Heavy oil hydroprocessing with group VI metal slurry catalyst

Abstract

A process for the preparation of a dispersed Group VIB metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting aqueous ammonia and a Group VIB metal compound, such as molybdenum oxide or tungsten oxide, to form water soluble compounds such as aqueous ammonium molybdates or tungstates. The aqueous ammonium molybdates or tungstates are sulfided at a relatively low temperature with hydrogen sulfide without feed oil. The slurry stream is then passed through a separator and ammonia is flashed and separated from the system, leaving a separator residue slurry. The separator residue slurry is then mixed with feed oil, hydrogen and hydrogen sulfide and sulfided at a relatively high temperature to produce a dispersed molybdenum sulfide or tungsten sulfide catalyst of high hydroprocessing activity. The catalyst slurry and feed oil can then be passed to a hydroprocessing reactor.

Description

Claims

1. A process comprising the preparation of a dispersed Group VIB metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a Group VIB metal compound in water to form an aqueous ammonium Group VIB metal compounds, reacting said aqueous ammonium Group VIB metal compounds with hydrogen sulfide essentially in the absence of feed oil in a low temperature sulfiding step at a temperature in the range 70.degree. to 350.degree. F., continuing the reaction of aqueous ammonium Group VIB metal compound with hydrogen sulfide in an intermediate temperature sulfiding step at a temperature in the range 180.degree. to 700.degree. F. which is higher than the temperature in said low temperature sulfiding step and essentially without feed oil, withdrawing an aqueous effluent stream from said intermediate temperature sulfiding step, passing said effluent stream to a separator zone, removing ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil and hydrogen sulfide to a high temperature sulfiding step wherein said oil is hydroprocessed at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said intermediate temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and withdrawing from said high temperature sulfiding step an aqueous-oil slurry containing dispersed Group VIB metal sulfide slurry catalyst.

2. The process of claim 1 including passing said aqueous oil slurry containing dispersed Group VIB metal sulfide slurry catalyst to a hydroprocessing reactor wherein said hydroprocessing reactor is operated at a temperature which is higher than the temperature in said high temperature sulfiding step.

3. A process comprising the preparation of a dispersed Group VIB metal sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a Group VIB metal compounds in water to form an aqueous ammonium Group VIB metal compounds, reacting said aqueous ammonia Group VIB metal compounds with hydrogen sulfide in a low temperature sulfiding step at a temperature in the range 70.degree. to 350.degree. F. substantially in the absence of feed oil, withdrawing an aqueous effluent stream from said low temperature sulfiding step, passing said aqueous effluent stream to a separator zone, removing ammonia from said effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a high temperature sulfiding step wherein said oil is hydroprocessed operated at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said low temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and withdrawing an aqueous-oil slurry containing dispersed Group VIB metal sulfide slurry catalyst.

4. The process of claim 3 including passing said aqueous-oil slurry containing dispersed Group VIB metal sulfide slurry catalyst to a hydroprocessing reactor wherein said hydroprocessing reactor is operated at a temperature which is higher than the temperature in said high temperature sulfiding step.

5. A process comprising the preparation of a dispersed molybdenum sulfide or tungsten sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting a thiosubstituted ammonium molybdate or ammonium tungstate, water, and hydrogen sulfide substantially in the absence of feed oil in a zone at a relatively low temperature in the range 70.degree. to 350.degree. F., withdrawing an aqueous effluent stream from said relatively low temperature zone, passing said effluent stream to a separator zone, removing ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a high temperature sulfiding zone wherein said oil is hydroprocessed at a temperature in the range of 500.degree. to 750.degree. F., the residence time in each of said sulfiding zones being at least 0.02 hours and removing an aqueous-oil slurry containing dispersed Group VIB metal sulfide catalyst.

6. The process of claim 5 including passing said aqueous-oil slurry containing dispersed Group VIB metal sulfide slurry catalyst to a hydroprocessing reactor wherein said hydroprocessing reactor is operated at a temperature in the range of 650.degree. to 950.degree. F. which is higher than the temperature in said high temperature sulfiding zone.

7. A process comprising the preparation of a dispersed molybdenum sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a molybdenum compound in water to form aqueous ammonium molybdates, reacting said aqueous ammonium molybdates with hydrogen sulfide essentially in the absence of feed oil in a low temperature sulfiding step at a temperature in the range of 70.degree. to 350.degree. F., continuing the reaction with hydrogen sulfide in an intermediate temperature sulfiding step at a temperature in the range 180.degree. to 700.degree. F. essentially without feed oil, said intermediate temperature sulfiding step operated at a temperature which is higher than the temperature in said low temperature sulfiding step, withdrawing an aqueous effluent stream from said intermediate temperature sulfiding step, passing said effluent stream to a separator zone, removing ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a high temperature sulfiding step at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said intermediate temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, withdrawing from said high temperature sulfiding step an aqueous-oil slurry containing dispersed molybdenum sulfide slurry catalyst and passing said catalyst to a hydroprocessing step.

8. The process of claim 7 wherein said hydroprocessing step is operated at a temperature higher than the temperature in said high temperature sulfiding step.

9. The process of claim 8 wherein said hydroprocessing step is operated at a temperature in the range of 650.degree. F. to 950.degree. F.

10. A process comprising the preparation of a dispersed molybdenum sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a molybdenum compound in water to form aqueous ammonium molybdate, reacting said aqueous ammonium molybdate with hydrogen sulfide in a low temperature sulfiding step at a temperature in the range 70.degree. to 350.degree. F. substantially in the absence of feed oil, withdrawing an aqueous effluent stream from said low temperature sulfiding step, passing said aqueous effluent stream to a separator zone, separating ammonia from said effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a high temperature sulfiding step wherein said oil is hydroprocessed at a temperature between 500.degree. and 750.degree. F., the residence time in each of said sulfiding steps being at least 0.02 hours, and withdrawing an aqueous-oil slurry containing dispersed molybdenum sulfide slurry catalyst.

11. The process of claim 10 including passing said aqueous-oil slurry containing dispersed molybdenum sulfide catalyst to a hydroprocessing step wherein said hydroprocessing step is operated at a temperature which is higher than the temperature in said sulfiding step.

12. A process comprising the preparation of a dispersed molybdenum sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting thiosubstituted ammonium molybdate, water, and hydrogen sulfide substantially in the absence of hydrocarbon oil in a relatively low temperature sulfiding step at a temperature in the range 180.degree. to 700.degree. F., withdrawing an aqueous effluent stream from said relatively low temperature sulfiding step, passing said effluent stream to a separator zone, separating ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a relatively high temperature sulfiding step at a temperature in the range 500.degree. to 750.degree. F. which is higher than the temperature in said low temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, recovering an aqueous-oil slurry containing dispersed molybdenum sulfide catalyst and passing said catalyst to a hydroprocessing step.

13. The process of claim 12 wherein said hydroprocessing step is operated at a temperature above the temperature of said high temperature sulfiding step.

14. A process comprising the preparation of a dispersed tungsten sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting ammonia and a tungsten compound in water to form aqueous ammonium tungstates, reacting said aqueous ammonium tungstates with hydrogen sulfide in a low temperature sulfiding step at a temperature in the range 70.degree. to 350.degree. F. essentially in the absence of feed oil, continuing the reaction with hydrogen sulfide in an intermediate temperature sulfiding step at a temperature in the range 180.degree. to 700.degree. F. essentially without feed oil, said intermediate temperature sulfiding step operated at a temperature higher than the temperature in said low temperature sulfiding step, withdrawing an aqueous effluent stream from said intermediate temperature sulfiding step, passing said effluent stream to a separator step, separating ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue together with hydrocarbon oil, hydrogen and hydrogen sulfide to a high temperature sulfiding step operated at a temperature in the range of 500.degree. to 750.degree. F. which is higher than the temperature in said intermediate temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, withdrawing from said high temperature sulfiding step an aqueous-oil slurry containing dispersed tungsten sulfide catalyst and passing said catalyst with feed oil and hydrogen to a hydroprocessing step.

15. The process of claim 14 wherein said hydroprocessing step is operated at a temperature higher than the temperature in said high temperature sulfiding step.

16. A process comprising the preparation of a dispersed tungsten sulfide hydrocarbon oil hydroprocessing catalyst comprising reacting thiosubstituted ammonium tungstate, water and hydrogen sulfide substantially in the absence of feed oil in a sulfiding step at a relatively low temperature in the range 180.degree. to 700.degree. F., withdrawing an aqueous effluent stream from said relatively low temperature sulfiding step, passing said effluent stream to a separator zone, separating ammonia from said aqueous effluent stream in said separator zone leaving a separator residue, passing said separator residue with feed hydrocarbon oil, hydrogen and hydrogen sulfide to a sulfiding step wherein said feed oil is hydroprocessed at a relatively high temperature in the range 500.degree. to 750.degree. F. which is above the temperature in said low temperature sulfiding step, the residence time in each of said sulfiding steps being at least 0.02 hours, and recovering an aqueous-oil slurry containing dispersed tungsten sulfide catalyst.

17. The process of claim 16 including passing said aqueous-oil slurry containing dispersed tungsten sulfide catalyst to a hydroprocessing step wherein said hydroprocessing step is operated at a temperature which is higher than the temperature in said sulfiding step.