Catalyst preparation reactors from catalyst precursor used for feeding reactors to upgrade heavy hydrocarbonaceous feedstocks

Patent metadata

Field	Value
Publication number	US-9233363-B2
Application number	US-201113808469-A
Country	US
Kind code	B2
Filing date	Jul 5, 2011
Priority date	Jul 6, 2010
Publication date	Jan 12, 2016
Grant date	Jan 12, 2016

Abstract

A process for upgrading heavy hydrocarbonaceous feedstocks in at least one hydroconversion reactor for hydroconversion of the heavy hydrocarbonaceous feedstocks and in at least one hydrotreatment reactor for hydrotreatment of the heavy hydrocarbonaceous feedstocks, comprising the preparation of two or more catalysts, each catalyst being prepared from one or more catalyst precursor in at least one specific preparation reactor, the catalyst precursor containing at least one transition metal selected from group IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB or IIB of the periodic table of elements, and each preparation reactor feeding one or more hydroconversion or hydrotreatment reactor, each catalyst contained in preparation reactors being dedicated to hydroconversion or hydrotreatment of the feedstocks.

First claim

The invention claimed is:

1. A process for hydroprocessing of heavy hydrocarbonaceous feedstock in at least one hydroconversion reactor for hydroconversion of said heavy hydrocarbonaceous feedstocks and in at least one hydrotreatment reactor for hydrotreatment of said heavy hydrocarbonaceous feedstocks, said process comprising the preparation of two or more catalysts, each catalyst being prepared from one or more catalyst precursors in at least one specific preparation reactor, each preparation reactor feeding one or more hydroconversion or hydrotreatment reactors, and each catalyst contained in a preparation reactor being individually dedicated to hydroconversion or hydrotreatment of said feedstock, and
wherein said catalyst(s) dedicated to hydroconversion reactor contain at least one transition metal selected from group VB, VIB, VIII, in an active state, and said catalyst(s) dedicated to hydroconversion is prepared from a precursor which is an organometallic coordination compound of formula (C 1 C 2 ML n (I), where
M is a transition metal selected from group IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB or IIB of the periodic table of elements,
—C 1 and —C 2 are monocyclic or polycyclic aryl hydrocarbon ligands that are pi-bonded to M, —C 1 and —C 2 being the same or different, each of —C 1 or —C 2 comprising from 0 to 5 substituents R, each substituent R being the same or different, R being selected from:
a C3-C8 substituted or unsubstituted monocyclic or polycyclic ring structure that is partially unsaturated unsaturated or aromatic, fused or not fused to the ligand —C 1 or —C 2 ,
a C3-C8 substituted or unsubstituted, partially unsaturated or unsaturated, linear or branched, alicyclic hydrocarbyl radical,

a C1-C8, substituted or unsubstituted, linear or branched, saturated hydrocarbyl radical,
—C 1 and —C 2 being independent or connected via at least one substituent R,
-L is a ligand that is sigma-bonded to M, n is an integer equal to 0 to 3, each -L is, independently, a univalent ligand.

2. The process according to claim 1 , wherein each preparation reactor is fed with a part of the feedstock to upgrade.

3. The process according to claim 1 , wherein each preparation reactor is fed with a sulfiding agent.

4. The process according to claim 1 , wherein each preparation reactor is fed with hydrogen.

5. The process according to claim 1 , wherein each preparation reactor is fed with a dispersant agent.

6. The process according to claim 1 , wherein each dedicated catalyst is prepared in at least two preparation reactors.

7. The process according to claim 1 , wherein said catalyst(s) dedicated to hydrotreatment contain two transition metals in an active state, one transition metal being selected from group VB, VIB, VIII and another transition metal being selected from group VIII.

8. The process according to claim 7 , wherein said catalyst(s) dedicated to hydrotreatment contain Mo and Ni, or Mo and V, or Fe and Ni.

9. The process according to claim 1 , wherein said catalyst(s) dedicated to hydroconversion contain V, Mo or Fe.

10. The process according to claim 1 , wherein said catalyst(s) dedicated to hydroconversion contain from 20 ppm to 700 ppm of transition metal.

11. The process according to claim 10 , wherein said catalyst(s) dedicated to hydroconversion contain from 250 ppm to 650 ppm of transition metal.

12. The process according to claim 11 , wherein said catalyst(s) dedicated to hydroconversion contain from 300 ppm to 600 ppm of transition metal.

13. The process according to claim 1 , wherein the whole content of transition metals in said catalyst(s) dedicated to hydrotreatment ranges from 200 to 1000 ppm.

14. The process according to claim 13 , wherein the whole content of transition metals in said catalyst(s) dedicated to hydrotreatment ranges from 250 to 900 ppm.

15. The process according to claim 14 , wherein the whole content of transition metals in said catalyst(s) dedicated to hydrotreatment ranges from 300 to 500 ppm.

16. The process according to claim 1 , wherein said catalyst precursors for said catalyst(s) dedicated to hydrotreating are selected from naphtenates, octoates, oxides.

17. The process according to claim 1 , wherein the organometallic coordination compound is a metallocene compound presenting the general formula (II) below

wherein the R substituted or unsubstituted cyclopentadienyl ligands are pi-bonded to M, and L ligands are sigma-bonded to M, and where M, L, R and n are defined as in formula (I).

18. The process according to claim 1 , wherein -L is selected from Hydride (-L =—H), Halide (-L =—F, —Cl, —Br, —I), cyanide (-L =—CN), Alkoxide (-L =—OR), Thiolate (-L =—SR), Amide (-L =—NR 2 ), Phosphide (-L =—PR 2 ), Alkyl (-L =—CH 2 R or other), Alkenyl (-L =—CHCHR), Alkynyl (-L =—CCR), Acyl (-L =—COR), Isocyanide (-L =—CNR), Nitrosyl (-L =—NO), Diazenide (-L =—NNR), Imide (-L =═NR), L =-ER 3 or -EX 3 (with E =Si, Ge, Sn), -L =—PR 3 , —PX 3 , -AsR 3 , —SbR 3 , amines, L =ER 2 (with E =O, S, Se, Te), where X is an halogen atom and R is a C1-C8, preferably a C1-C6, linear or branched, alkyl, alkenyl Group or a C3-C8 alicyclic or aromatic group.

19. The process according to claim 1 wherein M in said catalyst(s) dedicated to hydrotreating are selected from Group IIA, IIB, IIIB, IVB, VB, VIB, VIIB or VIII of the periodic table of the elements.

20. The process according to claim 1 , wherein said carbonaceous feedstocks comprise an atomic H/C ratio of at least 0.25.

Assignees

• Borremans Didier
• Lacroix Maxime
• Le Lannic-Dromard Katell
• Vendrell Gloria
• Total Marketing Services

Inventors

• Borremans Didier
• Lacroix Maxime
• Le Lannic-Dromard Katell
• Vendrell Gloria

Classifications

• C10G49/04

  containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof · CPC title

• C10G65/12

  including cracking steps and other hydrotreatment steps · CPC title

• B01J2531/64

  Molybdenum · CPC title

• C10G65/02

  plural serial stages only · CPC title

• B01J2231/646

  of aromatic or heteroaromatic rings · CPC title