Hydrocracking catalyst for hydrocarbon oil, method for producing hydrocracking catalyst, and method for hydrocracking hydrocarbon oil with hydrocracking catalyst
The present invention relates to a hydrocracking catalyst for hydrocarbon oil comprising a support containing a framework-substituted zeolite-1 in which zirconium atoms and/or hafnium atoms form a part of a framework of an ultrastable y-type zeolite and a hydrogenative metal component carried thereon and a method for producing the same. The hydrocracking catalyst of the present invention makes it easy to diffuse heavy hydrocarbon oils such as VGO, DAO and the like into mesopores, is improved in a cracking activity and makes it possible to obtain a middle distillate at a high yield as compared with catalysts prepared by using zeolite comprising titanium and/or zirconium carried thereon.
1. A hydrocracking catalyst for hydrocarbon oil comprising a hydrogenative metal component carried on a support containing an ultra-stable Y-type zeolite, wherein the above ultra-stable Y-type zeolite is a framework-substituted zeolite (hereinafter referred to as a framework-substituted zeolite-1) in which a part of aluminum atoms constituting a zeolite framework thereof is substituted with 0.1-5 mass % zirconium atoms and 0.1-5 mass % titanium ions calculated on an oxide basis.
2. A hydrocracking catalyst for hydrocarbon oil according to claim 1 , wherein said zeolite-1 contains from 0.1 to 5 mass % hafnium atoms as calculated as the oxide basis.
3. The hydrocracking catalyst for hydrocarbon oil according to claim 1 , wherein the support contains the framework-substituted zeolite-1 and inorganic oxide excluding the framework-substituted zeolite-1.
4. The hydrocracking catalyst for hydrocarbon oil according to claim 3 , wherein the inorganic oxide is alumina and/or silica-alumina.
5. The hydrocracking catalyst for hydrocarbon oil according to claim 1 , wherein the support further contains a titanium-substituted zeolite of which at least a part of aluminum atoms constituting a framework of the ultra-stable Y-type zeolite is substituted only with titanium atoms.
6. The hydrocracking catalyst for hydrocarbon oil according to claim 5 , wherein said titanium-substituted zeolite contains from 0.1 to 5 mass % titanium atoms as calculated as the oxide basis.
7. The hydrocracking catalyst for hydrocarbon oil according to claim 5 , wherein the support comprises the framework-substituted zeolite-1, the titanium-substituted zeolite and inorganic oxide excluding the framework-substituted zeolite-1 and the framework-substituted zeolite-2.
8. The hydrocracking catalyst for hydrocarbon oil according to claim 1 , wherein the framework-zeolite-1 has the following characteristics:
(a) a crystal lattice constant of 2.430 to 2.450 nm,
(b) a specific surface area of 600 to 900 m 2 /g, and
(c) a molar ratio of SiO 2 to Al 2 O 3 of 20 to 100.
9. The hydrocracking catalyst for hydrocarbon oil according to claim 1 , having a specific surface area of 200 to 450 m 2 /g; a volume of pores having a diameter of 600 A or less of 0.40 to 0.75 ml/g; and a carrying amount of a hydrogenative metal component falls of 0.01 to 40 mass %.
10. A method for hydrocracking hydrocarbon oil, comprising:
hydrocracking hydrocarbon oil with the hydrocracking catalyst according to claim 1 .
11. The method for hydrocracking hydrocarbon oil according to claim 10 , further comprising:
filling a hydrotreating apparatus which is a flow reactor with the hydrocracking catalyst; and
treating a hydrocarbon oil having a boiling point of 375° C. to 833° C. in the presence of hydrogen at a reactor temperature of 300° C. to 500° C., a hydrogen pressure of 4 to 30 MPa, a liquid hourly space velocity (LHSV) of 0.1 to 10 h −1 , and a hydrogen/oil ratio of 500 to 2500 Nm 3 /m 3 .
12. The method for hydrocracking hydrocarbon oil according to claim 11 , wherein the flow reactor is a flow reactor selected from the group consisting of a stirred tank, a ebullient bed reactor, a baffled slurry tank, a fixed bed reactor, a rotating tubular reactor and a slurry-bed reactor.
13. The method for hydrocracking hydrocarbon oil according to claim 11 , wherein the hydrocarbon oil comprises refined oil obtained from (1) crude oil, (2) synthetic crude oil, (3) bitumen, (4) oil sand, (5) shale oil or (6) coal oil.
14. The method for hydrocracking hydrocarbon oil according to claim 11 , wherein the hydrocarbon oil comprises refined oil obtained from crude oil, synthetic crude oil, bitumen, oil sand, shale oil or coal oil, and said refined oil is a) vacuum gas oil (VGO), b) deasphalted oil (DAO) obtained from a solvent deasphalting process or demetalized oil, c) light coker gas oil or heavy coker gas oil obtained from a coker process, d) cycle oil obtained from a fluid catalytic cracking (FCC) process or e) gas oil obtained from a visbraking process.
15. The method for hydrocracking hydrocarbon oil according to claim 10 , further comprising:
filling a hydrotreating apparatus which is a flow reactor with the hydrocracking catalyst; and
treating a hydrocarbon oil having a boiling point of 375° C. to 650° C. in the presence of hydrogen at a reactor temperature of 330° C. to 450° C., a hydrogen pressure of 7 to 15 MPa, a liquid hourly space velocity (LHSV) of 0.2 to 1.5h −1 , and a hydrogen/oil ratio of 1000 to 2000 Nm 3 /m 3 to afford kerosene-gas oil.