Methods for producing a crude product

• US 7,749,374 B2
• Filed: 10/03/2007
• Issued: 07/06/2010
• Est. Priority Date: 10/06/2006
• Status: Expired due to Fees

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Bhan, Opinder Kishan, Wellington, Scott Lee
• Primary Examiner(s): Hill, Jr.; Robert J
• Assistant Examiner(s): MCCAIG, BRIAN A
• Application Number:
  US11/866,922
• Publication Number:
  US 20090057197A1
• Time in Patent Office: 1,007 Days
• Field of Search: 208/95, 208/123, 208/124
• US Class Current: 208/123
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 2235/00 Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
• CPC Class Codes: B01J 2235/15 X-ray diffraction
• CPC Class Codes: B01J 2235/30 Scanning electron microscopy; Transmission electron microscopy
• CPC Class Codes: B01J 23/22 Vanadium
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 23/883 and nickel
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/37 Crush or impact strength
• 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 35/66 Pore distribution
• CPC Class Codes: B01J 35/70 characterised by their crystalline properties, e.g. semi-crystalline catalysts comprising carbon B01J21/18; molecular sieves B01J29/00
• 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 37/0203 the impregnation liquid containing organic compounds
• CPC Class Codes: C10G 2300/206 Asphaltenes
• CPC Class Codes: C10G 2300/208 Sediments, e.g. bottom sediment and water or BSW
• CPC Class Codes: C10G 2300/302 Viscosity
• CPC Class Codes: C10G 2300/308 : Gravity, density, e.g. API
• CPC Class Codes: C10G 2300/4006 : Temperature
• CPC Class Codes: C10G 2300/4012 : Pressure
• CPC Class Codes: C10G 2300/4018 : Spatial velocity, e.g. LHSV, WHSV
• CPC Class Codes: C10G 45/04 : characterised by the catalyst used
• CPC Class Codes: C10G 45/08 : in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C10G 47/00 : Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions C10G15/00 takes precedence; destructive hydrogenation of non-melting solid carbonaceous or similar materials C10G1/06
• CPC Class Codes: C10G 47/10 : with catalysts deposited on a carrier
• CPC Class Codes: C10G 47/12 : Inorganic carriers
• CPC Class Codes: C10G 49/04 : containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C10G 65/12 : including cracking steps and other hydrotreatment steps

Abstract

Methods for conversion of a hydrocarbon feed to a total product are described. Contact of the hydrocarbon feed with one or more catalysts at selected contacting conditions produces the total product. The total product includes a crude product that is a liquid mixture at 25° C. and 0.101 MPa and has one or more properties that are changed relative to the respective property of the hydrocarbon feed. Selected contacting conditions include a partial pressure of at most 7 MPa. During contact a P-value of a hydrocarbon feed/total product mixture remains at least 1.0. The crude product has a residue content of at most 90% and/or a reduced viscosity of at most 50% as compared to the residue content and/or viscosity content of the hydrocarbon feed.

Claims

1. A method of producing a crude product, comprising:

contacting a hydrocarbon feed with one or more catalysts positioned in one or more contacting zones of a fixed bed reactor to produce a total product that includes the crude product, wherein the crude product is a liquid mixture at 25°

C. and 0.101 MPa, the hydrocarbon feed having, per gram of hydrocarbon feed, a total residue content of at least 0.1 grams, and at least one of the catalysts comprises one or more metals from Column 6 of the Periodic Table, and/or one or more compounds of one of more metals from Column 6 of the Periodic Table, wherein the Column 6 metal catalyst has a total molybdenum content of at least 0.0001 grams per gram of catalyst and at most 0.1 grams per gram of catalyst; and

controlling contacting conditions at a temperature of at least 300°

C., a partial pressure of hydrogen of at most 7 MPa, and a LHSV of at least 0.1 h<sup>−

1</sup> to produce the crude product, the crude product having a residue content of at most 60% of the hydrocarbon feed residue content, wherein the residue content is as determined by ASTM Method D5307.

2. The method of claim 1, wherein the hydrocarbon feed has an API gravity of at least 5, and contacting conditions are also controlled such that the crude product has an increase in API gravity of at least 5 relative to the hydrocarbon feed.

3. The method of claim 1, wherein the hydrocarbon feed has at least 0.01 grams of C5 asphaltenes per gram of hydrocarbon feed, and contacting conditions are also controlled such that the crude product has a C5 asphaltenes content of at most 90% of the hydrocarbon feed C5 asphaltenes content.

4. The method of claim 1, wherein the hydrocarbon feed has a viscosity of at least 1,000 cSt at 37.8°

C.

5. The method of claim 1, wherein the hydrocarbon feed has an API gravity of at most 10.

6. The method of claim 1, wherein at least one of metals of the Column 6 metal catalyst is molybdenum.

7. The method of claim 1, wherein the catalyst is a supported catalyst, and wherein the support comprises alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, or mixtures thereof.

8. The method of claim 1, wherein the Column 6 metal catalyst has a pore size distribution with a median pore diameter from 50 angstroms to 180 angstroms.

9. The method of claim 1, wherein the Column 6 metal catalyst has a surface area of at least 200 m²/g.

10. The method of claim 1, wherein the Column 6 metal catalyst further comprises nickel and/or cobalt.

11. The method of claim 1, wherein the Column 6 metal catalyst also includes one or more elements from Column 15 of the Periodic Table and/or one or more compounds of one or more elements from Column 15 of the Periodic Table.

12. The method of claim 11, wherein the additional catalyst has a molybdenum content of at least 0.1 grams per gram of catalyst.

13. The method of claim 1, wherein one or more of the catalysts also includes an additional catalyst, wherein the additional catalyst comprises one or more metals from Columns 6-10 of the Periodic Table and/or one or more compounds of one or more metals from Columns 6-10 of the Periodic Table.

14. The method of claim 1, wherein one or more of the catalysts also includes an additional catalyst, and the additional catalyst is positioned downstream of the Column 6 metal catalyst.

15. The method of claim 1, wherein the crude product has greater than 0 grams, but less than 0.01 grams of at least one of the catalysts.

16. The method of claim 1, wherein the method further comprises fractionating the crude product into one or more distillate fractions, and producing transportation fuel from at least one of the distillate fractions.

17. A method of producing a crude product, comprising:

contacting a hydrocarbon feed with one or more catalysts to produce a total product that includes the crude product, wherein the crude product is a liquid at 25°

C. and 0.101 MPa, the hydrocarbon feed having a viscosity of at least 10 cSt at 37.8°

C. and a total residue content of at least 0.1 grams per gram of hydrocarbon feed;

at least one of the catalysts comprises one or more metals from the Columns 6-10 of the Periodic Table and/or one or more compounds of one or more metals from Columns 6-10 of the Periodic Table, wherein the Columns 6-10 metal catalyst has a total molybdenum content of at least 0.0001 grams per gram of catalyst and at most 0.1 grams per gram of catalyst; and

controlling contacting conditions at a temperature from 370°

C. to 450°

C., a partial pressure of hydrogen of at most 7 MPa, and a liquid hourly space velocity (LHSV) of at least 0.1 h<sup>−

1</sup> to produce the crude product, the crude product having a viscosity at 37.8°

C. of at most 50% of the viscosity of the hydrocarbon feed at 37.8°

C. and having a residue content of at most 60% of the hydrocarbon feed residue content, and wherein a P-value of a hydrocarbon/total product mixture is at least 1.0 during contacting, wherein viscosity is as determined by ASTM Method D445, residue content is as determined by ASTM Method 5307, and P-value is as determined b ASTM Method D7060.

18. The method of claim 17, wherein the viscosity at 37.8°

C. of the hydrocarbon feed is at least 100 cSt.

19. The method of claim 17, wherein the viscosity at 37.8°

C. of crude product is at most 40% of the hydrocarbon feed viscosity at 37.8°

C.

20. The method of claim 17, wherein, after 500 hours of contacting a hydrocarbon feed with one or more catalysts, the P-value of the hydrocarbon feed/total product mixture, produced during contact of additional hydrocarbon feed with the one or more catalysts, is at least 1.0.

21. The method of claim 17, wherein the partial pressure of hydrogen is at most 6 MPa.

22. The method of claim 17, wherein the hydrocarbon feed has an API gravity of at most 10.

23. The method of claim 17, wherein the total product comprises C1 to C3 hydrocarbons and the total product has a C1 to C3 hydrocarbons content of at most 0.02 grams per gram of total product.

24. The method of claim 17, wherein contacting conditions are controlled at a liquid hourly space velocity of at least 0.5 h⁻

1.

25. The method of claim of claim 17, wherein the crude product has a hydrogen to carbon (H/C) ratio between 80% and 120% of the hydrocarbon feed H/C ratio.

26. The method of claim 17, wherein at most 0.003 grams of sediment per gram of total product/hydrocarbon feed mixture is formed during contacting.

27. The method of claim 17, wherein the Columns 6-10 metals catalyst comprises molybdenum.

28. The method of claim 17, wherein the Columns 6-10 catalyst has a total molybdenum content from 0.001 grams to 0.6 grams per gram of catalyst.

29. The method of claim 17, wherein the Columns 6-10 metals catalyst is a supported catalyst, and wherein the support comprises alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, or mixtures thereof.

30. The method of claim 17, wherein the Columns 6-10 metals catalyst has a pore size distribution with a median pore diameter from 50 angstroms to 150 angstroms.

31. The method of claim 17, wherein the Columns 6-10 metals catalyst has a surface area of at least 200 m²/g.

32. The method of claim 17, wherein the Columns 6-10 metals catalyst further comprises one or more elements from Column 15 of the Periodic Table and/or one or more compounds of one or more elements from Column 15 of the Periodic Table.

33. The method of claim 17, wherein the hydrocarbon feed is contacted with one or more catalysts in a fixed bed reactor.

34. The method of claim 17, further comprising heating the one or more catalysts to a temperature of at least 400°

C. in a time period of less than three weeks.

35. The method of claim 34, wherein the one or more catalysts are heated prior to contacting the hydrocarbon feed with the one or more catalyst.

36. The method of claim 17, wherein the method further comprises fractionating the crude product into one or more distillate fractions, and producing transportation fuel from at least one of the distillate fractions.

37. A method of producing a crude product, comprising:

contacting a hydrocarbon feed with hydrogen in the presence of one or more catalysts, wherein the one of the catalysts has a total molybdenum content of at least 0.0001 grams per gram of catalyst and at most 0.1 grams per gram of catalyst, to produce a total product that includes the crude product, wherein the crude product is a liquid mixture at 25°

C. and 0.101 MPa and the hydrocarbon feed has a viscosity of at least 10 cSt at 37.8°

C. and a residue content of at least 0.1 gram per gram of hydrocarbon feed; and

controlling contacting conditions at a partial pressure of hydrogen of at most 7 MPa and a temperature of at most 450°

C. such that a P-value of a hydrocarbon feed/total product mixture remains at least 1.0, a total consumption of hydrogen is at most 80 Nm³/m³, and the crude product has a viscosity of at most 50% at 37.8°

C. of the hydrocarbon feed viscosity and a residue content of at most 60% of the hydrocarbon feed residue content, wherein viscosity is as determined by ASTM Method D445, residue content is as determined by ASTM Method D5307, and P-value is as determined by ASTM Method D7060.

38. The method of claim 37, wherein the viscosity at 37.8°

C. of the hydrocarbon feed is at least 100 cSt.

39. The method of claim 37, wherein the viscosity at 37.8°

C. of crude product is at most 40% of the hydrocarbon feed viscosity at 37.8°

C.

40. The method of claim 37, wherein the partial pressure of hydrogen is at most 6 MPa.

41. The method of claim 37, wherein the hydrocarbon feed has an API gravity of at least 5.

42. The method of claim 37, wherein contacting conditions are controlled at a liquid hourly space velocity of at least 0.5 h⁻

1.

43. The method of claim 37, wherein at most 0.003 grams of sediment per gram of total product/hydrocarbon feed mixture is formed during contacting.

44. The method of claim 37, wherein at least one of the catalysts comprises one or more metals from Columns 6-10 of the Periodic Table and/or one or more compounds of one or more metals from Columns 6-10 of the Periodic Table.

45. The method of claim 44, wherein the Columns 6-10 metals catalyst has a total molybdenum content from 0.001 grams to 0.6 grams per gram of catalyst.

46. The method of claim 44, wherein the Columns 6-10 metals catalyst is a supported catalyst, and wherein the support comprises alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, or mixtures thereof.

47. The method of claim 44, wherein the Columns 6-10 metals catalyst has a pore size distribution with a median pore diameter from 50 angstroms to 150 angstroms.

48. The method of claim 44, wherein the Columns 6-10 metals catalyst has a surface area of at least 200 m²/g.

49. The method of claim 44, wherein the Columns 6-10 metals catalyst further comprises one or more elements from Column 15 of the Periodic Table and/or one or more compounds of one or more elements from Column 15 of the Periodic Table.

50. The method of claim 44, wherein one or more of the catalysts also includes an additional catalyst, wherein the additional catalyst comprises one or more metals from Columns 6-10 of the Periodic Table and/or one or more compounds of one or more metals from Columns 6-10 of the Periodic Table.

51. The method of claim 50, wherein the additional catalyst has a molybdenum content of at least 0.1 grams per gram of catalyst.

52. The method of claim 44, wherein contacting the hydrocarbon feed with one or more catalysts comprises:

contacting the hydrocarbon feed with the Columns 6-10 metals catalyst; and

contacting the hydrocarbon feed with an additional catalyst, wherein the additional catalyst comprises one or more metals from Columns 6-10 of the Periodic Table and/or one or more compounds of one or more metals from Columns 6-10 of the Periodic Table; and

wherein the additional catalyst is positioned downstream of the Column 6 metal catalyst.

53. The method of claim 37, wherein the hydrocarbon feed is contacted with one or more catalysts in a fixed bed reactor.

54. The method of claim 37, further comprising heating the one or more catalysts to a temperature of at least 400°

C. in a time period of less than three weeks.

55. The method of claim 54, wherein the one or more catalysts are heated prior to contacting the hydrocarbon feed with the one or more catalyst.

56. The method of claim 37, wherein the method further comprises fractionating the crude product into one or more distillate fractions, and producing transportation fuel from at least one of the distillate fractions.