Mixed oxides of transition metals, hydrotreatment catalysts obtained therefrom and preparation process

Patent metadata

Field	Value
Publication number	US-9522394-B2
Application number	US-201214007913-A
Country	US
Kind code	B2
Filing date	Mar 22, 2012
Priority date	Mar 30, 2011
Publication date	Dec 20, 2016
Grant date	Dec 20, 2016

Abstract

New sulfide metal catalysts are described, containing Ni, Mo and W, an element Z selected from Si, Al and mixtures thereof, and possibly an organic residue, obtained by sulfidation of mixed oxide precursors, also new, characterized in that they comprise an amorphous phase and a wolframite isostructural crystalline phase, the crystallinity degree of said mixed oxides being higher than 0 and lower than 100%, preferably higher than 0 and lower than 70%. The catalysts of the invention are useful as hydrotreatment catalysts, and in particular as hydrodesulfurization, hydrodenitrogenation and/or hydrodearomatization catalysts.

First claim

The invention claimed is:

1. Mixed oxides comprising formula (I):
Ni a Y b Z c O d .pC  (I)

possibly formed without a binder,
wherein Y is a mixture of Mo and W in a molar ratio Mo/W greater than 0.1 and less than 10,
Z is selected from Si, Al and mixtures thereof,
O is oxygen,
C is an organic component selected from a nitrogenated compound N, an organic residue R containing carbon and nitrogen, and a mixture of the residue R and nitrogenated compound N,
said nitrogenated compound N being an amine having formula (A)
R 1 R 2 R 3 N  (A)

wherein
R 1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and
R 2 and R 3 , equal to or different from each other, are selected from H and linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl possibly being equal to or different from R 1 ,
a, c and d are the number of moles of Ni, Z, and O, respectively,
b is the sum of the moles of W and Mo
p is the weight percentage of C with respect to the total weight of the compound having formula (I),
a, b, c, and d are greater than 0
a/b is greater than or equal to 0.6 and lower than or equal to 1.5,
(a+b)/c is greater than or equal to 0.3 and lower than or equal to 10,
d=(2a+6b+Hc)/2 wherein
H=4 when Z=Si
H=3 when Z=Al

and p is greater than or equal to 0 and lower than or equal to 40%,
wherein said mixed oxides of formula (I) are characterized in that their diffraction patterns show the presence of an amorphous phase and a wolframite isostructural monoclinic crystalline phase, whose XRD pattern comprises the reflections indicated in the following table:

No
2θ (°)

1
19.3 ± 0.2

2
24.0 ± 0.3

3
24.9 ± 0.3

4
30.9 ± 0.5

5
36.7 ± 0.5

6
41.7 ± 0.6

7
54.7 ± 0.7

8
66.0 ± 0.8

the crystallinity degree of said mixed oxides being greater than 0 and lower than 100%.

2. The mixed oxides according to claim 1 , comprising an amorphous phase and a wolframite isostructural crystalline phase having a crystallinity degree greater than 70% and lower than 100%, having formula (I1):
Ni a Y b Z c O d   (I1)

possibly formed without a binder,
wherein Y is a mixture of Mo and W in a molar ratio Mo/W greater than 0.1 and less than 10,
Z is selected from Si, Al and mixtures thereof,
O is oxygen,
a, c, and d are the number of moles of Ni, Z, and O, respectively, and are greater than 0
b is the sum of the moles of W and Mo, and is greater than 0
a/b is greater than or equal to 0.6 and lower than or equal to 1.5,
(a+b)/c is greater than or equal to 0.3 and lower than or equal to 10,
d=(2a+6b+Hc)/2 wherein
H=4 when Z=Si
H=3 when Z=Al.

3. The mixed oxides according to claim 1 , comprising an amorphous phase and a wolframite isostructural crystalline phase having a crystallinity degree greater than 0 and lower than or equal to 70%, having formula (I2):
Ni a Y b Z c O d .pC  (i2)

possibly formed without a binder,
wherein Y is a mixture of Mo and W in which the molar ratio Mo/W is greater than 0.1 and less than 10,
Z is selected from Si, Al and mixtures thereof,
O is oxygen,
C is an organic component selected from a nitrogenated compound N, an organic residue R containing carbon and nitrogen, and a mixture of the residue R and nitrogenated compound N,
said nitrogenated compound N being an amine having formula (A)
R 1 R 2 R 3 N  (A)

wherein
R 1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and
R 2 and R 3 , equal to or different from each other, are selected from H and linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl possibly being equal to or different from R 1 ,
a, c and d are the number of moles of Ni, Z, O, respectively,
b is the sum of the moles of W and Mo
p is the weight percentage of C with respect to the total weight of the compound having formula (I2),
a, b, c, and d are greater than 0
a/b is greater than or equal to 0.6 and lower than or equal to 1.5,
(a+b)/c is greater than or equal to 0.3 and lower than or equal to 10,
d =(2a+6b+Hc)/2 wherein
H=4 when Z=Si
H=3 when Z=Al

p is greater than 0 and lower than or equal to 40%.

4. The mixed oxides of claim 1 , in a shaped form with a binder.

5. The mixed oxides according to claim 1 , wherein Y is a mixture of Mo and W in a Mo/W molar ratio ranging from 0.2 to 9.

6. The mixed oxides according to claim 1 , wherein a/b ranges from 0.80 to 1.4.

7. The mixed oxides according to claim 6 , wherein a/b ranges from 0.98 to 1.3.

8. The mixed oxides according to claim 1 , wherein the organic component C is greater than 0 and less than or equal to 25% by weight.

9. The mixed oxides according to claim 1 , wherein the crystallinity degree is greater than or equal to 3% and less than 100%.

10. The mixed oxides according to claim 9 , wherein the crystallinity degree is greater than or equal to 6% and less than or equal to 90%.

11. The mixed oxides according to claim 3 , wherein the crystallinity degree is greater than or equal to 3% and less than or equal to 70%.

12. The mixed oxides according to claim 1 , wherein R is obtained from the nitrogenated compound N by means of thermal treatment.

13. The mixed oxides according to claim 1 , wherein the nitrogenated compounds N having formula (A) are n-hexylamine, n-heptylamine or n-octylamine.

14. The mixed oxides according to claim 1 , having an XRD pattern characterized by the presence of an amorphous phase and a crystalline phase with a wolframite isostructural monoclinic symmetry, wherein the peak positioned at about 30.90°±0.5° of 2-theta is the most intense peak.

Assignees

• Carati Angela
• Gagliardi Maria Frederica
• Ferrari Marco Massimo
• Zanardi Stefano
• Marella Marcello
• Tomaselli Michele
• Eni Spa

Inventors

• Carati Angela
• Gagliardi Maria Frederica
• Ferrari Marco Massimo
• Zanardi Stefano
• Marella Marcello
• Tomaselli Michele

Classifications

• B01J37/20

  Sulfiding · CPC title

• B01J23/002 Primary

  Mixed oxides other than spinels, e.g. perovskite · CPC title

• B01J31/34 Primary

  of chromium, molybdenum or tungsten · CPC title

• B01J23/8885 Primary

  containing also molybdenum · CPC title

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title