Hydroprocessing catalyst, preparation method thereof and use of same

Patent metadata

Field	Value
Publication number	US-9821302-B2
Application number	US-201514859888-A
Country	US
Kind code	B2
Filing date	Sep 21, 2015
Priority date	Jan 20, 2005
Publication date	Nov 21, 2017
Grant date	Nov 21, 2017

Abstract

The invention relates to a hydrocarbon hydroprocessing catalyst comprising a support based on at least one refractory oxide, at least one metal from group VIII and at least one metal from group VIB. The inventive catalyst is characterized in that it also comprises at least one organic compound having formula (I) or (II):

in which each R 1 represents independently an alkyl group at C 1-18 , an alkenyl group at C 2-18 , an aryl group at C 6-18 , a cycloalkyl group at C 3-8 , an alkylaryl or arylalkyl group at C 7-20 , or the two R 1 groups together form a divalent group at C 2-18 , and R 2 represents an alkylene group at C 1-18 , an arylene group at C 6-18 , a cycloalkylene group at C 3-7 , or a combination of same. The invention also relates to a method of preparing one such catalyst and to the use thereof for hydroprocessing or hydrocracking.

First claim

The invention claimed is:

1. An activated hydroprocessing catalyst comprising a carrier based on at least one refractory oxide, at least one metal of group VIII and at least one metal of group VIB of the Periodic Table of Elements, and at least one organic compound represented by formula (I), the at least one organic compound having at least two carboxylic ester functions and
wherein the activated catalyst is prepared by bringing the at least one organic compound in contact with a regenerated catalyst which comprises the at least one refractory oxide, at least one metal of group VIII and at least one metal of Group VIB followed by activation by sulfurization,

in which
each R 1 independently represents a C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 6 -C 18 aryl, C 3 -C 8 cycloalkyl, C 7 -C 20 alkylaryl or C 7 -C 20 aryalkyl group, or the two R 1 groups together form a C 2 -C 18 divalent group, and R 2 in formula (I) represents a C 1 -C 18 alkylene, C 7 -C 18 arylene or C 3 -C 7 cycloalkylene group, or a combination thereof, it being possible for the carbon chain of the hydrocarbon-based groups represented by R 1 and R 2 to contain or bear one or more heteroatoms selected from N, S and O, and for each of the groups R 1 and R 2 to bear one or more substituents of formula —C(═O)O—R 1 or —O—C(═O)—R 1 where R 1 has the meaning indicated above,
wherein the hydroprocessing catalyst has been subjected to a thermal treatment at a temperature between 60° C. and 180° C. following impregnation step during preparation of the hydroprocessing catalyst.

2. The activated hydroprocessing catalyst as claimed in claim 1 , wherein the organic compound of formula (I) is selected from malonic acid esters, adipic acid esters, glutaric acid esters, 1,6-dioxacyclodecane-2,5-dione, dimethyl 2-(methoxymethyl)succinate, dibutyl itaconate, diethyl 2,3-diacetylsuccinate, dimethyl cyclohexane-1,4-dicarboxylate, and dimethyl 3,3′-dithiodipropionate.

3. The activated hydroprocessing catalyst as claimed in claim 1 , wherein the number of carbon atoms separating the two groups >C═O of formula (I) is equal to 1, 2 or 4.

4. The activated hydroprocessing catalyst as claimed in claim 3 , wherein the organic compound of formula (I) is a C 1 -C 4 dialkyl succinate.

5. The activated hydroprocessing catalyst as claimed in claim 4 , wherein the organic compound of formula (I) is dimethyl succinate.

6. The activated hydroprocessing catalyst as claimed in claim 3 , wherein the number of carbon atoms separating the two groups >C═O of formula (I) is equal to 1 or 2.

7. The activated hydroprocessing catalyst as claimed in claim 1 , wherein the catalyst comprises at least 0.001 mol of at least one organic compound per mole of metals of groups VIB and VIII.

8. The activated hydroprocessing catalyst as claimed in claim 7 , wherein the catalyst comprises from 0.001 to 10 mol of at least one organic compound per mole of metals of groups VIB and VIII.

9. A method for preparing an activated hydroprocessing catalyst according to claim 1 , comprising in this order:
a step of bringing a regenerated catalyst comprising a carrier based on at least one refractory oxide, at least one metal of group VIII in the oxide state and at least one metal of group VIB in the oxide state into contact with at least one organic compound of formula (I)

in which
each R 1 independently represents a C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 6 -C 18 aryl, C 3 -C 8 cycloalkyl, C 7 -C 20 alkylaryl or C 7 -C 20 arylalkyl group, or the two R 1 groups together form a C 2 -C 18 divalent group, and R 2 in formula (I) represents a C 1 -C 18 alkylene, C 7 -C 18 arylene or C 3 -C 7 cycloalkylene group, or a combination thereof, it being possible for the carbon chain of the hydrocarbon-based groups represented by R 1 and R 2 to contain or bear one or more heteroatoms selected from N, S and O, and for each of the groups R 1 and R 2 to bear one or more substituents of formula —C(═O)O—R 1 or —O—C(═O)—R 1 where R 1 has the meaning indicated above, and
a step of activating the catalyst by sulfurization.

10. The method as claimed in claim 9 , wherein the step of bringing the at least one organic compound in contact with the catalyst is followed by at least one maturation step, at a temperature from 0 to 100° C., the duration of which is between a few minutes and a few years, said maturation step being optionally followed by at least one heat treatment step, at a temperature of from 60° C. and 180° C., and lasting from a few minutes to several days.

11. The method as claimed in claim 9 , wherein the catalyst is brought into contact with the compound(s) of formula (I) in the presence of at least one solvent and of at least one acid.

12. The method as claimed in claim 9 , wherein the organic compound(s) of formula (I) are at least partially soluble in the solvent.

13. The method as claimed in claim 11 , wherein the solvent is selected from water, toluene, xylenes, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, ethanol, tert-butanol, polyethylene glycol (PEG) white spirit and petroleum ether.

14. The method of preparation as claimed in claim 13 , wherein the solvent has a molecular weight from 118 to 1000.

15. The method of preparation as claimed in claim 14 , wherein the solvent is triethylene glycol.

16. The method of claim 12 , wherein the solvent is polyethylene glycol having a molecular weight from 118 to 1000.

17. The method of claim 16 , wherein the solvent is triethylene glycol.

18. The method as claimed in claim 9 , wherein the catalyst is brought into contact with the compound(s) of formula (I) ex situ, outside the hydroprocessing reactor.

19. The method as claimed in claim 9 , wherein the activation step comprises placing the catalyst in the presence of hydrogen and of at least one sulfurization agent preferably selected from hydrogen sulfide, elemental sulfur, CS 2 , mercaptans, sulfides and polysulfides, and hydrocarbon fractions with a boiling point of less than 400° C. containing sulfur compounds.

20. The method as claimed in claim 9 , wherein the sulfurization agent is dimethyl disulfide.

21. The method as claimed in claim 9 , wherein the catalyst is brought into contact with the compound(s) of formula (I) in the presence of at least one solvent or of at least one acid.

22. A method of using the activated hydroprocessing catalyst of claim 1 , the method comprising a step of bringing the activated catalyst in contact with hydrocarbons derived from petroleum fractions with a boiling point of between 40° C. and 560° C.

Assignees

• Total Marketing Services
• Ifp Energies Now
• Total Raffinage France

Inventors

• Cholley Thierry
• Dath Jean-Pierre
• Brun Claude
• Fremy Georges
• Humblot Francis

Classifications

• C10G45/08

  in combination with chromium, molybdenum, or tungsten metals, or compounds thereof · CPC title

• B01J23/882

  and cobalt · CPC title

• B01J37/0203

  the impregnation liquid containing organic compounds · CPC title

• B01J31/0209 Primary

  Esters of carboxylic or carbonic acids · CPC title

• B01J23/85

  Chromium, molybdenum or tungsten · CPC title