Bulk catalyst comprising metal oxidic particles and a process for the manufacture thereof
The invention relates to a bulk catalyst having improved activity in hydrodesulphurization, in particular in relatively low Group VIII over Group VIB metal molar ratios. The bulk catalyst comprises metal oxidic particles comprising one or more Group VIB metals and one or more-Group VIII metals which metal oxidic particles are obtainable by a process comprising the steps of reacting the compounds comprising one or more Group VIB metals and compounds comprising one or more Group VIII metals in hydrothermal conditions at a reaction temperature above the boiling temperature of the protic liquid, preferably in an autoclave at a reaction pressure above atmospheric pressure and. The invention also relates to the corresponding sulphided catalyst, to a process for the manufacture of said bulk catalyst and to the use of said catalyst for the hydrotreatment, in particular the hydrodesulphurization and hydrodenitrogenation of hydrocarbon feedstock.
1. A bulk catalyst comprising metal oxidic particles comprising one or more Group VIB metals and one or more Group VIII metals obtainable by a process comprising the steps of
i) combining in a reaction mixture one or more first compounds comprising one or more Group VIII metals and one or more second compounds comprising one or more Group VIB metals in the presence of a protic liquid, wherein the Group VIII metals to Group VIB metals molar ratio is below 1, and
ii) reacting the compounds under hydrothermal conditions at a reaction temperature above the boiling temperature of the protic liquid to form metal oxidic particles.
2. The bulk catalyst according to claim 1 , wherein the reaction pressure is above atmospheric pressure.
3. The bulk catalyst according to claim 1 , wherein the protic liquid is water and the reaction is done in hydrothermal conditions at a reaction temperature above 100° C. and a reaction pressure higher than 1 bar.
4. The bulk catalyst according to claim 1 , wherein the one or more first metal compounds and the one or more second metal compounds remain at least partly in the solid state during the entire reaction.
5. The bulk catalyst according to claim 1 , wherein the metal oxidic particles are dried and/or heat treated at a temperature below 375° C.
6. The bulk catalyst according to claim 1 , wherein the reaction mixture comprises a Group V metal.
7. The bulk catalyst according to claim 1 , wherein the metal oxidic particles comprise essentially one Group VIII metal, and essentially 2 Group VIB metals.
8. The bulk catalyst according to claim 1 , wherein the metal oxidic particles comprise essentially one Group VIII metal, and essentially one Group VIB metal.
9. A sulphided bulk catalyst characterized in that it is a bulk catalyst according to claim 1 that has been sulphided.
10. A process comprising reacting a hydrocarbon feedstock in the presence of hydrogen at elevated temperatures and elevated pressures with the bulk catalyst or sulphided bulk catalyst according to claim 1 .
11. A process for the manufacture of the bulk catalyst according to claim 1 , comprising metal oxidic particles obtainable by the steps of:
i) combining in a reaction mixture one or more first compounds comprising one or more Group VIII metals and one or more second compounds comprising one or more Group VIB metals in the presence of a protic liquid, wherein the Group VIII metals to Group VIB metals molar ratio is below 1, and
ii) reacting the compounds under hydrothermal conditions at a reaction temperature above the boiling temperature of the protic liquid at a reaction pressure above atmospheric pressure, to form metal oxidic particles,
the process further optionally comprising one or more of the following process steps:
iii) separating the metal oxidic particles from the reaction mixture,
iv) compositing the metal oxidic particles with 0.1 to 40 wt % of one or more materials selected from the group of binder materials, conventional hydroprocessing catalysts, cracking compounds, acidic promoters or mixtures thereof before, during or after the combining and/or reacting of the metal compounds,
v) spray-drying, (flash) drying, milling, kneading, slurry-mixing, dry or wet mixing, or combinations thereof,
vi) shaping,
vii) drying and/or thermally treating, and
viii) sulphiding.
12. The process according to claim 11 , wherein both the first and second metal compounds remain at least partly in the solid state during the entire reaction.
13. The process according to claim 12 , wherein both the first and second metal compounds are free from nitrogen atoms and wherein protic liquid separated from the obtained metal oxidic particles after the reaction (step iii) is re-used at least in part to form the reaction mixture in step i).