US 2016/0101410 A1 · MIXED OXIDES OF TRANSITION METALS, HYDROTREATMENT CATALYSTS OBTAINED THEREFROM, AND PREPARATION PROCESS COMPRISING SOL-GEL PROCESSES

Abstract

New sulfided metal catalysts are described, containing a metal X selected from Ni, Co and mixtures thereof, a metal Y selected from Mo, W and mixtures thereof, an element Z selected from Si, Al and mixtures thereof, and possibly an organic residue, obtained by the sulfidation of mixed oxide precursors, also new, having general formula (A) Xa Yb Zc Od.pC (A) possibly shaped without a binder, or by sulfidation of mixed oxides having formula (A), in shaped form with a binder, wherein X is selected from Ni, Co and mixtures thereof, Y is selected from Mo, W and mixtures thereof, Z is selected from Si, Al and mixtures thereof, O is oxygen, C is selected from: a nitrogenated compound N, an organic residue deriving from the partial calcination of the nitrogenated compound N, said nitrogenated compound N, when present, being selected from: a) an alkyl ammonium hydroxide having formula (I) RIRIIRIIIRIVNOH (I) wherein the groups RIRIV, the same or different, are aliphatic groups containing from 1 to 7 carbon atoms, b) an amine having formula (II) R1R2R3N (II) wherein R1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and R2 and R3, the same or different, are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to or different from. R1, a, b, c, d are the number of moles of the elements X, Y, Z, O, respectively, p is the weight percentage of C with respect to the total weight of the precursor having formula (A), a, b, c, d are higher than 0 a/b is higher than or equal to 0.3 and lower than or equal to 2, (a+b)/c is higher than or equal to 0.3 and lower than or equal to 10, preferably varying from 0.8 to 10 d=(2a+6b+Hc)/2 wherein H=4 when Z=Si H=3 when Z=Al and p is higher than or equal to 0 and lower than or equal to 40%. Said catalysts can be used as hydrotreating catalysts.

Claims39

Dependent claims

1-4. (canceled)

A sulfided metal compound comprising a metal X selected from Ni, Co or a mixture thereof, a metal Y selected from Mo, W or a mixture thereof, an element Z selected from Si, Al or a mixture thereof, and optionally an organic residue, prepared by the sulfidation of a mixed oxide or of a composition comprising a mixed oxide in shaped form with a binder wherein said mixed oxide has the formula (A):

XaYbZcOd.pC (A)
wherein
X is selected from Ni, Co or a mixture thereof,
Y is selected from Mo, W or a mixture thereof,
Z is selected from Si, Al or a mixture thereof,
O is oxygen
C is selected from:
a nitrogenated compound N, and
an organic residue deriving from the nitrogenated compound N by partial calcination,
wherein said nitrogenated compound N is selected from:
a) an alkyl ammonium hydroxide of formula (I)
RIRIIRIIIRIVNOH (I)
wherein RI, RII, RIII and RIV are the same or different and are an aliphatic group containing from 1 to 7 carbon atoms,
b) an amine of formula (II)
R1R2R3N (II)
wherein
R1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and
R2 and R3 are the same or different and are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to or different from R1
a, b, c, d are the number of moles of the elements X, Y, Z, O, respectively, p is the weight percentage of C with respect to the total weight of the compound of formula (A),
a, b, c, d are greater than 0
a/b is greater than or equal to 0.3 and less than or equal to 2,
(a+b)/c is greater than or equal to 0.3 and less 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 less than or equal to 40%.

23 more elements

A sol-gel process for preparing a mixed oxide of formula (A), comprising:

preparing a hydroalcohol solution/suspension comprising at least one soluble or partially soluble source of at least one element X, at least one soluble or partially soluble source of at least one element Y, at least one soluble source, which can be hydrolyzed or dispersed, of at least one element Z and a nitrogenated compound N selected from:
a) an alkyl ammonium hydroxide of formula (I)
RIRIIRIIIRIVNOH (I)
wherein RI, RII, RIII and RIV are the same or different and are aliphatic groups containing from 1 to 7 carbon atoms,
b) an amine of formula (II)
R1R2R3N (II)
wherein
R1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and
R2 and R3 are the same or different and are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to, or different from,R1:
wherein the molar ratio N/(X+Y) is higher greater than 0 and less than, or equal to 1,
obtaining the formation of a gel,
maintaining the gel under stirring,
maintaining the gel under static conditions,
drying the gel prepared in the previous step, obtaining the mixed oxide precursor of formula (A2)
XaYbZcOd.pC (A2)
wherein
X is selected from Ni, Co or a mixture thereof,
Y is selected from Mo, W or a mixture thereof,
Z is selected from Si, Al or a mixture thereof,
O is oxygen,
C is a nitrogenated compound N selected from the nitrogenated compounds mentioned above, having formula (I) or (II),
a, b, c, d are the number of moles of the elements X, Y, Z and O, respectively,
p is the weight percentage of C with respect to the total weight of the compound having formula (A2)
a, b, c, d are greater than 0
a/b is greater than or equal to 0.3 and less than or equal to 2,
(a+b)/c is greater than or equal to 0.3 and less 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 0 and less than or equal to 40%,
optionally subjecting the compound of formula (A2) resulting from the previous step, to partial or total calcination, respectively obtaining a compound having the same formula (A2) wherein C is an organic residue deriving from the calcination of the nitrogenated compound, or a mixed oxide of formula (A1)
XaYbZcOd (A1)
wherein X, Y, Z, O, a, b, c, d correspond to those of the previous formula (A2);
and
wherein said mixed oxide of formula (A) has the formula:
XaYbZcOd.pC (A)
wherein
X is selected from Ni, Co or a mixture thereof,
Y is selected from Mo, W or a mixture thereof,
Z is selected from Si, Al or a mixture thereof,
O is oxygen,
C is selected from:
a nitrogenated compound N,
an organic residue deriving from the nitrogenated compound N by partial calcination,
wherein said nitrogenated compound N is selected from:
a) an alkyl ammonium hydroxide of the formula (I)
RIRIIRIIIRIVNOH (I)
wherein the groups RI, RII, RIII and RIV are the same or different and are aliphatic groups containing from 1 to 7 carbon atoms,
b) an amine having formula (II)
R1R2R3N (II)
wherein
R1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and
R2 and R3 are the same or different and are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to or different from R1
a, b, c, d are the number of moles of the elements X, Y, Z, O, respectively,
p is the weight percentage of C with respect to the total weight, of the compound having formula (A),
a, b, c, d are greater than 0
a/b is greater than or equal to 0.3 and less than or equal to 2,
(a+b)/c is greater than or equal to 0.3 and less 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 less than or equal to 40%.

59 more elements

A sol-gel process for a preparing shaped mixed elides oxide of formula (A), optionally shaped with a binder, comprising:

I) preparing a hydroalcohol solution/suspension containing at least one soluble or partially soluble source of at least one element X, at least one soluble or partially soluble source of at least one element Y, at least one soluble, hydrolyzable or dispersible source of at least one element Z and a nitrogenated compound N selected from:
a) an alkyl ammonium hydroxide having of formula (I)
RIRIIRIIIRIVNOH (I)
wherein the groups RI-RIV are the same or different and are aliphatic groups containing from 1 to 7 carbon atoms,
b) an amine having formula (II)
R1R2R3N (II)
wherein R1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and
R2 and R3 are the same or different and are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to, or different from,R1;
II) obtaining the formation of a gel,
III) maintaining the gel under stirring, optionally after the addition of a soluble, hydrolyzable or dispersible source of an oxide MeO, in a weight ratio with the gel ranging from 5 to 50% by weight with respect to the theoretical weight of the oxides contained in the gel, and possibly optionally after the addition of a mineral or organic acid in a quantity ranging from 0.5 to 8.0 g per 100 g of source of the oxide MeO, for a time sufficient for obtaining a homogeneous paste having a consistency which is normally considered suitable for extrusion,
IV) extruding the product obtained from the previous step,
V) drying the extruded product obtained,
VI) at least partially calcining the extruded product obtained in the previous step, in an oxidizing or inert atmosphere
wherein said mixed oxide of formula (A) has the formula
XaYbZcOd.pC (A)
wherein
X is selected from Ni, Co or a mixture thereof,
Y is selected from Mo, W and mixtures thereof,
Z is selected from Si. Al and mixtures thereof,
O is oxygen
C is selected from:
a nitrogenated compound N,
an organic residue deriving from the nitrogenated compound N by partial calcination,
wherein said nitrogenated compound N is selected from:
a) an alkyl ammonium hydroxide of formula (I)
RIRIIRIIIRIVNOH (I)
wherein the groups RI, RII, RIII and RIV are the same or different and are aliphatic groups containing from 1 to 7 carbon atoms,
b) an amine of formula (II)
R1R2R3N (II)
wherein
R1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and
R2 and R3 are the same or different and are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to or different from R1
a, b, c, d are the number of moles of the elements X, Y, Z, O, respectively,
p is the weight, percentage of C with respect to the total weight of the compound having formula (A),
a, b, c, d are greater than 0
a/b is greater than or equal to 0.3 and less than or equal to 2,
(a+b)/c is greater than or equal to 0.3 and less 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 less than or equal to 40%.

38 more elements

A sol-gel process for preparing a mixed oxide of formula (A), shaped without a binder, comprising:

I) preparing a hydroalcohol solution/suspension containing at least one soluble or partially soluble source of at least one element X, at least one soluble or partially soluble source of at least one element Y, at least one soluble, hydrolyzable or dispersible source of at least one element Z and a nitrogenated compound N selected from:
a) an alkyl ammonium hydroxide of formula (I)
R1R2R3N (I)
wherein the groups RI-RIV are the same or different and are aliphatic groups containing from 1 to 7 carbon atoms,
b) an amine of formula (II)
R1R2R3N (II)
wherein R1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and
R2 and R3 are the same or different and are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to, or different from,R1;
II) obtaining the formation of a gel,
III) maintaining the gel at a temperature ranging from 25 to 80° C., for a time ranging from 1 to 48 hours
IV) drying an aliquot of the gel obtained in step III, subjecting it to at least partial calcination, and adding it, optionally after blandly disaggregating it, to the remaining gel as such, in a weight ratio, between at least partially calcined product and gel as such greater than or equal to 1,
V) extruding the product thus obtained,
VI) optionally drying the extruded product obtained,
VII) at least partially calcining the extruded product thus obtained, in an oxidizing or inert atmosphere
wherein said mixed oxide of formula (A) has the formula
wherein
X is selected from Ni, Co and mixtures thereof,
Y is selected from Mo, W and mixtures thereof.
Z is selected from Si, Al and mixtures thereof,
O is oxygen.
C is selected from:
a nitrogenated compound N,
an organic residue deriving from the nitrogenated compound N by partial calcination,
wherein said nitrogenated compound N is selected from:
a) an alkyl ammonium hydroxide of formula (I)
RIRIIRIIIRIVNOH (I)
wherein the groups RI, RII, RIII and RIV are the same or different and are aliphatic groups containing from 1 to 7 carbon atoms,
b) an amine of formula (II)
R1R2R3N (II)
wherein
R1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and
R2 and R3 are the same or different and are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to or different from R1
a, b, c, d are the number of moles of the elements X. Y. Z. O, respectively,
p is the weight percentage of C with respect to the total weight of the compound having formula (A),
a, b, c, d are greater than 0
a/b is greater than or equal to 0.3 and less than or equal to 2,
(a+b)/c is greater than or equal to 0.3 and less 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 less than or equal to 40%.

38 more elements

Dependencies are inferred from the claim text.

Mixed oxides of transition metals, hydrotreatment catalysts obtained therefrom, and preparation process comprising sol-gel processes

Life of this patent

Mixed oxides of transition metals, hydrotreatment catalysts obtained therefrom, and preparation process comprising sol-gel processes

Life of this patent

Abstract

Claims39