Catalyst composition preparation and use
A bulk metal oxide catalyst composition of the general formula (X)b(M)c(Z)d(O)e (I) wherein X represents at least one non-noble Group VIII metal; M represents at least one non-noble Group VIb metal; Z represents one or more elements selected from aluminium, silicon, magnesium, titanium, zirconium, boron, and zinc; one of b and c is the integer 1; and d and e and the other of b and c each are a number greater than 0 such that the molar ratio of b:c is in the range of from 0.5:1 to 5:1, the molar ratio of d:c is in the range of from 0.2:1 to 50:1, and the molar ratio of e:c is in the range of from 3.7:1 to 108:1; is prepared by controlled (co)precipitation of component metal compounds, refractory oxide material, and alkali compound in protic liquid. Resulting compositions find use in hydrotreatment processes involving particularly hydrodesulphurisation and hydrodenitrification.
1. A catalyst comprising a composition of the general formula, on an oxide basis,
(X) b (M) c (Z) d (O) e (I)
wherein
X represents at least one non-noble Group VIII metal;
M represents at least one Group VIb metal;
Z represents one or more elements selected from aluminium, silicon, magnesium, titanium, zirconium, boron and zinc;
O represents oxygen;
one of b and c is the integer 1; and
d, e, and the other of b and c each are a number greater than 0 such that the molar ratio of b:c is in the range of from 0.5:1 to 5:1, the molar ratio of d:c is in the range of from 0.1:1 to 50:1, and the molar ratio of e:c is in the range of from 3.6:1 to 108:1;
which is prepared by a precipitation process, wherein a refractory oxide material in an amount in the range of from 15 to 40 wt %, on an oxide basis, is precipitated with at least one non-noble Group VIII compound and at least one Group VIb metal compound; and which has an XRD diffraction pattern in which above 2θ=15°, there is a local maximum having a characteristic full width at a half maximum above 2.5° at each of a 2θ value in the range of from 25.5° to 28.0°; a 2θ value in the range of from 33.6° to 34.6°; and a 2θ value in the range of from 59.8° to 62.2°, and there is no reflection or local maximum having a characteristic full width at half maximum of 2.5° or below.
2. A catalyst as claimed in claim 1 , wherein the metals X and M are one of nickel and molybdenum, nickel and tungsten, and nickel, molybdenum and tungsten.
3. A catalyst as claimed in claim 2 , which is XRD-amorphous.
4. A catalyst as recited in claim 1 , wherein X represents nickel, cobalt or a combination of nickel and cobalt.
5. A catalyst as recited in claim 4 , wherein M represents molybdenum, tungsten or a combination of molybdenum and tungsten.
6. A catalyst as recited in claim 5 , wherein the molar ratio of b:c is in the range of from 0.75:1 to 3:1, the molar ratio of d:c is in the range of from 0.2:1 to 20:1, and the molar ratio is in the range of from 4.1:1 to 46:1.
7. A catalyst as recited in claim 6 , wherein the refractory oxide material is precipitated with the metals compounds in an amount in the range of from 15 to 25 wt %.
8. A catalyst as recited in claim 6 , wherein X is nickel, M is molybdenum, and Z is silicon, the molar ratio of b:c is in the range of from 1:1 to 2:1, the molar ratio of d:c is in the range of from 0.65:1 to 2:1, and the molar ratio is in the range of from 5.3:1 to 9.0:1.
9. A catalyst as recited in claim 8 , wherein the refractory oxide material is precipitated with the metals compounds in an amount in the range of from 15 to 25 wt %.
10. A catalyst as recited in claim 8 , wherein M represents molybdenum, tungsten or a combination of molybdenum and tungsten.
11. A catalyst as recited in claim 10 , wherein the molar ratio of b:c is in the range of from 0.75:1 to 3:1, the molar ratio of d:c is in the range of from 0.2:1 to 20:1, and the molar ratio is in the range of from 4.1:1 to 46:1.
12. A catalyst as recited in claim 11 , wherein X is nickel, M is molybdenum, and Z is silicon, the molar ratio of b:c is in the range of from 1:1 to 2:1, the molar ratio of d:c is in the range of from 0.65:1 to 2:1, and the molar ratio is in the range of from 5.3:1 to 9.0:1.
13. A catalyst as recited in claim 12 , wherein the refractory oxide material is precipitated with the metals compounds in an amount in the range of from 15 to 25 wt %.
14. An XRD-amorphous catalyst which has an XRD diffraction pattern in which above 2θ=15°, there is a local maximum having a characteristic full width at a half maximum above 2.5° at each of a 2θ value in the range of from 25.5° to 28.0°; a 2θ value in the range of from 33.6° to 34.6°; and a 2θ value in the range of from 59.8° to 62.2°, and there is no reflection or local maximum having a characteristic full width at half maximum of 2.5° or below.
15. A catalyst as claimed in claim 14 , wherein X is nickel, M is molybdenum, Z is silicon; the molar ratio of X:M is in the range of from 1:1 to 2:1 and the refractory oxide material is precipitated with the metals compounds in an amount in the range of from 15 to 30 wt %.
16. An XRD-amorphous catalyst as recited in claim 14 , wherein X represents nickel, cobalt or a combination of nickel and cobalt.
17. An XRD-amorphous catalyst as recited in claim 16 , wherein M represents molybdenum, tungsten or a combination of molybdenum and tungsten.
18. An XRD-amorphous catalyst as recited in claim 17 , wherein the molar ratio of b:c is in the range of from 0.75:1 to 3:1, the molar ratio of d:c is in the range of from 0.2:1 to 20:1, and the molar ratio is in the range of from 4.1:1 to 46:1.
19. An XRD-amorphous catalyst as recited in claim 18 , wherein the refractory oxide material is precipitated with the metals compounds in an amount in the range of from 15 to 25 wt %.
20. An XRD-amorphous catalyst as recited in claim 18 , wherein X is nickel, M is molybdenum, and Z is silicon, the molar ratio of b:c is in the range of from 1:1 to 2:1, the molar ratio of d:c is in the range of from 0.65:1 to 2:1, and the molar ratio is in the range of from 5.3:1 to 9.0:1.
21. An XRD-amorphous catalyst as recited in claim 20 , wherein the refractory oxide material is precipitated with the metals compounds in an amount in the range of from 15 to 25 wt %.
22. An XRD-amorphous catalyst as recited in claim 14 , wherein M represents molybdenum, tungsten or a combination of molybdenum and tungsten.
23. An XRD-amorphous catalyst as recited in claim 22 , wherein the molar ratio of b:c is in the range of from 0.75:1 to 3:1, the molar ratio of d:c is in the range of from 0.2:1 to 20:1, and the molar ratio is in the range of from 4.1:1 to 46:1.
24. An XRD-amorphous catalyst as recited in claim 23 , wherein X is nickel, M is molybdenum, and Z is silicon, the molar ratio of b:c is in the range of from 1:1 to 2:1, the molar ratio of d:c is in the range of from 0.65:1 to 2:1, and the molar ratio is in the range of from 5.3:1 to 9.0:1.
25. An XRD-amorphous catalyst as recited in claim 24 , wherein the refractory oxide material is precipitated with the metals compounds in an amount in the range of from 15 to 25 wt %.
26. A hydroprocessing method, comprising:
contacting under hydroprocessing conditions a hydrocarbon feed with a catalyst comprising a composition of the general formula, on an oxide basis,
(X) b (M) c (Z) d (O) e (I)
wherein
X represents at least one non-noble Group VIII metal;
M represents at least one Group VIb metal;
Z represents one or more elements selected from aluminum, silicon, magnesium, titanium, zirconium, boron and zinc;
O represents oxygen;
one of b and c is the integer 1; and
d, e, and the other of b and c each are a number greater than 0 such that the molar ratio of b:c is in the range of from 0.5:1 to 5:1, the molar ratio of d:c is in the range of from 0.2:1 to 50:1, and the molar ratio of e:c is in the range of from 3.7:1 to 108:1; which is prepared by a precipitation process, wherein a refractory oxide material in an amount in the range of from 15 to 40 wt %, on an oxide basis, is precipitated with at least one non-noble Group VIII compound and at least one Group VIb metal compound; and wherein said composition has an XRD diffraction pattern in which above 2θ=15°, there is a local maximum having a characteristic full width at a half maximum above 2.5° at each of a 2θ value in the range of from 25.5° to 28.0°; a 2θ value in the range of from 33.6° to 34.6°; and a 2θ value in the range of from 59.8° to 62.2°, and there is no reflection or local maximum having a characteristic full width at half maximum of 2.5° or below.
27. A hydroprocessing method as recited in claim 26 wherein said composition is XRD-amorphous.
28. A hydroprocessing method as recited in claim 27 wherein the metals X and M are one of nickel and molybdenum, nickel and tungsten, and nickel, molybdenum and tungsten.
29. A hydroprocessing method as recited in claim 28 , wherein said catalyst has an XRD diffraction pattern in which above 2θ=15°, there is a local maximum having a characteristic full width at a half maximum above 2.5° at each of a 2θ value in the range of from 25.5° to 28.0°; a 2θ value in the range of from 33.6° to 34.6°; and a 2θ value in the range of from 59.8° to 62.2°, and there is no reflection or local maximum having a characteristic full width at half maximum of 2.5° or below.
30. A hydroprocessing method as recited in claim 29 , wherein X is nickel, M is molybdenum, Z is silicon; the molar ratio of X:M is in the range of from 1:1 to 2:1 and the refractory oxide material is precipitated with the metals compounds in an amount in the range of from 15 to 30 wt %.