codes: C10G 2300/107 Atmospheric residues having a boiling point of at least about 538 °C

Abstract

A catalyst for hydrotreating a heavy hydrocarbon oil containing asphaltenes comprises a porous carrier composed of one or more inorganic oxides of at least one element selected from among those of Groups II, III and IV of the Periodic Table, and at least one catalytic metal component composited with the carrier. The metal of the catalytic metal component is selected from among those of Groups VB, VIB, VIII and IB of the Periodic Table. The catalyst contains about 1 to 30% by weight of such catalytic metal component and has the following pore characteristics with regard to its pores having a diameter of 75 Å or more: an average pore diameter APD of about 180 to 500 Å, a total pore volume PV, expressed in cc/g, being equal to or greater than a value X ##EQU1## the volume of pores with a diameter of about 180 to 500 Å being at least about 0.2 cc/g, the volume of pores with a diameter of at least 1,500 Å being not greater than about 0.03 cc/g, and a total surface area being at least about 60 m² /g. The catalyst has an average catalyst diameter ACD, expressed in millimeters, of not greater than a value of the formula, ACD=(APD/100)⁰.5. Disclosed also are a method of preparing such a catalyst, and a process for hydrotreating a heavy hydrocarbon oil containing asphaltenes in the presence of such a catalyst.

Claims

1. A process for hydrotreating a heavy hydrocarbon oil containing asphaltenes, said process comprising the step of:

reacting the heavy hydrocarbon oil with hydrogen at a temperature of between 300° and

500°

C., a hydrogen pressure of between 50 and 250 atm. and a liquid space velocity of between 0.1 and 10 hour^-1 in the presence of a catalyst comprising;

a porous carrier composed of one or more inorganic oxides of at least one member selected from the group consisting of the elements belonging to Groups II, III and IV of the Periodic Table; and

one or more catalytic metal components composited with said carrier, the metal of said catalytic metal components being selected from the group consisting of the metals belonging to groups VB, VIB, VIII and IB of the Periodic Table, said catalytic metal components being present in an amount of between about 0.1% and about 30% in terms of metal oxide based on the total weight of said catalyst, said catalyst having the following pore characteristics (a)-(c) with regard to its pores having a diameter of 75 Å

or more;

(a) an average pore diameter APD being between about 180 and about 500 Å

,

(b) a total pore volume PV in terms of cc/g being at least a value X calculated according to the following equation;

##EQU9## the volume of pores with a diameter of between about 180 and about 500 Å

being at least about 0.35 cc/g, the volume of pores with a diameter of at least 1500 Å

being not greater than about 0.03 cc/g, and

(c) a total surface area SA being at least about 104 m² /g, said catalyst having an average catalyst diameter ACD of at least about 0.6 mm.

2. A process as set forth in claim 1, wherein said total volume PV is not greater than a value X'"'"' calculated according to the following equation:

##EQU10## where ln is a symbol representing a natural logarithm.

3. A process as set forth in claim 1, wherein said average pore diameter APD is between 180 Å

and 400 Å

, said total pore volume PV being between 0.5 cc/g and 1.5 cc/g, said total surface area SA being at least 104 m² /g, the volume of pores with a diameter of not greater than 100 Å

being not greater than 0.1 cc/g, said average catalyst diameter ACD being between about 0.6 mm and about 1.5 mm.

4. A process as set forth in claim 1, wherein the volume of pores having a diameter of between 180 Å

and 400 Å

is at least a half of the total volume of pores having a diameter of between 180 Å and

500 Å

.

5. A process as set forth in claim 1, wherein said inorganic oxide is at least one member selected from the group consisting of alumina, silica, titania, boria, zirconia, silica-alumina, silica-magnesia, alumina-magnesia, alumina-titania, silica-titania, alumina-boria, alumina-zirconia and silica-zirconia.

6. A process as set forth in claim 1, wherein the metal of said one or more catalytic metal components is at least one member selected from the group consisting of vanadium, chromium, molybdenum, tungsten, cobalt, nickel and copper, said catalytic metal components being in the form of an elemental metal, an oxide, a sulfide or a mixture thereof.

7. A process as set forth in claim 1, further comprising separating the product from step (a) into a hydrogen-rich gas and a liquid product, separating said liquid product into a substantially asphaltene-free and heavy metal-free light oil fraction and a heavy fraction, and recycling said heavy fraction to step (a).

8. A process as set forth in claim 7, wherein said heavy hydrocarbon oil contains at least 2% by weight of asphaltenes and at least 80 ppm by weight of nickel and vanadium.

9. A process as set forth in any one of claims 1 through 4, further comprising the step of:

(b) reacting at least a part of the product from step (a) with hydrogen at a temperature of between 300° and

500°

C., a hydrogen pressure of between 50 and 250 atm. and a liquid space velocity of between 0.1 and 10 hours^-1 in the presence of a catalyst including a porous carrier containing alumina and having composited therewith a combination of first and second catalytic metal components, the metal of said first catalytic metal component being at least one member selected from the group consisting of the metals belonging to Group VIB of the Periodic Table, the metal of said second catalytic metal component being at least one member selected from the group consisting of the metals belonging to Group VIII of the Periodic Table, said catalyst having, with regard to its pores with a diameter of 75 Å

or more, the properties of;

an average pore diameter being between about 80 and about 250 Å

a total pore volume being between about 0.4 and about 1.5 cc/g, and a total surface area being between about 100 and about 400 m² /g.

10. A process as set forth in claim 9, wherein the metal of said first catalytic metal component of the catalyst of step (b) is selected from the group consisting of chromium, molybdenum and tungsten, and the metal of said second catalytic metal component of the catalyst of step (b) is selected from the group consisting of cobalt and nickel, said first and second catalytic metal component being present in amounts of between about 2 and about 40% by weight and between about 0.1 and about 10% by weight, in terms of oxide, based on the total weight of said catalyst of step (b), respectively.

11. A process as set forth in claim 9, wherein the catalyst of step (b) further includes an auxiliary catalytic component containing at least one member selected from the group consisting of titanium, boron, phosphorus and fluorine.

12. A process as set forth in claim 11, wherein said auxiliary catalytic component is selected from the group consisting of boron phosphate, boron fluoride and a mixture thereof.

13. A process as set forth in claim 9, wherein said alumina-containing carrier of the catalyst of step (b) is alumina or silica-alumina.

14. A process as set forth in claim 9, wherein a part of the reaction product from step (a) is separated into a hydrogen-rich gas and a liquid product, said liquid product being separated into a substantially asphaltene-free and heavy metal-free light oil fraction and a heavy fraction, said heavy fraction being recycled to step (a).

15. A process as set forth in claim 9, wherein the reaction product from step (b) is separated into a hydrogen-rich gas and a liquid product, said liquid product being separated into a substantially asphaltene-free and heavy metal-free light oil fraction and a heavy fraction, said heavy fraction being recycled to step (a) or (b).