Process of hydro-refining hydrocarbon oils

• US 4,008,149 A
• Filed: 03/19/1976
• Issued: 02/15/1977
• Est. Priority Date: 04/18/1975
• Status: Expired due to Term

• Current Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
• Original Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
• Inventors: Sakurada, Satoshi, Itoh, Takuji, Obayashi, Takashi, Okano, Shohei
• Primary Examiner(s): Crasanakis, George
• Application Number:
  US05/668,609
• Time in Patent Office: 333 Days
• Field of Search: 208/216, 208/217, 208/111, 208/254 H, 208/251 H
• US Class Current: 208/216.0PP
• CPC Class Codes: B01J 23/88 Molybdenum
• CPC Class Codes: B01J 23/882 and cobalt
• 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 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 35/67 monomodal
• CPC Class Codes: C10G 45/08 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof

Abstract

A hydro-refining catalyst comprising at least one hydrogenation metal component supported on an alumina or alumina-containing carrier containing from about 5 to about 25 wt. % silica, said catalyst having a specific surface area in the range of from about 250 to about 300 m² /g and a pore volume distribution characterized in that (1) the volume of pores having a diameter of 60 to 150 A is at least about 80% of the volume of pores having a diameter of 0 to 150 A, (2) the volume of pores having a diameter of 150 to 300 A is less than about 20% of the volume of pores of 0 to 300 A, (3) the volume of pores having a diameter of 150 to 2,000 A is less than about 0.01 ml/g, (4) the volume of pores having a diameter of 0 to 600 A is in the range of from about 0.45 to about 0.60 ml/g. The catalyst is used in the hydro-refining of heavy hydrocarbon oils containing sulfur, nitrogen and metal contaminants.

Claims

1. A process for hydro-refining hydrocarbon oils which comprises contacting a hydrocarbon oil containing sulfur compounds, nitrogen compounds, asphalt and metal-containing compounds with hydrogen and with a hydro-refining catalyst under hydro-refining reaction conditions to remove sulfur, nitrogen and metals from said oil, said catalyst comprising at least one hydrogenation metal selected from Group VI-B and at least one hydrogenation metal selected from Group VIII of the Periodic Table supported on an alumina carrier containing from about 5 to about 25 weight % silica, said catalyst having a specific surface area in the range of from about 250 to about 300 m² /g and a pore volume distribution characterized in that (1) the volume of pores having a diameter of 60 - 150A is at least about 80% of the volume of pores having a diameter of 0 - 150A, (2) the volume of pores having a diameter of 150-300A is less than about 20% of the volume of pores of 0 - 300A, (3) the volume of pores having a diameter of 0 - 600A is in the range of from about 0.45 to about 0.60 ml/g, as measured by the nitrogen adsorption method, and (4) the volume of pores having a diameter of 150 - 2000A as measured by the mercury porosimetric method, is less than about 0.01 ml/g.

2. A process according to claim 1 wherein said hydrocarbon oil is selected from the group consisting of atmospheric residual oils, vacuum residual oils, vacuum gas oil, heavy cracking oils and mixtures thereof.

3. A process according to claim 1 wherein said hydro-refining reaction conditions include a reaction temperature of from about 350°

to about 450°

C., a reaction pressure of from about 30 to about 200 Kg/cm², a hydrogen-containing gas flow rate of from about 50 to about 1500 1/1 and a liquid space velocity of from about 0.2 to about 2.0 V/h/V.

4. A process according to claim 1 wherein said catalyst is presulfided before said contacting with said hydrocarbon oil.

5. A process according to claim 1 wherein said hydrogenation metal comprises metal oxide or metal sulfide of said Group VI-B metal and said Group VIII metal.

6. A process according to claim 5 wherein said carrier contains from about 8 to about 20 weight % silica.

7. A process according to claim 1 wherein said hydrogenation metal comprises a mixture of molybdenum and cobalt.

8. A process according to claim 1 wherein said hydrogenation metal comprises a mixture of molybdenum and nickel.

9. A process according to claim 1 wherein said carrier contains from about 1 to about 10 weight % based on the alumina of a refractory inorganic oxide selected from the group consisting of magnesia, calcium oxide, zirconia, titania, boria, hafnia and crystalline zeolites.

10. A process according to claim 1 wherein said hydrogenation metal comprises from about 0.1 to about 20 weight %, based on the catalyst, of a Group VIII metal and from about 5 to about 20 weight %, based on the catalyst, of a Group VI metal.