Catalyst composition preparation and use

• US 8,088,706 B2
• Filed: 04/29/2009
• Issued: 01/03/2012
• Est. Priority Date: 02/24/2003
• Status: Active Grant

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Domokos, Laszlo, Jongkind, Hermanus, Van Veen, Johannes Anthonius Robert
• Primary Examiner(s): Nguyen, Cam N.
• Application Number:
  US12/432,278
• Publication Number:
  US 20090209414A1
• Time in Patent Office: 979 Days
• Field of Search: 502/236, 502/238, 502/242, 502/253, 502/263, 502/322, 502/323, 502/332, 502/335, 502/337, 502/342, 502/343, 502/407, 502/415, 502/439, 502254-260, 502305-309, 502314-316, 502327-329, 502349-351
• US Class Current: 502/257
• CPC Class Codes: B01J 21/06 Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 23/85 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 23/883 and nickel
• CPC Class Codes: B01J 23/8885 containing also molybdenum
• CPC Class Codes: B01J 37/03 Precipitation; Co-precipitation
• CPC Class Codes: C10G 45/06 containing nickel or cobalt metal, or compounds thereof

Abstract

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 aluminum, 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 hydrodesulphurization and hydrodenitrification.

Claims

1. A process for the preparation of a catalyst composition having 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 the group consisting of 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 0.1;

1 to 50;

1, and the molar ratio of e;

c is in the range of from 3.6;

1 to 108;

1;

said process comprises heating a composition of the general formula

(NH₄)_a(X)_b(M)_c(Z)_d(O)_e 

 

(II)

in which a is a number greater than 0 and X, M, Z, O, b, c, d and e are as defined above, at a temperature in the range of from 100 to 600°

C.,

wherein the composition of general formula II is in the form of, or is recovered from, a slurry optionally after ageing at a temperature in the range of from 20 to 95°

C. for a minimum of 10 minutes, said slurry being obtained by coprecipitating, at a temperature and for a time sufficient to produce the composition II, at least one non-noble Group VIII metal compound, at least one Group VIB metal compound, at least one refractory oxide material and an alkali compound, in a protic liquid, at least one of the metal compounds being partly in solid state and partly in dissolved state.

2. A process as claimed in claim 1, wherein said heating of the composition II is at a temperature not exceeding 350°

C.

3. A process as claimed in claim 2, wherein the coprecipitation is carried out at a temperature in the range of from 25 to 95°

C., for a period of time in the range of from 10 minutes to 2 hours, at an alkali concentration of from 0.2 mol per mol of metals M+X, on an oxide basis, to 50 mol per mol of metals M+X, on an oxide basis, and with an initial slurry concentration in the range of from 2 to 40 wt % nominal solids content.

4. A process as claimed in claim 3, wherein the alkali compound is ammonia or a material that will generate ammonium ions in the protic liquid used.

5. A process as claimed in claim 4, wherein the alkali concentration is in the range of from 0.75 to 5 mol nitrogen per mol of metals M+X, on an oxide basis.

6. A process as claimed in claim 5, wherein the composition of the general formula I is further subjected to any one or more of the following process steps carried out in any appropriate order:

cooling;

optionally isolating;

drying;

shaping, preferably by extrusion using no extrusion aids;

calcining;

sulfiding.

7. A process for the preparation of a catalyst composition, said process comprises heating a composition having the general formula

(NH₄)_a(X)_b(M)_c(Z)_d(O)_e 

 

(II)

in which a is a number greater than 0 and X, M, Z, O, b, c, d and e are as defined in claim 1, at a temperature in the range of from 100 to 600°

C. to yield said composition having 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 the group consisting of 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 0.1;

1 to 50;

1, and the molar ratio of e;

c is in the range of from 3.6;

1 to 108;

1.

8. A bulk metal oxide catalyst composition prepared by a process as claimed in any one of claims 1 to 6.