HYDROCRACKING CATALYST, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF

Abstract

Disclosed is a hydrocracking catalyst, a preparation method and an application thereof. The catalyst comprises a carrier, silicon dioxide and active ingredients loaded on the carrier, wherein the carrier comprises Y molecular sieves and SAPO-34 molecular sieves. The preparation method of the hydrocracking catalyst comprises the following steps: (1) mixing materials comprising Y molecular sieves and SAPO-34 molecular sieves, and then subjecting the mixture to molding, drying and calcinating to obtain a carrier; (2) introducing silane and the active ingredients into the carrier prepared in the step (1), subsequently performing the drying and calcinating to prepare the hydrocracking catalyst. The catalyst prepared with the method can be used for hydrocracking reaction, thereby significantly increase yield of jet fuel.

Claims

1. A hydrocracking catalyst comprising a carrier, silica and active ingredients loaded on the carrier, wherein the carrier comprises Y molecular sieves and SAPO-34 molecular sieves, and based on the weight of the carrier, the content of Y molecular sieves is within a range of 2-35 wt %, and the content of SAPO-34 molecular sieves is within a range of 2-25 wt %; the active ingredients comprise VIB group metal and/or VIII group metal; based on the weight of the catalyst, the content of silica loaded on the carrier is within a range of 0.5-5 wt %; the content of the VIB group metal in terms of oxide is within a range of 10-25 wt %; and the content of the VIII group metal in terms of oxide is within a range of 4-10 wt %.

2. The catalyst of claim 1, wherein the silica and the active ingredients are jointly distributed on the outer surface of the carrier and the inner surface of a pore channel of the carrier.

3. The catalyst of claim 1, wherein the Y molecular sieves have the following properties: the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 is within a range of 25-150, the specific surface area is within a range of 550-1,000 m.sup.2/g, and the total pore volume is within a range of 0.3-0.6 mL/g.

4. The catalyst of claim 1, wherein the SAPO-34 molecular sieves have a molar ratio of SiO.sub.2/Al.sub.2O.sub.3 within a range of 0.05-0.5, a specific surface area within a range of 200-800 m.sup.2/g, and a total pore volume within a range of 0.3-0.6 mL/g.

5. The catalyst of claim 1, wherein the carrier further comprises a binder, and the content of the binder in the carrier is within a range of 15-85 wt %.

6. The catalyst of claim 1, wherein the catalyst has the specific surface area within a range of 120-500 m.sup.2/g, the pore volume within a range of 0.30-0.65 mL/g; the pore volume of the pore diameter of 4-10 nm accounts for 65-95% of the total pore volume.

7. A preparation method of the hydrocracking catalyst, the method comprises the following steps: (1) subjecting the materials comprising Y molecular sieves and SAPO-34 molecular sieves to molding, drying and calcinating to obtain a carrier; (2) introducing silane and active ingredients into the carrier prepared in the step (1), wherein the active ingredients comprise VIB group metal and/or VIII group metal, and then carrying out drying and calcinating.

8. The method of claim 7, wherein the materials in step (1) further comprise a binder or a precursor thereof, or the binder or the precursor thereof is added during the forming process.

9. The method of claim 7, wherein the materials in the step (1) further comprise microcrystalline cellulose, and the content of the microcrystalline cellulose in the material is within a range of 0.2-6 wt %.

10. The method of claim 7, wherein the drying conditions in the step (1) comprise a drying temperature within a range of 60-180° C., and a drying time within a range of 0.5-20 hours; the calcinating conditions comprise a calcinating temperature within a range of 350-750° C., and a calcinating time within a range of 0.5-20 hours.

11. The method of claim 7, wherein the Y molecular sieves have the following properties: the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 is within a range of 25-150, the specific surface area is within a range of 550-1,000 m.sup.2/g, and the total pore volume is within a range of 0.3-0.6 mL/g; the SAPO-34 molecular sieves in the catalyst have a molar ratio of SiO.sub.2/Al.sub.2O.sub.3 within a range of 0.05-0.5, a specific surface area within a range of 200-800 m.sup.2/g, and a total pore volume within a range of 0.3-0.6 mL/g.

12. The method of claim 7, wherein the silane in step (2) is one or more selected from the group consisting of aminosilane, alkylsilane, and sulfur-containing silane.

13. The method of claim 7, wherein in the step (2), the active ingredients and the silane are introduced simultaneously or separately.

14. The method of claim 13, wherein the solvent in the impregnation liquid is water.

15. The method of claim 7, wherein in step (2), the drying temperature is within a range of 60-200° C., and the drying time is within a range of 0.5-20 hours; calcinating temperature is within a range of 300-500° C., and the calcinating time is within a range of 0.5-20 hours.

16. (canceled)

17. A process for producing jet fuel, the process comprises contacting a heavy feedstock oil under hydrocracking conditions with a hydrocracking catalyst in claim 1.

18. The process of claim 17, wherein the hydrocracking conditions comprise a reaction temperature within a range of 340-430° C., a hydrogen partial pressure within a range of 5-20 MPa, a hydrogen-oil volume ratio within a range of 500-2000:1, and a liquid hourly space velocity within a range of 0.5-1.8h.sup.−1.

19. The catalyst of claim 1, wherein based on the weight of the carrier, the content of Y molecular sieves is within a range of 8-25 wt %, and the content of SAPO-34 molecular sieves is within a range of 2-8 wt %; the VIB group metal is molybdenum (Mo) and/or tungsten (W), the VIII group metal is cobalt (Co) and/or nickel (Ni); based on the weight of the catalyst, the content of silica loaded on the carrier is within a range of 1-4 wt %; the content of the VIB group metal in terms of oxide is within a range of 15-20 wt %; and the content of the VIII group metal in terms of oxide is within a range of 5-8 wt %.

20. The catalyst of claim 19, wherein based on the weight of the carrier, the content of Y molecular sieves is within a range of 10-20 wt %, and the content of SAPO-34 molecular sieves is within a range of 2.5-6 wt %; and based on the weight of the catalyst, the content of silica loaded on the carrier is within a range of 1.5-3 wt %.

21. The catalyst of claim 6, wherein the catalyst has the specific surface area within a range of 170-300 m.sup.2/g, the pore volume within a range of 0.35-0.60mL/g; the pore volume of the pore diameter of 4-10nm accounts for 70-90% of the total pore volume.

Description

DETAILED DESCRIPTION

[0015] The terminals and any value of the ranges disclosed herein are not limited to the precise ranges or values, such ranges or values shall be comprehended as comprising the values adjacent to the ranges or values. As for numerical ranges, the endpoint values of the various ranges, the endpoint values and the individual point value of the various ranges, and the individual point values may be combined with one another to produce one or more new numerical ranges, which should be deemed have been specifically disclosed herein.

[0016] According to the present disclosure, the carrier of the catalyst comprises Y molecular sieves and SAPO-34 molecular sieves, after calcinating the carrier impregnated with silane, the silica is generated in situ from silane and loaded on the carrier, the silica and the active ingredients are jointly distributed on the outer surface and the inner surface of a pore channel of the carrier.

[0017] Preferably, the Y molecular sieves in the above catalyst have the following properties: the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 is within a range of 25-150, the specific surface area is within a range of 550-1,000 m.sup.2/g, and the total pore volume is within a range of 0.30-0.60 mL/g.

[0018] According to a preferable embodiment of the present disclosure, the SAPO-34 molecular sieves in the catalyst have a molar ratio of SiO.sub.2/Al.sub.2O.sub.3 within a range of 0.05-0.5, a specific surface area within a range of 200-800 m.sup.2/g, and a total pore volume within a range of 0.30-0.60 mL/g.

[0019] According to a preferred embodiment of the present disclosure, the catalyst further comprises phosphorus (P), the content of P in terms of oxide is within a range of 1.2-1.6 wt %, based on the total amount of the catalyst. Such that the hydrocracking effect and the jet fuel yield can be further improved. The reason may reside in an existence of phosphorus, especially the introduction of phosphorus into the impregnation liquid, causes the impregnation liquid to become a stable phosphomolybdic heteropoly acid system, and the active ingredients are uniformly dispersed on the carrier surface to form more active centers for reaction.

[0020] According to a preferred embodiment of the present disclosure, in regard to the shaped catalyst, the carrier further comprises a binder, such as one or more selected from the group consisting of alumina, amorphous silica-alumina and silica, and the content of the binder in the carrier is within a range of 15-85 wt %, preferably 25-80 wt %, and more preferably 30-50 wt %, based on the weight of the carrier.

[0021] According to a preferred embodiment of the present disclosure, the hydrocracking catalyst among the above-mentioned catalysts has the following properties: the specific surface area is within a range of 120-500 m.sup.2/g, preferably 170-300 m.sup.2/g, and more preferably 180-200 m.sup.2/g; the pore volume is within a range of 0.30-0.65 mL/g, preferably 0.35-0.60 mL/g, and more preferably 0.35-0.4 mL/g; the pore volume of the pore diameter of 4-l0nm accounts for 65-95%, preferably 70-90%, more preferably 75-85% of the total pore volume.

[0022] In the present disclosure, unless otherwise specified, the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 is measured with chemical analysis using the ZSX100e type Wavelength Dispersive X-ray Fluorescence Spectrometer (XRF) manufactured by the Rigaku Corporation in Japan.

[0023] The specific surface area, the pore volume and the pore distribution are measured by a low-temperature liquid nitrogen physical adsorption method according to the National Standard GB/T-19587-A2004 of China, and using a low-temperature nitrogen adsorption instrument with ASAP2420 model of Micromeritics Corporation in the United States of America (USA).

[0024] In the present disclosure, the composition of the catalyst is obtained by calculation according to the feeding amount.

[0025] According to the preparation method of the hydrocracking catalyst provided by the present disclosure, the method comprises the following steps:

[0026] (1) subjecting the materials comprising Y molecular sieves and SAPO-34 molecular sieves to molding, drying and calcinating to obtain a carrier;

[0027] (2) introducing silane and active ingredients into the carrier prepared in the step (1), wherein the active ingredients comprise VIB group metal and/or VIII group metal, and then carrying out drying and calcinating.

[0028] It is preferable that the materials in the step (1) further comprise a binder or a precursor thereof, or the binder or the precursor thereof is added during the molding process.

[0029] According to a preferred embodiment of the present disclosure, in the step (1) of the aforementioned method, the materials further comprise microcrystalline cellulose. Preferably, the content of the microcrystalline cellulose in the materials is within a range of 0.2-6 wt %, preferably 0.5-4 wt %. The inclusion of microcrystalline cellulose can improve the pore structure of the carrier, such that the catalyst containing the carrier can further improve the yield of jet fuel. The present disclosure does not impose special requirement on the physical properties of microcrystalline cellulose, all kinds of commercially available microcrystalline cellulose can be used in the present disclosure.

[0030] According to a preferred embodiment of the present disclosure, in the step (1) of the aforementioned method, the drying conditions are as follows: the drying temperature is within a range of 60-180° C., preferably 90-120° C.; the drying time is within a range of 0.5-20.0 hours, preferably 3.0-6.0 hours; the calcinating conditions are as follows: the calcinating temperature is within a range of 350-750° C., preferably 500-650° C.; the calcinating time is within a range of 0.5-20.0 hours, preferably 3.0-6.0 hours. The shape of the carrier can be molded as required, such as a dentate sphere, a three-leaf clover shape, a four-leaf clover shape, a cylindrical strip shape, or other suitable shape. The calcinating is performed in an oxygen-containing atmosphere, and the oxygen concentration is not particularly limited, and may be a pure oxygen atmosphere, an air atmosphere, or the like. The drying may be performed in an air atmosphere, or an inert atmosphere such as a nitrogen atmosphere.

[0031] In the present disclosure, the silane is used for subsequently forming silica by calcinating, and is attached to the outer surface of the carrier and the inner surface of the pore passage, thus the silane may be an organosilicon compound which meets the above conditions. Preferably, the silane in step (2) of the aforementioned method is one or more selected from the group consisting of aminosilane, alkylsilane, sulfur-containing silane, and siloxane. The aminosilane refers to an organic compound which contains amino group and silicon atoms in the molecule and only contains five elements N, H, Si, O and C, the amino group may be one or more selected from the group consisting of a primary amine group, a secondary amine group and a tertiary amine group, the number of the amino group may be one or more; it is preferable that the number of carbon atoms of the aminosilane is not more than 9 or the molecular weight is not more than 230, for example, the aminosilane may be one or more selected from the group consisting of 3-aminopropyltrimethoxysilane, aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-diethylenetriaminepropylmethyldimethoxysilane, and N-aminoethyl-3-aminopropylmethyldimethoxysilane or a combination thereof. The alkylsilane refers to an organic compound containing only four elements H, Si, O and C in a molecule, preferably the alkylsilane has not more than 19 carbon atoms, and may be, for example, one or more selected from the group consisting of diphenyl dimethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, methyltriacetoxysilane, dodecyltriethoxysilane and hexadecyltrimethoxysilane or a combination thereof. The sulfur-containing silane refers to an organic compound containing only five elements S, H, Si, O and C in a molecule, preferably the carbon atom number of the sulfur-containing silane is not more than 18, and for example, the sulfur-containing silane may be one or more selected from the group consisting of bis-[3-(triethoxy silicon)propyl]-tetrasulfide, mercaptopropyl trimethoxy silane and 3-mercaptopropyl triethoxy silane or a combination thereof. The siloxane refers to a polymer having a main chain of Si—O—Si and the repeating units of R.sub.2SiO, wherein R may be various alkyl groups with 1-4 carbon atoms.

[0032] In step (2) of the aforementioned method, the silane or active ingredient is introduced into the carrier by means of impregnation method, which is either an incipient-wetness impregnation method, or an excess impregnation; either a stepwise impregnation or a co-impregnation, preferably an equal volume impregnation. The impregnation methods are well known among those skilled in the art.

[0033] The active ingredients are preferably water-soluble salts of the respective active ingredients, such as chlorides and/or nitrates.

[0034] According to a preferred embodiment of the present disclosure, the method further comprises loading phosphorus onto the carrier obtained in step (1). The impregnation of the phosphorus onto the carrier can be carried out simultaneously with the active ingredients and the silane or in stages, preferably simultaneously. It is preferable that the phosphoric acid is used for providing phosphorus.

[0035] The final product catalyst is prepared by impregnating the carrier with a solution containing silane or active ingredients, and carrying out drying and calcinating. The drying conditions are conventional, the drying temperature is within a range of 60-200° C., preferably 90-130° C., and the drying time is within a range of 0.5-20 hours, preferably 1-6 hours. The calcinating temperature is within a range of 300-500° C., preferably 380-450° C., and the calcinating time is within a range of 0.5-20 hours, preferably 1-6 hours.

[0036] In the step (2) of the above-mentioned method, the active ingredients and the silane may be introduced simultaneously or separately, preferably simultaneously; when the active ingredients and the silane are introduced simultaneously, the molar ratio of the silane to the VIB group metal in the impregnation liquid is 0.01:1-10: 1, preferably 0.01:1-5:1.

[0037] According to the method, silane is impregnated on the carrier with a loading mode similar to that of the active ingredients, and then subjecting the carrier to calcinating, such that silica is generated in situ and loaded on the carrier, the silica and the active ingredients are jointly distributed on the outer surface of the carrier and the inner surface of a pore channel, thereby significantly increase the yield of jet fuel in the hydrocracking product.

[0038] The solvent in the impregnation liquid is preferably water, further preferably, the impregnation liquid comprises one or more selected from the group of glycerol, N,N-dimethylformamide, acetone, dimethyl sulfoxide, ethanolamine, diethanolamine, triethanolamine and ammonium citrate; the molar ratio of one or more selected from the group of glycerol, N,N-dimethylformamide, acetone, dimethyl sulfoxide, ethanolamine, diethanolamine, triethanolamine and ammonium citrate to the VIII group metal is preferably within a range of 0.01:1-8:1, and preferably 0.01:1-4:1.

[0039] The hydrocracking catalyst of the present disclosure is applicable to the hydrocracking process for producing jet fuel, the operating conditions are as follows: the reaction temperature is within a range of 340-430° C., preferably 355-385° C.; the hydrogen partial pressure is within a range of 5-20 MPa, preferably 8-15 MPa; the hydrogen-oil volume ratio is within a range of 500-2000: 1, preferably 750-1500:1; and the liquid hourly space velocity is within a range of 0.5-1.8 h.sup.−1, preferably 0.7-1.5 h.sup.−1.

[0040] The hydrocracking catalyst of the present disclosure is suitable for processing heavy feedstock oil, which including one or more selected from the group consisting of reduced pressure distillate oil, coking gas oil, catalytic cracking gas oil, catalytic cracking cycle oil or a combination thereof. Preferably, the heavy feedstock oil is hydrocarbons with a boiling point of 300-600° C., and the nitrogen content is generally within a range of 50-2,800 mg/g.

[0041] In order to better illustrate the present disclosure, the functions and effects of the present disclosure will be further described below with reference to examples and comparative examples, but the scope of the present disclosure is not limited to these examples. In the following examples and comparative examples, unless otherwise specified, % represents % by mass, the alumina represents γ-alumina. The molar ratio of SiO.sub.2/Al.sub.2O.sub.3 is measured with chemical analysis using the ZSX100e type Wavelength Dispersive X-ray Fluorescence Spectrometer (XRF) manufactured by the Rigaku Corporation in Japan; the specific surface area, the pore volume and the pore distribution are measured by a low-temperature liquid nitrogen physical adsorption method according to the National Standard GB/T-19587-A2004 of China, and using a low-temperature nitrogen adsorption instrument with ASAP2420 model of Micromeritics Corporation in the United States of America (USA); the composition of the catalyst is obtained by calculation according to the feeding amount.

EXAMPL 1

[0042] (1) Preparation of the Hydrocracking Catalyst Carrier

[0043] 20 g of Y molecular sieves (the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 was 85, the specific surface area was 756 m.sup.2/g, the total pore volume was 0.38 mL/g) and 8 g of SAPO-34 molecular sieves (the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 was 0.25, the specific surface area was 728 m.sup.2/g, the total pore volume was 0.32 mL/g), 80 g of alumina and 4.2 g of microcrystalline cellulose were added into a rolling machine for carrying out rolling compaction, after the dry mixing was performed for 5 minutes, 85 g of aqueous solution containing 3.85 g of nitric acid was added, the mixture was subjected to rolling compaction for 20 minutes, and rolled into a paste, the strip-extruding was carried out, and the extruded strips were subjected to drying at 120° C. for 3 hours and calcinating at 500° C. for 3 hours to obtain a carrier Z1.

[0044] (2) Preparation of the Catalyst

[0045] The carrier Z1 was impregnated in an incipient-wetness impregnation method with an impregnation liquid containing Mo, Ni, P, bis[3-(triethoxysilyl)propyl]-tetrasulfide (CAS#: 40372-72-3), N,N-dimethylformamide and water, wherein the molar ratio of the bis-[3-(triethoxysilyl)propyl]-tetrasulfide to the Mo contained in the final catalyst was 0.05:1, the molar ratio of the N,N-dimethylformamide to the Ni contained in the final catalyst was 0.04:1, the impregnated carrier was subjected to drying at 120° C. for 3 hours, and calcinating at 390° C. for 2 hours, the finally prepared catalyst was labeled as C-1, the properties of the catalyst were shown in Table 1.

EXAMPLE 2

[0046] (1) Preparation of the Hydrocracking Catalyst Carrier

[0047] 25 g of Y molecular sieves (the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 was 65, the specific surface area was 750 m.sup.2/g, the total pore volume was 0.48 mL/g) and 6 g of SAPO-34 molecular sieves (the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 was 0.05, the specific surface area was 550 m.sup.2/g, the total pore volume was 0.35 mL/g), 70 g of silica and 2.8 g of microcrystalline cellulose were added into a rolling machine for carrying out rolling compaction, after the dry mixing was performed for 6 minutes, 80 g of aqueous solution containing 3.54 g of nitric acid was added, the mixture was subjected to rolling compaction for 25 minutes, and rolled into a paste, the strip-extruding was carried out, and the extruded strips were subjected to drying at 120° C. for 3 hours and calcinating at 550° C. for 3 hours to obtain a carrier Z2.

[0048] (2) Preparation of the Catalyst

[0049] The carrier Z2 was impregnated in an incipient-wetness impregnation method with an impregnation liquid containing Mo, Ni, P, N-aminoethyl-3-aminopropylmethyldimethoxysilane (CAS #: 3069-29-2), glycerol and water, wherein the molar ratio of the N-aminoethyl-3-aminopropylmethyldimethoxysilane to the Mo contained in the final catalyst was 0.08:1, the molar ratio of the glycerol to the Ni contained in the final catalyst was 0.08:1, the impregnated carrier was subjected to drying at 120° C. for 3 hours, and calcinating at 410° C. for 2 hours, the finally prepared catalyst was labeled as C-2, the properties of the catalyst were shown in Table 1.

EXAMPLE 3

[0050] (1) Preparation of the Hydrocracking Catalyst Carrier

[0051] 25 g of Y molecular sieves (the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 was 150, the specific surface area was 1,000 m.sup.2/g, the total pore volume was 0.6 mL/g) and 7 g of SAPO-34 molecular sieves (the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 was 0.5, the specific surface area was 500 m.sup.2/g, the total pore volume was 0.55 mL/g), 75 g of amorphous silica-alumina (the specific surface area was 425m.sup.2/g, and the pore volume was 1.2 mL/g), and 2.0 g of microcrystalline cellulose were added into a rolling machine for carrying out rolling compaction, after the dry mixing was performed for 5 minutes, 88 g of aqueous solution containing 9.5 g of acetic acid was added, the mixture was subjected to rolling compaction for 30 minutes, and rolled into a paste, the strip-extruding was carried out, and the extruded strips were subjected to drying at 120° C. for 3 hours and calcinating at 560° C. for 3 hours to obtain a carrier Z3.

[0052] (2) Preparation of the Catalyst

[0053] The carrier Z3 was impregnated in an incipient-wetness impregnation method with an impregnation liquid containing Mo, Ni, P, methyl triacetoxysilane (CAS#: 4253-34-3), dimethyl sulfoxide and water, wherein the molar ratio of the methyl triacetoxysilane to the Mo contained in the final catalyst was 0.08:1, the molar ratio of the dimethyl sulfoxide to the Ni contained in the final catalyst was 0.1:1, the impregnated carrier was subjected to drying at 120° C. for 3 hours, and calcinating at 380° C. for 2 hours, the finally prepared catalyst was labeled as C-3, the properties of the catalyst were shown in Table 1.

EXAMPLE 4

[0054] (1) Preparation of the Hydrocracking Catalyst Carrier

[0055] 26 g of Y molecular sieves (the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 was 60, the specific surface area was 750 m.sup.2/g, the total pore volume was 0.52 mL/g) and 8 g of SAPO-34 molecular sieves (the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 was 0.08, the specific surface area was 685 m.sup.2/g, the total pore volume was 0.38 mL/g), 75 g of alumina and 4.0 g of microcrystalline cellulose were added into a rolling machine for carrying out rolling compaction, after the dry mixing was performed for 5 minutes, 80 g of aqueous solution containing 10 g of acetic acid (with the concentration of 36 wt %) was added, the mixture was subjected to rolling compaction for 18 minutes, and rolled into a paste, the strip-extruding was carried out, and the extruded strips were subjected to drying at 110° C. for 3 hours and calcinating at 580° C. for 4 hours to obtain a carrier Z4.

[0056] (2) Preparation of the Catalyst

[0057] The carrier Z4 was impregnated in an equal volume with an impregnation liquid containing Mo, Ni, P, mercaptopropyl trimethoxy silane (CAS#: 4420-74-0) , oxalic acid and water, wherein the molar ratio of the mercaptopropyl trimethoxy silane to the Mo contained in the final catalyst was 0.1:1, the molar ratio of the oxalic acid to the Ni contained in the final catalyst was 0.12:1, the impregnated carrier was subjected to drying at 120° C. for 3 hours, and calcinating at 440° C. for 2 hours, the finally prepared catalyst was labeled as C-4, the properties of the catalyst were shown in Table 1.

EXAMPLE 5

[0058] (1) Preparation of the Hydrocracking Catalyst Carrier

[0059] 25 g of Y molecular sieves (the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 was 62, the specific surface area was 746 m.sup.2/g, the total pore volume was 0.53 mL/g) and 9 g of SAPO-34 molecular sieves (the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 was 0.07, the specific surface area was 722 m.sup.2/g, the total pore volume was 0.51 mL/g), 86 g of alumina and 4 g of microcrystalline cellulose were added into a rolling machine for carrying out rolling compaction, after the dry mixing was performed for 6 minutes, 78 g of aqueous solution containing 5 g of acetic acid and 1.54 g of nitric acid was added, the mixture was subjected to rolling compaction for 20 minutes, and rolled into a paste, the strip-extruding was carried out, and the extruded strips were subjected to drying at 100° C. for 6 hours and calcinating at 600° C. for 3 hours to obtain a carrier Z5.

[0060] (2) Preparation of the Catalyst

[0061] The carrier Z5 was impregnated in an incipient-wetness impregnation method with an impregnation liquid containing Mo, Ni, P, dodecyl triethoxysilane (CAS#: 3069-21-4), diethanolamine and water, wherein the molar ratio of the dodecyl triethoxysilane to the Mo contained in the final catalyst was 0.2:1, the molar ratio of the diethanolamine to the Ni contained in the final catalyst was 0.2:1, the impregnated carrier was subjected to drying at 120° C. for 3 hours, and calcinating at 400° C. for 2 hours, the finally prepared catalyst was labeled as C-5, the properties of the catalyst were shown in Table 1.

EXAMPLE 6

[0062] (1) Preparation of the Hydrocracking Catalyst Carrier

[0063] The preparation was carried out in the same manner as in the step (1) of the Example 5, except that the microcrystalline cellulose was not added, so as to obtain a carrier Z6.

[0064] (2) Preparation of the Catalyst

[0065] The preparation was performed in the same manner as in the step (2) of the Example 5, except that the carrier Z5 was replaced with the aforementioned carrier Z6, the finally prepared catalyst was labeled as C-6. The properties of the catalyst were shown in Table 1.

EXAMPLE 7

[0066] (1) Preparation of the Hydrocracking Catalyst Carrier

[0067] The carrier was prepared with the same method as in the Example 5.

[0068] (2) Preparation of the Catalyst

[0069] The preparation was performed in the same manner as in the step (2) of the Example 5, except that impregnation liquid did not contain glycol amine, the finally prepared catalyst was labeled as C-7. The properties of the catalyst were shown in Table 1.

COMPARATIVE EXAMPLE 1

[0070] (1) Preparation of the Hydrocracking Catalyst Carrier

[0071] The preparation was carried out in the same manner as in the step (1) of the Example 5, except that the microcrystalline cellulose was not added, so as to obtain a carrier DZ1.

[0072] (2) Preparation of the Catalyst

[0073] The preparation was performed in the same manner as in the step (2) of the Example 5, except that the carrier Z5 was replaced with the aforementioned carrier DZ1, and the impregnation liquid did not contain diethanolamine and dodecyl triethoxy silane, the finally prepared catalyst was labeled as DC-1. The properties of the catalyst were shown in Table 1.

COMPARATIVE EXAMPLE 2

[0074] (1) Preparation of the Hydrocracking Catalyst Carrier

[0075] The preparation was carried out in the same manner as in the step (1) of the Example 5, except that the microcrystalline cellulose was not added, and the SAPO-34 molecular sieves were replaced with the same weight of Y molecular sieve, i.e., the added amount of Y molecular sieves was 34 g, so as to obtain a carrier DZ2.

[0076] (2) Preparation of the Catalyst

[0077] The preparation was performed in the same manner as in the step (2) of the Example 5, except that the carrier Z5 was replaced with the aforementioned carrier DZ2, the finally prepared catalyst was labeled as DC-2. The properties of the catalyst were shown in Table 1.

COMPARATIVE EXAMPLE 3

[0078] (1) Preparation of Hydrocracking Catalyst Carrier

[0079] The preparation was carried out in the same manner as in the step (1) of the Example 5, except that the microcrystalline cellulose was not added, and the SAPO-34 molecular sieves were replaced with the same weight of Y molecular sieve, i.e., the added amount of Y molecular sieves was 34 g, so as to obtain a carrier DZ3.

[0080] (2) Preparation of the Catalyst

[0081] The preparation was performed in the same manner as in the step (2) of the Example 5, except that the carrier Z5 was replaced with the aforementioned carrier DZ3, the finally prepared catalyst was labeled as DC-3. The properties of the catalyst were shown in Table 1.

COMPARATIVE EXAMPLE 4

[0082] (1) Preparation of the Hydrocracking Catalyst Carrier

[0083] The preparation was carried out in the same manner as in the step (1) of the Example 5, except that the microcrystalline cellulose was not added, and the SAPO-34 molecular sieves were replaced with the same weight of SAPO-11 molecular sieves (the molar ratio of SiO.sub.2/Al.sub.2O.sub.3 was 0.3, the specific surface area was 735 m.sup.2/g, and the total pore volume was 0.52 mL/g), so as to obtain a carrier DZ4.

[0084] (2) Preparation of the Catalyst

[0085] The preparation was performed in the same manner as in the step (2) of the Example 5, except that the carrier Z5 was replaced with the aforementioned carrier DZ4, the finally prepared catalyst was labeled as DC-4. The properties of the catalyst were shown in Table 1.

EXAMPLE 8

[0086] (1) Preparation of the Hydrocracking Catalyst Carrier

[0087] The preparation was carried out in the same manner as in the step (1) of the Example 5, except that the pore volume of the secondary pores of the Y molecular sieves having a pore diameter of 1.7-10 nm accounted for 50% of the total pore volume, so as to obtain a carrier Z8.

[0088] (2) Preparation of the Catalyst

[0089] The preparation was performed in the same manner as in the step (2) of the Example 5, except that the carrier Z5 was replaced with the aforementioned carrier Z8, the finally prepared catalyst was labeled as C-8. The properties of the catalyst were shown in Table 1.

TABLE-US-00001 TABLE 1 Physicochemical properties of the catalysts Items C-1 C-2 C-3 C-4 C-5 DC-1 DC-2 DC-3 Y molecular 19 25 24 24.3 21.7 19 28 — sieve, wt % SAPO-34, wt % 7 6 6.8 7.4 7.8 7.7 — 7.0 SiO.sub.2, % 1.8 2.2 2.5 1.6 2.8 — — MoO.sub.3, wt % 21.2 20.0 21.1 21.5 21.0 21.1 21.6 21.3 NiO, wt % 5.9 6.0 6.1 6.0 6.1 6.2 6.0 6.1 P, wt % 1.35 1.42 1.38 1.36 1.43 1.41 1.40 1.35 Specific surface 186 184 193 185 190 182 181 192 area, m.sup.2/g Pore volume, ml/g 0.37 0.39 0.38 0.36 0.37 0.32 0.31 0.34 Pore distribution, 85 83 81 79 83 75 77 70 4-10 nm

TABLE-US-00002 TABLE 1 Physicochemical properties of the catalyst (continued) Items C-5 C-6 C-7 C-8 DC-4 Y molecular sieve 21.7 21.7 24.3 21.7 21.7 content, wt % SAPO-34 content, wt % 7.8 7.8 7.4 7.8 0 SiO.sub.2 content, % 2.8 2.8 1.6 2.8 2.8 MoO.sub.3, wt % 21.0 21.2 21.8 22.0 21.6 NiO, wt % 6.1 6.1 6.0 6.1 6.1 P, wt % 1.43 1.38 1.37 1.43 1.43 Specific surface area, 190 189 185 188 185 m.sup.2/g Pore volume, ml/g 0.37 0.37 0.36 0.38 0.38 Pore distribution, 83 C-6 C-7 85 84 4-10 nm Note: the SiO.sub.2 content in Table 1 was the amount of silica loaded by the carrier, and was calculated according to the feeding amount of silane.

[0090] The catalysts obtained in the above examples and comparative examples were subjected to activity evaluation tests. The test was performed in a 200 ml small-scale test device using an one-stage process with connection in series (i.e. hydrofining and hydrocracking were processed in series), the hydrofining catalyst comprising: 23.3 wt % of MoO.sub.3, 3.7 wt % of NiO, 1.38 wt % of phosphorus (P), and the balance was alumina carrier. The properties of the feedstock oil in use were shown in Table 2, and the operating conditions were as follows: the reactor inlet pressure was 14.7 MPa, the volume ratio of hydrogen-oil at the reactor inlet was 1200:1, the liquid hourly volume space velocity at the refining stage was 1.0 h.sup.−1, the average reaction temperature was 375° C.; the liquid hourly volume space velocity at the cracking stage was 1.4 h.sup.−1, the average reaction temperature was 383° C., and the catalyst activity results were shown in Table 3.

TABLE-US-00003 TABLE 2 Properties of the feedstock oil Feedstock oil Iran VGO Density 0.893 Distillation range, ° C. 310-552 Freezing point, ° C. 29 Aromatic hydrocarbons, wt % 38.2 BMCI value 45.7

TABLE-US-00004 TABLE 3 Evaluation results of catalysts Catalyst number C-1 C-2 C-3 C-4 C-5 DC-1 DC-2 DC-3 Heavy naphtha 8.5 9.1 9.6 8.8 8.7 8.1 7.6 5.2 (82-132° C.) yield, % Potential aromatic 61.5 61.6 62.5 61.8 65.3 62.5 59.2 43.6 hydrocarbon content, wt % Jet fuel (132- 40.2 40.3 39.8 38.9 39.2 32.7 30.5 20.2 282° C.) yield, % Smoke point, mm 26 25 25 25 27 23 21 19 Diesel oil (282- 18.5 17.6 17.9 18.3 18.1 20.3 21.5 15.3 370° C.) yield, % Cetane number 78.2 76.5 73.2 70.9 73.5 74.1 58.6 49.8 Tail oil (>370° C.) 30.8 30.9 31.7 32.2 31.9 35.8 36.5 58.5 yield, % BMCI value 11.5 11.2 11.7 11.1 11.5 12.8 13.6 26.8

TABLE-US-00005 TABLE 3 Evaluation results of catalysts (continued) Catalyst number C-5 C-6 C-7 C-8 DC-4 Heavy naphtha 8.7 8.3 9.1 8.5 6.5 (82-132° C.) yield, % Potential aromatic hydro- 65.3 61.4 62.1 62.6 58.6 carbon content, wt % Jet fuel (132-282° C.) 39.2 37.5 35.8 33.8 30.2 yield, % Smoke point, mm 27 25 24 25 23 Diesel oil (282-370° C.) 18.1 17.3 18.2 17.9 16.2 yield, % Cetane number 73.5 70.5 71.2 72.1 55.8 Tail oil ( >370° C.) 31.9 33.5 32.6 30.5 45.2 yield, % BMCI value 11.5 11.8 11.7 11.6 13.5

[0091] The evaluation results in Table 3 demonstrate that the catalysts of the present disclosure have the characteristics such as high jet fuel yield, excellent product properties, and low BMCI value of tail oil.