Hydrocracking catalyst for heavy oil and method for hydrotreating heavy oil using same
Provided is a catalyst for hydrocracking of heavy oil which is excellent in both functions of cracking activity and desulfurization activity with respect to heavy oil by striking a balance between the cracking activity and desulfurization activity and which includes a support including a crystalline aluminosilicate and a porous inorganic oxide excluding the crystalline aluminosilicate, with an active metal being supported on the support, in which (a) the support includes the crystalline aluminosilicate in an amount of 45% by mass or greater and smaller than 60% by mass and the porous inorganic oxide excluding the crystalline aluminosilicate in an amount of greater than 40% by mass and 55% by mass or smaller, based on the sum of an amount of the crystalline aluminosilicate and an amount of the porous inorganic oxide excluding the crystalline aluminosilicate, (b) the active metal is at least one kind of metal selected from metals belonging to Groups 6, 8, 9, and 10 of the Periodic Table, and (c) the catalyst for hydrocracking of heavy oil has a distribution of pores in which an entire pore volume of pores defined as pores having a diameter of 5 to 1000 nm is 0.40 dm 3 /kg or greater, and a volume of intermediate mesopores having a diameter of 10 nm or larger and smaller than 20 nm accounts for 60% or greater of the entire pore volume.
1. A catalyst for hydrocracking of heavy oil, comprising a support which includes a crystalline aluminosilicate and a porous inorganic oxide excluding the crystalline aluminosilicate, with an active metal being supported on the support, wherein
(a) the support comprises the crystalline aluminosilicate in an amount of 45% by mass or greater and smaller than 60% by mass and the porous inorganic oxide excluding the crystalline aluminosilicate in an amount of greater than 40% by mass and 55% by mass or smaller, based on a sum of an amount of the crystalline aluminosilicate and an amount of the porous inorganic oxide excluding the crystalline aluminosilicate,
(b) the active metal is at least one kind of metal selected from metals belonging to Groups 6, 8, 9, and 10 of the Periodic Table, and
(c) the catalyst for hydrocracking of heavy oil has a distribution of pores in which an entire pore volume of pores defined as pores having a diameter of 5 to 1000 nm is 0.40 dm 3 /kg or greater, a volume of intermediate mesopores having a diameter of 10 nm or larger and smaller than 20 nm accounts for 60% or greater of the entire pore volume, and the pore volume of macropores defined as pores having a diameter of larger than 50 nm and 1000 nm or smaller accounts for 10% or greater of the entire pore volume.
2. The catalyst for hydrocracking of heavy oil according to claim 1 , wherein the catalyst for hydrocracking of heavy oil comprises enlarged mesopores having a diameter of 20 to 50 nm, whose volume accounts for 10% or greater and 20% or smaller of the entire pore volume.
3. The catalyst for hydrocracking of heavy oil according to claim 1 , wherein the catalyst for hydrocracking of heavy oil comprises intermediate mesopores having a diameter of 10 nm or larger and smaller than 20 nm, whose volume accounts for greater than 65% and 75% or smaller of a mesopore volume, which is a pore volume of pores defined as pores having a diameter of 5 to 50 nm.
4. The catalyst for hydrocracking of heavy oil according to claim 1 , wherein the mesopore volume accounts for 85 to 90% of the entire pore volume.
5. The catalyst for hydrocracking of heavy oil according to claim 1 , wherein the support used for the catalyst for hydrocracking of heavy oil has an average pore diameter of 14 nm or greater and mesopores defined as pores having a diameter of 5 to 50 nm show a maximum value of 13 to 15 nm.
6. The catalyst for hydrocracking of heavy oil according to claim 1 , wherein the crystalline aluminosilicate comprises one of an ultrastable Y-type zeolite and an ultrastable Y-type zeolite supporting a metal.
7. The catalyst for hydrocracking of heavy oil according to claim 1 , wherein the porous inorganic oxide excluding the crystalline aluminosilicate comprises, as a main component, alumina which is produced via a process in which an alumina hydrate (boehmite gel) is obtained as an intermediate through a neutralization reaction of an aqueous solution containing an aluminum salt, the alumina hydrate showing a relative peak high of boehmite crystals following equation (1) of 65 to 85 which is a value obtained by X-ray diffraction analysis (XRD),
Relative peak height=( B/A )×100 (1),
wherein B represents the measured value of the peak high of the boehmite crystals of the alumina hydrate, and A represents the measured value of the peak high of boehmite crystals of a standard substance at 2θ: 10° to 20°, wherein the standard substance has the following characteristics:
Composition: Al 2 O 3 : 76%, Na 2 O: 0.002%,
Loose bulk density: 700 to 800 g/l,
Packed bulk density: 800 to 1100 g/l,
Particle size (d 50 ): 40 μm,
Surface area (BET specific surface area): 220 m 2 /g,
Pore volume: 0.55 ml/g, and
Crystallite Size: 7.0 nm.
8. A hydroprocessing method for heavy oil, comprising a process of contacting a catalyst for hydrocracking of heavy oil with a composition comprising a heavy oil or residue thereof,
wherein
(a) the support comprises the crystalline aluminosilicate in an amount of 45% by mass or greater and smaller than 60% by mass and the porous inorganic oxide excluding the crystalline aluminosilicate in an amount of greater than 40% by mass and 55% by mass or smaller, based on a sum of an amount of the crystalline aluminosilicate and an amount of the porous inorganic oxide excluding the crystalline aluminosilicate,
(b) the active metal is at least one kind of metal selected from metals belonging to Groups 6, 8, 9, and 10 of the Periodic Table, and
(c) the catalyst for hydrocracking of heavy oil has a distribution of pores in which an entire pore volume of pores defined as pores having a diameter of 5 to 1000 nm is 0.40 dm 3 /kg or greater, a volume of intermediate mesopores having a diameter of 10 nm or larger and smaller than 20 nm accounts for 60% or greater of the entire pore volume, and the pore volume of macropores defined as pores having a diameter of larger than 50 nm and 1000 nm or smaller accounts for 10% or greater of the entire pore volume.
9. The hydroprocessing method according to claim 8 , wherein the porous inorganic oxide excluding the crystalline aluminosilicate comprises alumina as a main component.
10. The hydroprocessing method according to claim 9 , wherein the alumina is produced via following steps (i) and (ii), and
(i) a step of obtaining an alumina hydrate (boehmite) having a pH of 6 to 11 by carrying out a reaction between an aqueous solution containing an aluminum salt and a neutralizer,
(ii) a steps of washing, aging, drying, and kneading the resultant alumina hydrate,
the alumina hydrate showing a relative peak high of boehmite crystals following equation (1) of 65 to 85 which is a value obtained by X-ray diffraction analysis (XRD),
Relative peak high=( B/A )×100 (1)
wherein B represents the measured value of the peak high of the boehmite crystals of the alumina hydrate, and A represents the measured value of the peak high of boehmite crystals of a standard substance at 2θ: 10° to 20°, wherein the standard substance has the following characteristics:
Composition: Al 2 O 3 : 76%, Na 2 O: 0.002%,
Loose bulk density: 700 to 800 g/l,
Packed bulk density: 800 to 1100 g/l,
Particle size (do): 40 μm,
Surface area (BET specific surface area): 220 m 2 /g,
Pore volume: 0.55 ml/g, and
Crystallite Size: 7.0 nm.
11. The hydroprocessing method according to claim 10 , using aluminum sulfate as the aluminum salt, and residual amount of sulfate (SO 4 2− ) in the alumina hydrate after washing is 1% by mass or smaller.