Hydrotreatment catalyst, method for production and use thereof
View Patent ↗The invention relates to a catalyst for hydroconversion of hydrocarbons, comprising a support made from at least one refractory oxide, at least one group VIII metal and at least one group VIB metal, characterized in further comprising at least one organic compound with at least two thiol functions separated by at least one oxygenated group of formula (I): HS—CxHyOz—SH (I), where x=1 to 20, preferably 2 to 9 and for example x=6, y=2 to 60, preferably 4 to 12 and z=1 to 10, preferably 1 to 6. The invention further relates to a method for preparation, a method for activation of said catalyst and use of the catalyst for the hydrotreatment and/or hydrocracking of hydrocarbons.
1. A hydrotreating catalyst comprising a support 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 the Elements, characterized in that it further includes at least one organic compound comprising at least two thiol functional groups separated by at least one oxygen-containing group of formula (I):
HS—C X H y O z —SH (I)
in which x is an integer from 1 to 20, y is an integer from 2 to 60, and z is an integer from 1 to 10, and in which at least one oxygen-containing group is a ketone or ether functional group.
2. The catalyst as claimed in claim 1 , characterized in that the oxygen-containing group(s) is (are) a ketone or ether functional group.
3. The catalyst as claimed in claim 1 , characterized in that at least one oxygen-containing group is an ether functional group.
4. The catalyst as claimed in one of the preceding claims, characterized in that the organic compound of formula (I) is chosen from 2-mercaptoethyl ether and 1,8-dimercaptodioxaoctane (DMDO).
5. The catalyst as claimed claim 1 , characterized in that the organic compound of formula (I) is 1,8-dimercaptodioxaoctane (DMDO).
6. The catalyst as claimed in claim 1 , comprising 0.1 to 10% by weight of a metal of Group VIII, and 1 to 20% by weight of a metal of Group VIB.
7. The catalyst as claimed in claim 1 , comprising at least 0.001 mol of organic compound(s) of formula (I) per mole of metals of Groups VIB and VIII.
8. A method of preparing a hydrotreating catalyst as claimed in claim 1 , which comprises bringing a catalyst, comprising a support based on at least one refractory oxide, at least one compound of a metal of Group VIII and at least one compound of a metal of Group VIB, into contact with at least one organic compound comprising at least two thiol functional groups separated by at least one oxygen-containing group of formula (I):
HS—C X H y O z —SH (I)
in which x is an integer from 1 to 20, y is an integer from 2 to 60, and z is an integer from 1 to 10, and in which at least one oxygen-containing group is a ketone or ether functional group.
9. The method of preparation as claimed in claim 8 , characterized in that at least one oxygen-containing group is an ether functional group.
10. The method of preparation as claimed in either of claims 8 or 9 , characterized in that the catalyst comprising a support based on at least one refractory oxide, at least one compound of a metal of Group VIII and at least one compound of a metal of Group VIB is a regenerated catalyst.
11. The method of preparation as claimed in claim 8 , such that the contacting step is followed by at least one maturation step at a temperature from 0 to 100° C., the duration of which is from a few minutes to a few years, said maturation step being optionally followed by at least one heat treatment step at a temperature of 50 to 250° C. and of a duration of a few minutes to a few days.
12. The method of preparation as claimed in claim 8 , characterized in that the step of bringing the catalyst into contact with the compound(s) of formula (I) takes place in the presence of at least one solvent and/or at least one acid.
13. The method of preparation as claimed in claim 12 , characterized in that the organic compound(s) of formula (I) is (are) at least partly soluble in the solvent used.
14. The method of preparation as claimed in either of claim 12 or 13 , characterized in that the solvent is chosen from water, toluene, xylenes, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, ethanol, tert-butanol, polyethylene glycol (PEG), white spirit and petroleum ether.
15. The method of preparation as claimed in claim 14 , characterized in that said polyethylene glycol (PEG) has a molecular weight of from 118 to 1000.
16. The method of preparation as claimed in claim 8 , characterized in that the step of bringing the catalyst into contact with the compound(s) of formula (I) takes place ex situ, outside a hydrotreatment reactor.
17. The method of preparation as claimed in claim 8 , characterized in that the step of bringing the catalyst into contact with the compound(s) of formula (I) takes place in the presence of hydrogen and at least one sulfurizing agent within a hydrotreatment reactor.
18. The method of preparation as claimed in claim 8 , characterized in that the oxygen-containing group(s) is (are) a ketone or ether functional group.
19. A method for the in situ or ex situ activation of a hydrotreating catalyst as claimed in claim 1 or prepared as claimed in claim 8 , characterized in that said catalyst is brought into the presence of hydrogen and at least one sulfurizing agent.
20. A method for hydrotreatment and/or hydrocracking of hydrocarbons, comprising contacting said hydrocarbons with a catalyst activated by the method as claimed in claim 19 .