Process For Preparing a Catalytic Composition For the Hydroconversion of Petroleum Fractions

• US 20080280754A1
• Filed: 08/22/2006
• Published: 11/13/2008
• Est. Priority Date: 08/31/2005
• Status: Active Grant

• Current Assignee: Instituto Mexicano Del Petrã³Leo (Gobierno Federal De Los Estados Unidos Mexicanos)
• Original Assignee: Instituto Mexicano Del Petrã³Leo (Gobierno Federal De Los Estados Unidos Mexicanos)
• Inventors: Lozada y Cassou, Marcelo, Cortes Jacome, Maria Antonia, Angeles Chavez, Carlos, Lopez Salinas, Esteban, Ferrat Torres, Gerardo, Toledo Antonio, Jose Antonio, Mosqueira Mondragon, Maria de Lourdes, Perez Luna, Miguel, Escobar Aguilar, Jose, Mora Vallejo, Rodolfo Juventino, Perez Moreno, Victor
• Granted Patent: US 8,946,110 B2
• Time in Patent Office: Days
• US Class Current: 502/177
• CPC Class Codes: B01J 23/85 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 23/883 and nickel
• CPC Class Codes: B01J 27/0515 with iron group metals or platinum group metals
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 37/0018 Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• CPC Class Codes: B01J 37/03 Precipitation; Co-precipitation
• CPC Class Codes: B01J 37/084 Decomposition of carbon-containing compounds into carbon
• CPC Class Codes: B01J 37/20 Sulfiding
• CPC Class Codes: C10G 45/08 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C10G 45/50 in combination with chromium, molybdenum or tungsten metal, or compounds thereof

Abstract

The invention relates to a method of preparing a catalytic composition comprising at least one non-noble metal from group VIII and at least one metal from group VIB of the periodic table. The invention also relates to the catalytic composition thus produced, which has a high specific activity in reactions involving the hydroprocessing of light and intermediate fractions, preferably in reactions involving the hydrotreatment of hydrocarbon streams, including hydrodesulphurisation (HDS), hydrodenitrogenation (HDN) and hydro-dearomatisation (HDA).

Claims

1. A process for the preparation of a catalytic composition made up of at least one Group VIII non-noble metal and at least one Group VIB metal, and of an organic compound as a carbon precursor, which are found in a completely soluble state in a solvent.

2. The preparation process in accordance with claim 1, which consists of the following stages:

a) Solution and mixture of the precursor salts in a solvent that may be water, alcohol, such as methanol, ethanol, propanol, butanol, and/or water-alcohol mixture;

b) Solution of the organic component and/or surface active agent in the solvent;

c) Mixture of the solutions obtained in subsections (a) and (b);

d) Addition of a basic hydroxide solution and/or ammonium carbonate to the solution (c) at a pH comprised between 5 and 14, preferably from 8 to 12;

e) Increase in the temperature for the solution obtained in subsection (d) to a temperature comprised between 50 and 200°

C., preferably between 60 and 100°

C.;

f) Homogenization of the solution in subsection (e);

g) Crystallization of the solution obtained in subsection (f) through evaporation of the solvent;

h) Filtering or centrifugation of the crystallized suspension obtained in subsection (g) for the separation of the crystals and recovery of mother liquors in the event that the evaporation has not been completed;

i) Washing of the solid obtained in subsection (h) with sufficient deionized water and/or water/alcohol mixture;

j) Drying of the solid obtained in subsection (i) at a temperature comprised between 50 and 300°

C., preferably from 80 to 150°

C.;

k) Thermal treatment of the solid obtained in subsection (j) in inert atmosphere, such as nitrogen, helium, argon, etc., at a temperature comprised between 200 and 1000°

C., preferably between 300 and 600°

C.;

l) Sulfiding of the material obtained whether it be in subsection (i) or in subsection (j) in a gaseous flow made up of 10 vol. % hydrogen sulfide or with a hydrocarbon fraction containing at least 0.2 wt. % in of sulfur with a hydrogen flow at a temperature comprised between 200 and 600°

C., preferably from 250 to 500°

C., and a pressure comprised between 1 and 100 Kg/cm².

3. The preparation process in accordance with claim 1, in which all the Group VIII metal and Group VIB metal precursor salts are found completely dissolved in a liquid used as solvent.

4. The preparation process in accordance with claim 1, in which the completely dissolved precursor salts are mixed with a solution that contains an organic compound.

5. The preparation process in accordance with claim 1 where the solvent used comprises water and/or alcohol and/or alcohol-water mixture.

6. The preparation process in accordance with claim 1, where the organic compound added comprises a surface active agent such as a cationic, anionic, or neutral surfactant, or a quaternary ammonium salt (R4N⁺) that may be in its chloride, bromide, fluoride, hydroxide, etc. form.

7. The preparation process in accordance with claim 1, where the Group VIII non-noble metal includes nickel, cobalt, and/or iron, or a mixture of these metals.

8. The preparation process in accordance with claim 7, where the nickel and/or cobalt represent 100 wt. % of the Group VIII non-noble metals calculated as oxides.

9. The preparation process in accordance with claim 1, where the Group VIB metal includes molybdenum and/or tungsten and/or chromium.

10. The preparation process in accordance with claim 1, where the molybdenum represents at least 50 wt. % of the Group VIB metals selected, preferably at least 80 wt. %;

and more preferably, 100 wt. % of the Group VIB metals is molybdenum.

11. The preparation process in accordance with claim 2 that comprises a stage of addition of a basic solution that may be selected from a hydroxide and/or ammonium carbonate and/or urea or a quaternary ammonium salt, in order to maintain a pH between 5 and 14, preferably between 8 and 12.

12. The preparation process in accordance with claim 2, where the homogenization stage of the solutions takes place at a temperature and at a pH such that all the selected precursor salts are found in a completely soluble state.

13. The preparation process in accordance with claim 2, where the homogenization stage of the solutions takes place at a time comprised between 5 min and 24 h, preferably between 5 min and 10 h.

14. The preparation process in accordance with claim 2, where the solution'"'"'s crystallization stage is carried out by partial evaporation of the solvent to a crystallizer and/or by total evaporation of the solvent in an evaporator.

15. The preparation process in accordance with claim 2, where the solution'"'"'s crystallization stage is carried out by evaporation of the solvent at a temperature comprised between 80 and 200°

C.

16. The preparation process in accordance with claim 2, where a stage for filtering and/or centrifugation, recovery, and recirculation of mother liquors is included in the event that the evaporation and/or crystallization has not been complete.

17. The preparation process in accordance with claim 2, where the thermal treatment in inert atmosphere stage is carried out at a temperature comprised between 200 and 1000°

C., preferably between 300 and 600°

C., in a flow of nitrogen, helium, argon, or mixture of them, with a flow of at least 0.01 L/g.min.

18. The preparation process in accordance with claim 2, where the thermal treatment should not be carried out in oxidizing atmosphere for any reason.

19. The preparation process in accordance with claim 2, where the sulfiding stage is carried out directly on the dry material, without any previous thermal treatment.

20. The preparation process in accordance with claim 2, where the sulfiding stage is carried out on the thermally treated material in inert atmosphere.

21. The preparation process in accordance with claim 2, where the sulfiding stage is carried out either on the dry or thermally treated material in gaseous flow made up of a mixture of hydrogen sulfide (H₂S), carbon disulfide (C₂S), dimethyl disulfide (DMDS), thiophene, etc., and hydrogen at a temperature comprised between 200 and 600°

C., preferably between 250 and 500°

C. at atmospheric pressure.

22. The preparation process in accordance with claim 2, where the sulfiding stage is carried out either on the dry or thermally treated material in the presence of a liquid fraction of hydrocarbons that contains at least 0.1 wt. % of sulfur and hydrogen at pressures comprised between 1 and 100 Kg/cm², at temperatures comprised between 200 and 600°

C., preferably between 250 and 500°

C.

23. The preparation process in accordance with claim 2 including an inorganic oxide like a binder such as alumina, silica, titania, silica-alumina, alumina-titania, zirconia, zirconia-titania, zirconia-alumina, amorphous silico-aluminates, and/or crystallines, clays in the homogenization stage of the mixture of precursor salts.

24. The preparation process in accordance with claim 2 that considers the addition of an inorganic oxide like a binder, after the crystallization stage in the wet and/or dry material.

25. The preparation process in accordance with claim 2 that considers the addition of an inorganic oxide as a binder, after the material has been thermally treated and/or sulfided.

26. The preparation process in accordance with claim 2 that considers the formulation of extrudes in the material containing an inorganic oxide like a binder added in any of the stages.

27. The catalytic composition that includes at least one Group VIII non-noble metal, at least one Group VIB non-noble metal, and carbon;

and optionally, may contain an inorganic oxide as a binder that can be in its oxidized state and/or partially reduced and/or sulfided.

28. A catalytic composition in accordance with claim 27, where the Group VIII non-noble metal corresponds to nickel and/or cobalt or a mixture of them, whose concentration varies between 20 and 50 wt. % of the total composition of the oxides involved.

29. A catalytic composition in accordance with claim 27, where the Group VIB metal corresponds preferably to molybdenum and/or tungsten, whose composition varies between 30 and 50% of the total composition determined as oxides of the metals involved.

30. A catalytic composition in accordance with claim 29, where the Group VIB metal is preferably molybdenum.

31. A catalytic composition in accordance with claim 27, where the carbon is found in an amorphous state, or forming carbides with the Group VIB and Group VIII metals, whose concentration varies between 0.05 and 5 wt. % of the total concentration of the oxides involved.

32. A catalytic composition in accordance with the claim 27, in which the Group VIII and the Group VIB metals comprise between 50 and 100 wt. % of the total catalytic composition determined as oxides.

33. A catalytic composition in accordance with claim 27, whose x-ray diffraction pattern corresponds to the alpha or beta molybdate phase of the Group VIII metal, in the event that the metal selected from the Group VIB is molybdenum an/or tungstate of the Group VIII metal in the event that the metal selected is tungsten.

34. A catalytic composition in accordance with claim 27, whose x-ray diffraction pattern corresponds to the alpha or beta nickel molybdate phase, or cobalt molybdate or nickel molybdate and cobalt, in the event that the metal selected from Group VIB is molybdenum and/or tungstate or cobalt tungstate, or nickel cobalt tungstate in the event that the metal selected from Group VIB is tungsten.

35. A catalytic composition in accordance with claim 27 that includes the sulfides of at least one Group VIII non-noble metal, and the sulfides of at least one Group VIB metal, and/or mixed sulfides of Group VIII and Group VIB metals.

36. A catalytic composition in accordance with claim 35, wherein at least part of the Group VIB metal sulfides and the Group VIII metal sulfides present a morphology of fullerene nanospheres with a stacking level between 2 and 20 structural layers.

37. A catalytic composition in accordance with claim 27 characterized because it presents a high hydrodesulfuration, hydrogenating, and hydrodenitrogenating activity in hydroprocessing reactions of hydrocarbon fractions.

38. A catalytic composition in accordance with claim 27, characterized because it presents a high activity toward hydrodesulfuration and hydrodenitrogenation for the production of fuels with ultra low sulfur and nitrogen contents.