Catalyst and process for hydroconversion of a heavy feedstock

• US 9,371,496 B2
• Filed: 05/20/2013
• Issued: 06/21/2016
• Est. Priority Date: 05/21/2012
• Status: Active Grant

• Current Assignee: Shell USA Incorporated (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Kester, John George, Komar, David Andrew, Sherwood, David Edward
• Primary Examiner(s): Bullock, In Suk
• Assistant Examiner(s): MUELLER, DEREK N
• Application Number:
  US13/897,756
• Publication Number:
  US 20130306517A1
• Time in Patent Office: 1,128 Days
• US Class Current: 1/1
• CPC Class Codes: B01J 23/883 and nickel
• CPC Class Codes: B01J 27/19 Molybdenum
• CPC Class Codes: B01J 27/199 with chromium, molybdenum, tungsten or polonium
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/50 characterised by their shape or configuration
• CPC Class Codes: B01J 35/56 Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/0036 Grinding
• CPC Class Codes: B01J 37/0201 Impregnation
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: C10G 2300/1077 Vacuum residues
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 45/08 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C10G 49/04 containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C10G 65/00 Treatment of hydrocarbon oils by two or more hydrotreatment processes only
• CPC Class Codes: C10G 65/12 including cracking steps and other hydrotreatment steps

Abstract

A hydroconversion catalyst comprising a Group VIB metal component, a Group VIII metal component and a carrier material is disclosed wherein said catalyst has a total surface area of 240 to 360 m²/g; a total pore volume of 0.5 to 0.9 cc/g; and a pore volume distribution such that greater than 60% of pore volume are in pores present as micropores of diameter between 55 and 115 Å, less than 0.12 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å and less than 10% of pore volume are in pores present as macropores of diameters greater than 250 Å.

Claims

1. A hydroprocessing catalyst for treating heavy hydrocarbon feedstocks, wherein said catalyst comprises:

a calcined particle comprising a co-mulled mixture made by co-mulling inorganic oxide powder or powders, solution or solutions containing molybdenum and Group VIII metals and optionally water, acid and flocculating agent, and then forming said co-mulled mixture into a particle that is calcined to thereby provide said calcined particle, said calcined particles having;

a. a total surface area of 240 to 360 m²/g;

b. a total pore volume of 0.5 to 0.9 cc/g; and

c. a pore volume distribution such that greater than 60% of pore volume are in pores present as micropores of diameter between 55 and 115 Å

, less than 0.12 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å

, greater than 5% of the total pore volume is in pores of diameter greater than 210 Å

, and less than 10% of pore volume are in pores present as macropores of diameters greater than 250 Å

.

2. The catalyst of claim 1, wherein said calcined particle has a shape comprising a first end, a second end and a wall disposed between said ends, said wall comprising 3 or 4 lobes formed in the length of the wall.

3. The catalyst of claim 1, wherein said inorganic oxide material is selected from the group consisting of alumina, silica and alumina-silica.

4. The catalyst of claim 1, wherein said calcined mixture has a molybdenum content in the range of from 1 weight percent to 24 weight percent with the weight percent being based upon the molybdenum as MoO₃ and the total weight of the calcined mixture, a nickel content in the range of from 0.2 weight percent to 6 weight percent based on the nickel as NiO and the total weight of the calcined mixture, and a phosphorous content in the range from 0 weight percent to 6 weight percent, with the weight percent being based upon the phosphorous as P₂O₅ and the total weight of the calcined mixture.

5. The catalyst of claim 2, wherein each calcined particle has an outer circle diameter of D_O, an inner circle diameter of D_I, and a height of H;

the ratio of D_O to D_I is between about 1.5 to 3.0;

the ratio of H to D_O is between about 1 to about 4; and

the outer circle diameter D_o is between about 0.75 and 2 millimeters.

6. The catalyst of claim 5, wherein the catalyst has a total surface area of 245-285 m²/g, a total pore volume of 0.65-0.75 cc/g, and a pore volume distribution such that greater than 75% of pore volume are in pores present as micropores of diameter between 55 and 115 Å

, less than 0.10 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å and

0-9% of pore volume are in pores present as macropores of diameters greater than 250 Å

.

7. The catalyst of claim 1, wherein said calcined mixture has a molybdenum content in the range of from 7.5 weight percent to 11 weight percent with the weight percent being based upon the molybdenum as MoO₃ and the total weight of the calcined mixture, a nickel content in the range of from 1.5 weight percent to 3.5 weight percent based on the nickel as NiO and the total weight of the calcined mixture, and a phosphorous content in the range from 0 weight percent to 2 weight percent, with the weight percent being based upon the phosphorous as P₂O₅ and the total weight of the calcined mixture.

8. The catalyst of claim 5, wherein said calcined particle has three truncated lobes with rounded intersections of the lobes.

12. A process comprising:

contacting a heavy hydrocarbon feedstock having a nickel content in the range of from 0.1 ppmw to 250 ppmw, a vanadium content in the range of from 0.3 ppmw to 250 ppmw, and a sulfur content in the range of from 0.5 wt % to 8 wt % with any one of the catalyst of claims 1 through 8.

9. A method of making a highly stable heavy hydrocarbon hydrodesulfurization, metal removal and pitch conversion catalyst, wherein said method comprises:

a. forming a co-mulled mixture by co-mulling solid inorganic oxide powders, solution or solutions containing molybdenum and Group VIII metals and optionally water, acid and flocculating agent;

b. extruding said co-mulled mixture into particles to form a shape comprising a first end, a second end and a wall disposed between said ends, said wall comprising 3 or 4 lobes formed in the length of the wall wherein each lobe; and

c. calcining said particles at temperatures such that greater than 60% of pore volume are in pores present as micropores of diameter between 55 and 115 Å

, less than 0.12 cc/g of pore volume are in pores present at pores of diameter greater than 160 Å

, greater than 5% of the total pore volume is in pores of diameter greater than 210 Å

, and less than 10% of pore volume are in pores present as macropores of diameters greater than 250 Å

; and

d. wherein said calcined particle has a shape comprising a first end, a second end and a wall disposed between said ends, said wall comprising 3 or 4 lobes formed in the length of the wall, wherein each calcined particle has an outer circle diameter of D_O, an inner circle diameter of D_I, and a height of H;

the ratio of D_O to D_I is between about 1.5 to 3.0;

the ratio of H to D_O is between about 1 to about 4; and

the outer circle diameter D_o is between about 0.75 and 2 millimeters.

10. The method of claim 9, wherein said calcining step is conducted under a controlled temperature condition in which the calcination temperature is in the range of from about 482°

C. (900°

F.) to about 787.7°

C. (1450°

F.) for a calcination time period that is effective to provide said calcined mixture having a desired pore structure.

11. The method of claim 10, wherein said inorganic oxide material is selected from the group consisting of alumina, silica and alumina-silica.