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US 12,011,710 B1Granted
Tetrametallic bulk hydroprocessing catalysts
AssigneeChevron U.S.A. Inc.
InventorsXiaoying Ouyang, Viorel Duma, Alexander Kuperman, Ibrahim Uckung, Theodorus Ludovicus Michael Maesen, Axel Brait, Charles Wilson
Life of this patent
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Abstract
Bulk catalysts comprised of nickel, molybdenum, tungsten and titanium and methods for synthesizing bulk catalysts are provided. The catalysts are useful for hydroprocessing, particularly hydrodesulfurization and hydrodenitrogenation, of hydrocarbon feedstocks.
Claims40
A method for preparing a bulk catalyst from a bulk catalyst precursor having a formula of
- Av[Ni(OH)x(L)Py]z[MomW1-mO4][Ti(OH)nO2-n/2]w
- wherein:
- (i) A is an alkali metal cation, a rare earth metal cation, an ammonium cation, an organic ammonium cation, phosphonium cation, or a combination thereof;
- (ii) L is an organic compound-based component;
- and
- (iii) 0≤y≤−2/p, 0≤x<2;
- 0≤v<2;
- 0<z;
- 0<m<1;
- 0<n<4;
- 0.1<w/(z+1)<10;
- the method comprising:
- (a) combining in a reaction mixture:
- (i) a Ni-containing precursor;
- (ii) a Mo-containing precursor;
- (iii) a W-containing precursor;
- (iv) a Ti-containing precursor;
- (v) an organic compound-based component;
- and
- (vi) a protic liquid;
- and
- (b) reacting the mixture under conditions sufficient to cause precipitation of the bulk catalyst precursor, wherein the steps (a) and (b) are carried out at a temperature of no more than 200° C.;
- (c) recovering a bulk catalyst precursor defined by a region of a quaternary phase diagram wherein the region is defined by ten points ABCDEFGHIJ and wherein the ten points, on a metal oxide basis (wt. %), are:
- A (Ni=39, Mo=1, W=41, Ti=20), B (Ni=39, Mo=1, W=72, Ti=20), C (Ni=9, Mo=17, W=54, Ti=20), D (Ni=31, Mo=25, W=24, Ti=20), E(Ni=40, Mo=14, W=f26, Ti=20), F(Ni=34, Mo=1, W=36, Ti=30), G (Ni=7, Mo=1, W=63, Ti=30), H(Ni=8, Mo=15, W=48, Ti=30), I(Ni=27, Mo=22, W=21, Ti=30), and J(Ni=35, Mo=12, W=23, Ti=30);
- and
- (d) sulfiding the bulk catalyst precursor to form a bulk catalyst.
23 more elements
A method for preparing a bulk catalyst from a bulk catalyst precursor having a formula of
- Av[Ni(OH)x(L)Py]z[MomW1-mO4][Ti(OH)nO2-n/2]w
- wherein:
- (i) A is an alkali metal cation, a rare earth metal cation, an ammonium cation, an organic ammonium cation, phosphonium cation, or a combination thereof;
- (ii) L is an organic compound-based component;
- and
- (iii) 0≤y≤−2/p;
- 0≤x<2;
- 0≤v<2;
- 0<z;
- 0<m<1;
- 0<n<4;
- 0.1<w/(z+1)<10;
- the method comprising:
- (a) combining in a reaction mixture:
- (i) a Ni-containing precursor;
- (ii) a Mo-containing precursor;
- (iii) a W-containing precursor;
- (iv) an organic compound-based component;
- and
- (v) a protic liquid;
- and
- (b) reacting the mixture under conditions sufficient to cause precipitation of an intermediate bulk catalyst precursor;
- and
- (c) compositing the intermediate bulk catalyst precursor with a Ti-containing precursor to form the bulk catalyst precursor;
- wherein the steps (a)-(c) are carried out at a temperature of no more than 200° C.;
- and
- (d) recovering a bulk catalyst precursor defined by a region of a quaternary phase diagram wherein the region is defined by ten points ABCDEFGHIJ and wherein the ten points, on a metal oxide basis (wt. %), are:
- A (Ni=39, Mo=1, W=41, Ti=20), B(Ni=39, Mo=1, W=72, Ti=20), C (Ni=9, Mo=17, W=54, Ti=20), D (Ni=31, Mo=25, W=24, Ti=20), E(Ni=40, Mo=14, W=26, Ti=20), F(Ni=34, Mo=1, W=36, Ti=30), G (Ni=7, Mo=1, W=63, Ti=30), H(Ni=8, Mo=15, W=48, Ti=30), I (Ni=27, Mo=22, W=21, Ti=30), and J(Ni=35, Mo=12, W=23, Ti=30);
- and
- (e) sulfiding the bulk catalyst precursor to form a bulk catalyst.
27 more elements
A method for preparing a bulk catalyst from a bulk catalyst precursor having a formula of
- Av[Ni(OH)x(L)Py]z[MomW1-mO4][Ti(OH)nO2-n/2]w
- wherein:
- (i) A is an alkali metal cation, a rare earth metal cation, an ammonium cation, an organic ammonium cation, phosphonium cation, or a combination thereof;
- (ii) L is an organic compound-based component;
- and
- (iii) 0≤y≤−2/p, 0≤x<2;
- 0≤v<2;
- 0<z;
- 0<m<1;
- 0<n<4;
- 0.1<w/(z+1)<10;
- the method comprising:
- (a) combining in a reaction mixture:
- (i) a Ni-containing precursor;
- (ii) a Mo-containing precursor;
- (iii) a W-containing precursor;
- (iv) a Ti-containing precursor;
- (v) an organic compound-based component;
- and
- (vi) a protic liquid;
- and
- (b) reacting the mixture under conditions sufficient to cause precipitation of the bulk catalyst precursor, wherein the steps (a) and (b) are carried out at a temperature of no more than 200° C.;
- (c) recovering a bulk catalyst precursor defined by a region of a quaternary phase diagram wherein the region is defined by eight points ABCDEFGH and wherein the eight points, on a metal oxide basis (wt. %), are:
- A (Ni=52.5, Mo=3.5, W=14, Ti=30), B(Ni=38.5, Mo=17.5, W=14, Ti=30), C(Ni=21, Mo=17.5, W=31.5, Ti=30), D (Ni=35, Mo=3.5, W=31.5, Ti=30), E(Ni=60, Mo=4, W=16, Ti=20), F(Ni=44, Mo=20, W=16, Ti=20), G (Ni=24, Mo=20, W=36, Ti=20), and H (Ni=40, Mo=4, W=36, Ti=20);
- and
- (d) sulfiding the bulk catalyst precursor to form a bulk catalyst.
23 more elements
A method for preparing a bulk catalyst from a bulk catalyst precursor having a formula of
- Av[Ni(OH)x(L)Py]z[MomW1-mO4][Ti(OH)nO2-n/2]w
- wherein:
- (i) A is an alkali metal cation, a rare earth metal cation, an ammonium cation, an organic ammonium cation, phosphonium cation, or a combination thereof;
- (ii) L is an organic compound-based component;
- and
- (iii) 0≤y≤−2/p;
- 0≤x<2;
- 0≤v<2;
- 0<z;
- 0<m<1;
- 0<n<4;
- 0.1<w/(z+1)<10;
- the method comprising:
- (a) combining in a reaction mixture:
- (i) a Ni-containing precursor;
- (ii) a Mo-containing precursor;
- (iii) a W-containing precursor;
- (iv) an organic compound-based component;
- and
- (v) a protic liquid;
- and
- (b) reacting the mixture under conditions sufficient to cause precipitation of an intermediate bulk catalyst precursor;
- and
- (c) compositing the intermediate bulk catalyst precursor with a Ti-containing precursor to form the bulk catalyst precursor;
- wherein the steps (a)-(c) are carried out at a temperature of no more than 200° C.;
- and
- (d) recovering a bulk catalyst precursor defined by a region of a quaternary phase diagram wherein the region is defined by eight points ABCDEFGH and wherein the eight points, on a metal oxide basis (wt. %), are:
- A (Ni=52.5, Mo=3.5, W=14, Ti=30), B(Ni=38.5, Mo=17.5, W=14, Ti=30), C(Ni=21, Mo=17.5, W=31.5, Ti=30), D(Ni=35, Mo=3.5, W=31.5, Ti=30), E(Ni=60, Mo=4, W=16, Ti=20), F(Ni=44, Mo=20, W=16, Ti=20), G (Ni=24, Mo=20, W=36, Ti=20), and H(Ni=40, Mo=4, W=36, Ti=20);
- and
- (e) sulfiding the bulk catalyst precursor to form a bulk catalyst.
27 more elements
Dependencies are inferred from the claim text.