CN106669861A - Hydrocracking catalyst grading method and catalytic diesel oil hydrogenation conversion process - Google Patents
Hydrocracking catalyst grading method and catalytic diesel oil hydrogenation conversion process Download PDFInfo
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Abstract
The invention discloses a hydrocracking catalyst grading method and a catalytic diesel oil hydrogenation conversion process. The hydrocracking catalyst grading method comprises the following content: a hydrocracking reactor is divided into 2-8 reaction zones along the material flow direction, each reaction zone is filled with a mixture of a hydrocracking catalyst and a regenerated catalyst at the mass ratio of the hydrocracking catalyst to the regenerated catalyst being 10:1-1:10; and along the material flow direction, the mass ratio of the hydrocracking catalyst to the regenerated catalyst in each reaction zone is gradually reduced. The invention simultaneously provides a catalytic diesel oil hydrogenation conversion process by above catalyst grading. By filling the hydrocracking reactor with catalysts with different reaction properties, diesel oil/gasoline fraction hydrogenation selectivity during the conversion process is raised, and yield of high-octane gasoline product is increased.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst grading method and catalytic diesel oil hydroconversion process.
Background technology
In recent years, as the country processes the increasingly heaviness of crude quality, the raw material that catalytic cracking is processed also heaviness and in poor quality increasingly, in addition many enterprises are in order to reach the purpose for improving quality of gasoline or propylene enhancing, catalytic cracking unit has been carried out to transform or improve the operating severity of catalytic cracking unit, the quality for causing the product of catalytic cracking, particularly catalytic diesel oil more deteriorates.
To improve the utilization rate of petroleum resources, improve the total quality level of petrol and diesel oil fuel, realize that product blending is optimized and the maximized target of value of the product, meet the domestic novel technique that is hydrocracked to clean fuel increasing need, high aromatics diesel hydro-conversion production high added value naphtha component and low-sulfur cleaning diesel fuel and there is good application prospect.Both at home and abroad researcher has been also carried out substantial amounts of research work.Foreign countries catalytic cracking light cycle oil are converted into the relevant report of ultra-low-sulphur diesel and high octane value gasoline blending component using hydrocracking process technology.Such as：The meeting of nineteen ninety-five NPRA, David A.Pappal et al. are described by Mobil, Akzo
A kind of single-stage hydrocracking technology of Nobel/Nippon Ketjen and M.W.Kellogg companies exploitation.NPRA meetings in 2005, Vasant P. Thakkar et al. describe the LCO UnicrackingTM technologies of Uop Inc.'s exploitation.It is reported that, the catalytic cycle oil ingredient of low value can be converted into high octane gasoline component and fine-quality diesel oil blending component by both the above technology.The technical process is while ensureing that unconverted diesel component is fully hydrogenated with saturation raising diesel product Cetane number, the yield and octane number of gasoline component is a good and bad important indicator of the technology, therefore, how on the premise of diesel quality is ensured, diesel oil/gasoline component hydrogenation selectivity is improved, the key that gasoline products yield is the technology is improved.
Sinopec Fushun Petrochemical Research Institute develops catalytic diesel oil hydro-conversion technology（FD2G）And supporting catalyst.FD2G technologies adopt high temperature, the process conditions of low pressure, while being equipped with high cracking activity, the hydrocracking catalyst of low hydrogenation activity realizes the design object that catalytic diesel oil Efficient Conversion produces high-knock rating gasoline.This technology is showing the characteristics of being different from conventional hydrocracking process during commercial Application：First, compared to other hydrocracking technology processes, FD2G technical processes differ larger in start of run product slates and product quality with design object, gasoline products octane number and gasoline yield are substantially low, its reactivity worth presents the phenomenon for gradually improving in start of run, gradually improves until reaching a preferable metastable level as the duration of runs extends product slates and gasoline product quality.This process is more slow（Typically more than 1 month）The outstanding behaviours on commercial plant is that gasoline product quality is not up to standard in the start of run quite a long time, have impact on the benefit of enterprise, and further run to last stage reaction, reaction condition is harsher, as increasing for coke content all there occurs serious carbon deposit on strong acid and non-strong acid on catalyst, and active metal is assembled, the loss of catalyst activity reactivity worth is serious, therefore, significantly decline from reaction conversion ratio, product slates and product quality, it is impossible to meet reaction and require, at this moment catalyst needs to be regenerated.At present, the regeneration of Cracking catalyst hydrocracking catalyst after the operating of catalytic diesel oil hydroconversion process process is processed, usually more than at a temperature of 400 DEG C of even more highs, the calcination process in air atmosphere, complete the effect of de- charcoal and metal redistribution, so with the removing of carbide, one side catalyst meleic acid amount product can be recovered well, on the other hand, active metal on catalyst completes to disperse again, and the method regenerated catalyst is close in total acid/strong acid distribution with fresh dose.
The reaction process process of catalytic diesel oil hydro-conversion production high-knock rating gasoline is typically catalytic diesel oil raw material and first passes around preatreating reactors hydrodenitrogeneration reaction, then, denitrification reaction generates oil and carries out hydrocracking reaction generation high octane gasoline component into the hydrocracking reactor of back.In catalytic diesel oil hydroconversion process cracker, along the direction of reaction stream, as gasoline component content gradually increases in the intensification reaction stream of reaction depth, diesel component content is gradually reduced.Therefore, reactor is from top to bottom for the percentage contribution of diesel product and gasoline products is gradually changed.In reactor from top to bottom catalyst for diesel oil reaction contribution be gradually reduced, and to gasoline reaction contribution gradually increase.Therefore, for the technical goal of diesel oil/gasoline component selective reaction in realizing catalyst system to reacting cut, preferably course of reaction should be that reactor upper catalyst agent has preferable open loop and hydrogenation saturability, complete open loop, chain rupture and the hydrogenation saturation of diesel oil distillate, improve diesel product Cetane number, increasing gasoline yield product；And reactor lower part is due to being enriched gasoline fraction, in order to the octane number and yield that improve gasoline products then require that catalyst reduces as far as possible the saturability of gasoline fraction and further ring-opening reaction ability.Traditional catalytic diesel oil hydroconversion process cracker single catalyst system cannot meet such reaction requirement, therefore, the technology awaits further perfect.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of hydrocracking catalyst grading method and catalytic diesel oil hydroconversion process, realize improving conversion process diesel oil/gasoline component hydrogenation and Cracking Selectivity by the catalyst system of the grading loading differential responses performance in cracker, increase production the target of high octane gasoline products.
The hydrocracking catalyst grading method of the present invention, including herein below：Hydrocracking reactor is divided into 2 ~ 8 reaction zones along Flow of Goods and Materials direction, it is preferably divided into 3 ~ 6 reaction zones, mixed packing hydrocracking catalyst and regenerated catalyst in each reaction zone, the hydrocracking catalyst in each reaction zone is 10 with the mass ratio of regenerated catalyst:1~1:10, preferably 6:1~1:6, along Flow of Goods and Materials direction, the hydrocracking catalyst in each reaction zone is gradually reduced with the mass ratio of regenerated catalyst；Wherein described regenerated catalyst is the hydrocracking catalyst processed through regeneration after inactivation, and regenerated catalyst has following property：Specific surface area is 50 ~ 130m2/ g, pore volume is 0.07 ~ 0.15ml/g, carbon content 10wt% ~ 20wt%, 0.08 ~ 0.25mmol/L of total meleic acid amount；Regenerated catalyst is divided into carbon deposit area and non-carbon deposit area by the position that carbon deposit is present, wherein non-carbon deposit area is any point and 25 ~ 250 μ m thick scopes on cross-section center line direction, 50 ~ 200 μm of preferred scope in the outer most edge of regenerated catalyst particles cross section.
The preparation process of described regenerated catalyst is regeneration process, including：
（1）Carry out nitrogen displacement to regenerating furnace, oxygen 1 ~ 4v% of volume content in adjustment regeneration furnace atmosphere, and it is preheated to 400 ~ 800 DEG C；
（2）The hydrocracking catalyst inactivated after operating in catalytic diesel oil hydroconversion process is transferred to step（1）Regenerating furnace in quick roasting 5 ~ 30 minutes, take out product of roasting, be cooled to room temperature, then repeat above-mentioned quick roasting-taking-up-cooling procedure 1 ~ 4 time, obtain regenerated catalyst.
Catalytic diesel oil hydroconversion process of the present invention refers to that Sinopec Fushun Petrochemical Research Institute develops catalytic diesel oil hydro-conversion technology（FD2G）, general process conditions are as follows：Refining stage operating condition：4.0 ~ 10.0MPa of reaction pressure, 320 ~ 420 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1；Cracking zone operating condition：4.0 ~ 10.0MPa of reaction pressure, 360 ~ 440 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1.
Process raw material in catalytic diesel oil hydroconversion process of the present invention as catalytic diesel oil inferior, catalytic diesel oil density is 0.90 ~ 1.0g/cm3, boiling range scope at 180 ~ 400 DEG C, 500 ~ 2000ppm of nitrogen content, 5000 ~ 15000ppm of sulfur content, 60 ~ 90m% of arene content.
Step（2）The hydrocracking catalyst of the inactivation, with following property：Specific surface area is 40 ~ 100m2/ g, pore volume is 0.05 ~ 0.10ml/g, carbon content 12wt% ~ 25wt%, 0.05 ~ 0.2mmol/L of total meleic acid amount.
Hydrocracking catalyst of the present invention is conventional business-like light oil type hydrogen cracking fresh catalyst, such as HC-185, HC-190, FC-24, FC-24B, or the hydrocracking catalyst that is prepared according to prior art.Above-mentioned hydrocracking catalyst generally includes the silica-alumina supports and hydrogenation active metals of Y molecular sieve, and according to mass percent meter, the silica-alumina supports containing Y molecular sieve are 70% ~ 92%, and hydrogenation active metals are calculated as 8% ~ 30% with oxide；The specific surface area of the hydrocracking catalyst is 200 ~ 400m2/ g, pore volume is 0.2 ~ 0.5ml/g；The hydrogenation active metals can be the group VIII in the periodic table of elements and/or group vi metallic element, and wherein group VIII active metal can be Ni and/or Co, and group vi active metal is being W and/or Mo；The group VIII active metallic content is generally 2% ~ 10%, and the VIth VI races active metallic content is generally 5% ~ 20%.Described Y molecular sieve content in the carrier is generally 30% ~ 90%, preferably 40% ~ 70%, and remainder is amorphous silica-alumina and/or aluminum oxide；The Y molecular sieve property is as follows：700～900m of specific surface area2/ g, 0.35～0.60ml/g of total pore volume, relative crystallinity 90%～130%, cell parameter 2.437～2.460, meleic acid 0.5～1.5mmol/g of amount.
Catalyst of the present invention is（It is solid）It is granular, rather than the amorphous state such as powder.Used as the shape of the particle, it is conventional use of variously-shaped to enumerate this area hydrocracking catalyst, such as can further enumerate spherical and column.As described spherical, such as can enumerate spheroidal and elliposoidal etc.；As the column, such as can enumerate cylindric, flat column and profiled-cross-section（Such as clover, bunge bedstraw herb etc.）Column etc..
In the present invention, so-called " cross section of catalyst granules " refers to minimum dimension direction along a catalyst granules exposed whole surface after the geometric center cutting of its shape.Such as, the catalyst granules for it is spherical when, the cross section refers to exposed whole surface after the radius or short-axis direction along the ball is cut by its centre of sphere.Or, when the catalyst granules is column, the cross section refer to perpendicular to the length dimension direction of the post cut by the central point of the length dimension after exposed whole surface.
In the present invention, the periphery of the exposed surface is referred to as into the outer most edge of the cross section, by the geometric center（Than the centre of sphere as the aforementioned or the central point of length dimension）Central point referred to as on the cross section.
Present invention simultaneously provides a kind of catalytic diesel oil hydroconversion process, including herein below：
I, under the conditions of hydrofining technology, the mixed material of catalytic cracking diesel oil and hydrogen is introduced into hydrogenation reactor and Hydrobon catalyst haptoreaction；
II, under the conditions of hydrocracking process, hydrofining reaction effluent be directly entered according to above-mentioned hydrocracking catalyst grading method load hydrocracking reactor, the hydrocracking catalyst bed haptoreaction with grading loading in reactor；
III, step（II）Obtain that hydrocracking reaction effluent is separated and fractionation obtains naphtha component and diesel component, wherein naphtha component directly goes out device as high-knock rating gasoline blend component, diesel component can directly go out device blended diesel, be also recycled into cracker and further react.
Step（I）Described hydrofining technology condition is：4.0 ~ 10.0MPa of reaction pressure, 320 ~ 420 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1.
Step（I）Described hydrocracking process condition is：4.0 ~ 10.0MPa of reaction pressure, 360 ~ 440 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1.
Step（I）Described Hydrobon catalyst can use commercially available prod, it is also possible to be prepared according to this area Conventional wisdom.Hydrobon catalyst used by the present invention can adopt conventional hydrocracking pretreatment catalyst, typically with group vib and/or group VIII metal as active component, with aluminum oxide or silicon-containing alumina as carrier.Vib metals are generally Mo and/or W, and group VIII metal is generally Co and/or Ni.On the basis of the weight of catalyst, vib metals content is calculated as 8wt%～28wt% with oxide, and group VIII tenor is calculated as 2wt%～15wt% with oxide.
The inventive method is measured by ESEM, x-ray photoelectron power spectrum etc. to the non-carbon deposit area thickness of phosphorus content and regenerated catalyst of catalyst.
Catalytic reaction process and reaction stream composition have following rule in catalytic diesel oil hydrocracking process process cracker：The further saturation of the gasoline component of course of reaction open loop, fracture and conversion process generation mainly including diesel oil distillate and open loop in cracker, for this two classes reaction, the open loop of diesel oil distillate, fracture are conducive to improving diesel product Cetane number and increasing gasoline yield, and react the further reaction of the gasoline component for generating then for yield of gasoline and product quality are unfavorable.In the face of this contradiction, conventional single catalyst system cannot be taken into account.And the present inventor's Jing analyses find, the ratio along logistics direction, diesel oil distillate and gasoline fraction in cracker is gradually changed, and gasoline component gradually increases and diesel component is gradually decreased, it may be said that reactor top（Logistics direction from top to bottom）Meet the open loop of diesel oil distillate, hydrogenation reaction with greater need for the higher acidity of catalyst, hydrogenation capability, and bottom diesel component ratio declines, gasoline proportionality rises, accordingly, it would be desirable to reduce catalyst activity and the saturation to gasoline component, cracking reaction.
Fresh hydrocracking catalyst has higher cracking and hydrogenation activity, is conducive to abundant hydrogenation and the conversion of diesel oil distillate；The present invention regenerates the hydrocracking catalyst for processing using specific process, catalytic inner duct and activated centre are covered by carbon deposit and are shielded, its activated centre is mainly in catalyst surface, therefore, outer surface reaction can be considered as, speed away catalyst after reactant and catalyst haptoreaction, advantageously reduces the secondary cracking and hydrogenation saturation of the gasoline component of primary first-order equation generation, and course of reaction is significantly improved to polycyclic/mononuclear aromatics hydrogenation and selectivity of ring-opening.In cracker catalyst grading distribution scheme of the present invention, logistics direction is as a example by from top to bottom, from reactor top to reactor lower part, by gradually stepping up ratio of the regenerative agent in mixed catalyst, improve the technological reaction process diesel oil/gasoline component hydrogenation and cracking reaction selectivity, while diesel product quality is ensured, gasoline products octane number and yield are improved.
Specific embodiment
Next step further describes the technical characterstic of the present invention by embodiment, but these embodiments can not limit the present invention.
Heretofore described catalytic diesel oil hydroconversion process refers to that Sinopec Fushun Petrochemical Research Institute develops catalytic diesel oil hydro-conversion technology（FD2G）, general process conditions are as follows：
Refining stage operating condition：4.0 ~ 10.0MPa of reaction pressure, 320 ~ 420 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1.
Cracking zone operating condition：4.0 ~ 10.0MPa of reaction pressure, 360 ~ 440 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1.
Step（One）Process raw material in described catalytic diesel oil hydroconversion process as catalytic diesel oil inferior, catalytic diesel oil density is 0.90 ~ 1.0g/cm3, boiling range scope at 180 ~ 400 DEG C, 500 ~ 2000ppm of nitrogen content, 5000 ~ 15000ppm of sulfur content, 60 ~ 90m% of arene content.
Embodiment 1
（1）Regenerating furnace nitrogen displacement is heated to 500 DEG C to oxygen volume content 2v%；
（2）Take catalytic diesel oil hydro-conversion commercial plant operating after spent agent as step（1）Preheated regeneration kiln roasting 15 minutes；
（3）Take out step（2）Catalyst after roasting, as room temperature decentralization .5h is set to 0；
（4）Regenerating furnace nitrogen displacement is heated to 600 DEG C to oxygen volume content 1v%；
（5）By step（3）Placing to the catalyst of room temperature adds regeneration kiln roasting to obtain within 10 minutes the regenerated catalyst of embodiment 1, numbering Z-1；
Embodiment 2
（1）Regenerating furnace nitrogen displacement is heated to 550 DEG C to oxygen volume content 2v%；
（2）Take catalytic diesel oil hydro-conversion commercial plant operating after spent agent as step（1）Preheated regeneration kiln roasting 10 minutes；
（3）Take out step（2）Catalyst after roasting, as room temperature decentralization .5h is set to 0；
（4）Regenerating furnace nitrogen displacement is heated to 500 DEG C to oxygen volume content 1v%；
（5）By step（3）Place to the catalyst of room temperature and add regeneration kiln roasting 15 minutes；
（6）Take out step（5）Catalyst after after baking, as placing 1h under room temperature；
（7）Regenerating furnace nitrogen displacement is heated to 500 DEG C to oxygen volume content 1v%；
（8）By step（6）Placing to the catalyst of room temperature adds regeneration kiln roasting to obtain within 15 minutes the regenerated catalyst of embodiment 2, numbering Z-2；
Embodiment 3
（1）Regenerating furnace nitrogen displacement is heated to 600 to oxygen volume content 3v%；
（2）Take catalytic diesel oil hydro-conversion commercial plant operating after spent agent as step（1）Preheated regeneration kiln roasting 15 minutes；
（3）Take out step（2）Catalyst after roasting, as room temperature decentralization .5h is set to 0；
（4）Regenerating furnace nitrogen displacement is heated to 600 DEG C to oxygen volume content 2v%；
（5）By step（3）Place to the catalyst of room temperature and add regeneration kiln roasting 10 minutes；
（6）Take out step（5）Catalyst after after baking, as placing 1h under room temperature；
（7）Regenerating furnace nitrogen displacement is heated to 600 DEG C to oxygen volume content 1v%；
（8）By step（6）Placing to the catalyst of room temperature adds regeneration kiln roasting to obtain within 10 minutes the regenerated catalyst of embodiment 3, numbering Z-3；
Embodiment 4
（1）Regenerating furnace nitrogen displacement is heated to 700 DEG C to oxygen volume content 1.5v%；
（2）Take catalytic diesel oil hydro-conversion commercial plant operating after spent agent as step（1）Preheated regeneration kiln roasting 5 minutes；
（3）Take out step（2）Catalyst after roasting, as room temperature decentralization .5h is set to 0；
（4）Regenerating furnace nitrogen displacement is heated to 550 DEG C to oxygen volume content 1v%；
（5）By step（3）Placing to the catalyst of room temperature adds regeneration kiln roasting to obtain within 10 minutes the regenerated catalyst of embodiment 4, numbering Z-4；
Comparative example 1
（1）The hydrocracking catalyst spent agent after the operating of catalytic diesel oil hydro-conversion commercial plant is taken as in regenerating furnace；
（2）Air is passed through in regenerating furnace, then, with 25 DEG C/h heating rates 550 DEG C is warming up to, constant temperature calcining 4h obtains the regenerative agent of comparative example 1, numbering B-1；
Embodiment 5
In order to further illustrate effect of the embodiment catalyst grade with system, midget plant comparative evaluation test has been carried out.With catalytic diesel oil as reaction raw materials oil, technological process is once passed through using single hop series connection, the pretreatment catalyst that catalyst refining stage is adopted is the widely used FF-36 hydrogenation pretreatment catalysts in this area, and cracking zone loads respectively A/Z-1, A/Z-2, A/Z-3, A/B-1, B-2 and several levels of more than A match somebody with somebody system.The raw materials used property of evaluation test, catalyst, cracking zone subregion, appreciation condition and evaluation result are listed in table 1 ~ 5.
The new agent of table 1 and industrial operation catalyst physico-chemical property.
The embodiment of table 2 and comparative example catalyst physico-chemical property.
The raw material oil nature of table 3.
The appreciation condition of table 4.
The embodiment of table 5 and comparative example evaluating catalyst result.
Claims (10)
1. a kind of hydrocracking catalyst grading method, it is characterised in that including herein below：Hydrocracking reactor is divided into 2 ~ 8 reaction zones along Flow of Goods and Materials direction, mixed packing hydrocracking catalyst and regenerated catalyst in each reaction zone, the hydrocracking catalyst in each reaction zone is 10 with the mass ratio of regenerated catalyst:1~1:10, along Flow of Goods and Materials direction, the hydrocracking catalyst in each reaction zone is gradually reduced with the mass ratio of regenerated catalyst；Wherein described regenerated catalyst is the hydrocracking catalyst processed through regeneration after inactivation, and regenerated catalyst has following property：Specific surface area is 50 ~ 130m2/ g, pore volume is 0.07 ~ 0.15ml/g, carbon content 10wt% ~ 20wt%, 0.08 ~ 0.25mmol/L of total meleic acid amount；Regenerated catalyst is divided into carbon deposit area and non-carbon deposit area by the position that carbon deposit is present, wherein non-carbon deposit area is any point and 25 ~ 250 μ m thick scopes on cross-section center line direction in the outer most edge of regenerated catalyst particles cross section.
2. according to the grading method described in claim 1, it is characterised in that：The non-carbon deposit area of the regenerated catalyst stated is any point and 50 ~ 200 μ m thick scopes on cross-section center line direction in the outer most edge of regenerated catalyst particles cross section.
3. according to the grading method described in claim 1, it is characterised in that：The preparation process of described regenerated catalyst, including：（1）Carry out nitrogen displacement to regenerating furnace, oxygen 1 ~ 4v% of volume content in adjustment regeneration furnace atmosphere, and it is preheated to 400 ~ 800 DEG C；（2）The hydrocracking catalyst inactivated after operating in catalytic diesel oil hydroconversion process is transferred to step（1）Regenerating furnace in quick roasting 5 ~ 30 minutes, take out product of roasting, be cooled to room temperature, then repeat above-mentioned quick roasting-taking-up-cooling procedure 1 ~ 4 time, obtain regenerated catalyst.
4. according to the grading method described in claim 3, it is characterised in that：Step（2）The hydrocracking catalyst of the inactivation, with following property：Specific surface area is 40 ~ 100m2/ g, pore volume is 0.05 ~ 0.10ml/g, carbon content 12wt% ~ 25wt%, 0.05 ~ 0.2mmol/L of total meleic acid amount.
5. according to the grading method described in claim 1, it is characterised in that：Described hydrocracking catalyst includes the silica-alumina supports and hydrogenation active metals of Y molecular sieve, and according to mass percent meter, the silica-alumina supports containing Y molecular sieve are 70% ~ 92%, and hydrogenation active metals are calculated as 8% ~ 30% with oxide；The specific surface area of the hydrocracking catalyst is 200 ~ 400m2/ g, pore volume is 0.2 ~ 0.5ml/g；The hydrogenation active metals are the group VIII in the periodic table of elements and/or group vi metallic element, and wherein group VIII active metal is Ni and/or Co, and group vi active metal is being W and/or Mo；The group VIII active metallic content is 2% ~ 10%, and group vi active metallic content is 5% ~ 20%；Described Y molecular sieve content in the carrier is 30% ~ 90%, and remainder is amorphous silica-alumina and/or aluminum oxide.
6. according to the grading method described in claim 5, it is characterised in that：The Y molecular sieve property is as follows：700～900m of specific surface area2/ g, 0.35～0.60ml/g of total pore volume, relative crystallinity 90%～130%, cell parameter 2.437～2.460, meleic acid 0.5～1.5mmol/g of amount.
7. a kind of catalytic diesel oil hydroconversion process, it is characterised in that including herein below：I, under the conditions of hydrofining technology, the mixed material of catalytic cracking diesel oil and hydrogen is introduced into hydrogenation reactor and Hydrobon catalyst haptoreaction；II, under the conditions of hydrocracking process, hydrofining reaction effluent is directly entered the hydrocracking reactor according to the hydrocracking catalyst grading method filling described in claim 1 ~ 4 any claim, the hydrocracking catalyst bed haptoreaction with grading loading in reactor；III, step（II）Obtain that hydrocracking reaction effluent is separated and fractionation obtains naphtha component and diesel component.
8. according to the technique described in claim 7, it is characterised in that：Step（I）Described hydrofining technology condition is：4.0 ~ 10.0MPa of reaction pressure, 320 ~ 420 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1.
9. according to the technique described in claim 7, it is characterised in that：Step（I）Described hydrocracking process condition is：4.0 ~ 10.0MPa of reaction pressure, 360 ~ 440 DEG C of reaction temperature, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200：1~2000：1.
10. according to the technique described in claim 7, it is characterised in that：Step（I）Process raw material in described catalytic diesel oil hydroconversion process as catalytic diesel oil inferior, catalytic diesel oil density is 0.90 ~ 1.0g/cm3, boiling range scope at 180 ~ 400 DEG C, 500 ~ 2000ppm of nitrogen content, 5000 ~ 15000ppm of sulfur content, 60 ~ 90m% of arene content.
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