CN106669861B - Hydrocracking catalyst grading method and catalytic diesel oil hydroconversion process - Google Patents
Hydrocracking catalyst grading method and catalytic diesel oil hydroconversion process Download PDFInfo
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Abstract
The invention discloses a kind of hydrocracking catalyst grading method and catalytic diesel oil hydroconversion process.Hydrocracking catalyst grading method of the invention, including the following contents: 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 mass ratio of hydrocracking catalyst and regenerated catalyst in each reaction zone is 10:1 ~ 1:10, along Flow of Goods and Materials direction, the mass ratio of hydrocracking catalyst and regenerated catalyst in each reaction zone is gradually reduced.Present invention simultaneously provides a kind of catalytic diesel oil hydroconversion process matched using above-mentioned catalyst grade.The present invention improves conversion process diesel oil/gasoline component hydrogenation selectivity, improves the yield of high octane gasoline products by the catalyst of the grading loading differential responses performance in cracker.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst grading method and catalytic diesel oil hydroconversion process.
Background technique
In recent years, with the increasingly heaviness of domestic processed crude quality, the raw material that catalytic cracking is processed is also increasingly
Heaviness and in poor quality, many enterprises fill catalytic cracking to achieve the purpose that improve quality of gasoline or propylene enhancing in addition
The operating severity for having carried out being transformed or improve catalytic cracking unit is set, the product of catalytic cracking, especially catalysis bavin are caused
The quality of oil more deteriorates.
For the utilization rate for improving petroleum resources, the total quality for improving petrol and diesel oil fuel is horizontal, realizes that product blending is optimal
Change and the maximized target of value of the product, satisfaction are domestic to clean fuel increasing need, high aromatics diesel hydro-conversion
Production high added value naphtha component and low-sulfur cleaning diesel fuel be hydrocracked novel technique have well application before
Scape.Domestic and international researcher has also carried out a large amount of research work.Foreign countries have will catalysis using hydrocracking process technology
Cracking light cycle oil is converted into the relevant report of ultra-low-sulphur diesel and high octane value gasoline blending component.Such as: nineteen ninety-five NPRA
Meeting, David A.Pappal et al. are described by Mobil, Akzo Nobel/Nippon Ketjen and M.W.Kellogg company
A kind of single-stage hydrocracking technology of exploitation.NPRA meeting in 2005, Vasant P. Thakkar et al. describe UOP
The LCO UnicrackingTM technology of company's exploitation.It is reported that both the above technology can be by the catalytic cycle oil group of low value
Divide and is converted into high octane gasoline component and fine-quality diesel oil blending component.The technical process is guaranteeing that unconverted diesel component is abundant
While adding hydrogen saturation to improve diesel product Cetane number, the yield and octane number of gasoline component are a weights of the technology superiority and inferiority
Index is wanted, therefore, how under the premise of guaranteeing diesel quality, diesel oil/gasoline component hydrogenation selectivity is improved, improves gasoline and produce
Product yield is the key that the technology.
Sinopec Fushun Petrochemical Research Institute develops catalytic diesel oil hydro-conversion technology (FD2G) and mating catalysis
Agent.FD2G technology using high temperature, low pressure process conditions, while be equipped with high cracking activity, being hydrocracked for low hydrogenation activity is urged
Agent realizes the design object of catalytic diesel oil Efficient Conversion production high-knock rating gasoline.This technology is during industrial application
Show the characteristics of being different from conventional hydrocracking process: firstly, compared to other hydrocracking technology processes, FD2G technology mistake
Journey differs larger with design object in start of run product distribution and product quality, and gasoline products octane number and gasoline yield are bright
Show relatively low, reactivity worth shows the phenomenon that gradually improving in start of run, as the duration of runs extends product distribution and vapour
Oil product quality gradually improves until reaching a preferable metastable level.This process is more slowly (generally at 1
Month or more), outstanding behaviours is that gasoline product quality is not up to standard in the start of run quite a long time on commercial plant, shadow
The benefit of Xiang Liao enterprise, and last stage reaction is further run to, reaction condition is harsher, with the increase catalyst of coke content
Serious carbon deposit all has occurred on upper strong acid and non-strong acid, and active metal is assembled, catalyst activity reactivity energy loss
It loses seriously, therefore, from reaction conversion ratio, product distribution and the equal sharp fall of product quality, is unable to satisfy reaction and requires, at this moment
Catalyst is regenerated.Currently, Cracking catalyst hydrocracking catalyst after the operating of catalytic diesel oil hydroconversion process process
The regeneration treatment of agent, usually be greater than 400 DEG C it is even higher at a temperature of, the calcination process in air atmosphere completes de- charcoal
And the effect of metal redistribution, in this way with the removing of carbide, one side catalyst meleic acid amount product can be obtained very
Good recovery, on the other hand, the active metal completion on catalyst disperse again, and this method regenerated catalyst is in total acid/strong
Acid distribution is upper to be approached with fresh dose.
Catalytic diesel oil hydro-conversion production high-knock rating gasoline reaction process process be usually catalytic diesel oil raw material first
It is reacted by preatreating reactors hydrodenitrogeneration, then, denitrification reaction generates the hydrocracking reactor progress that oil enters back
Hydrocracking reaction generates high octane gasoline component.In catalytic diesel oil hydroconversion process cracker, along reaction
The direction of logistics, as gasoline component content gradually increases in the intensification reaction stream of reaction depth, diesel component content is gradually
Decline.Therefore, reactor from top to bottom gradually changes the percentage contribution of diesel product and gasoline products.In reactor
Inside from top to bottom catalyst is gradually reduced the reaction contribution of diesel oil, and gradually increases to the reaction of gasoline contribution.Cause
This, in order to realize catalyst system to diesel oil/gasoline component selective reaction technical goal in reaction fraction, ideal reaction
Process should be that reactor upper catalyst agent has preferable open loop and adds hydrogen saturability, complete the open loop of diesel oil distillate, break
Chain and plus hydrogen saturation, improve diesel product Cetane number, increasing gasoline yield product；And reactor lower part is evaporated due to being enriched gasoline
Point, in order to improve gasoline products octane number and yield then require catalyst as far as possible and reduce the saturability of gasoline fraction with
Further ring-opening reaction ability.Traditional catalytic diesel oil hydroconversion process cracker single catalyst system is unable to satisfy
Such reaction requirement, therefore, the technology need to be further improved.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of hydrocracking catalyst grading methods and catalytic diesel oil to add
Hydrogen conversion process realizes that raising is transformed by the catalyst system of the grading loading differential responses performance in cracker
Journey diesel oil/gasoline component adds hydrogen and Cracking Selectivity, increases production the target of high octane gasoline products.
Hydrocracking catalyst grading method of the invention, including the following contents: by hydrocracking reactor along material stream
Dynamic direction is divided into 2 ~ 8 reaction zones, is preferably divided into 3 ~ 6 reaction zones, mixed packing hydrocracking catalyst in each reaction zone
Agent and regenerated catalyst, the mass ratio of hydrocracking catalyst and regenerated catalyst in each reaction zone are 10:1 ~ 1:10, preferably
6:1 ~ 1:6, along Flow of Goods and Materials direction, the mass ratio of hydrocracking catalyst and regenerated catalyst in each reaction zone gradually subtracts
It is small；Wherein the regenerated catalyst is the hydrocracking catalyst after inactivated by regeneration treatment, and regenerated catalyst has such as
Lower property: specific surface area is 50 ~ 130m20.07 ~ 0.15ml/g of/g, Kong Rongwei, carbon content 10wt% ~ 20wt%, total meleic acid amount
0.08~0.25mmol/L；Regenerated catalyst is divided into carbon deposit area and non-carbon deposit area by position existing for carbon deposit, wherein non-carbon deposit area is
Any point and 25 ~ 250 μ m thick ranges on cross-section center line direction, excellent in the outer most edge of regenerated catalyst particles cross section
Select 50 ~ 200 μm of range.
Preparation process, that is, regeneration process of the regenerated catalyst, comprising:
(1) nitrogen displacement, oxygen 1 ~ 4v% of volume content in adjustment regeneration furnace atmosphere are carried out to regenerating furnace, and is preheated to 400
~800℃；
(2) hydrocracking catalyst inactivated after operating in catalytic diesel oil hydroconversion process is transferred to step (1)
It is quickly roasted in regenerating furnace 5 ~ 30 minutes, takes 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: reaction pressure 4.0 ~
10.0MPa, 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 operation
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.
It is processed raw material in catalytic diesel oil hydroconversion process of the present invention as catalytic diesel oil inferior, catalytic diesel oil density
For 0.90 ~ 1.0g/cm3, boiling range range is at 180 ~ 400 DEG C, 500 ~ 2000ppm of nitrogen content, 5000 ~ 15000ppm of sulfur content, virtue
60 ~ 90m% of hydrocarbon content.
The hydrocracking catalyst of step (2) described inactivation has the property that specific surface area is 40 ~ 100m2/ g, hole
Hold 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 commercialized light oil type hydrogen cracking fresh catalyst, such as
HC-185, HC-190, FC-24, FC-24B etc. are also possible to the hydrocracking catalyst prepared according to the prior art.
The silica-alumina supports and hydrogenation active metals that above-mentioned hydrocracking catalyst generally includes Y molecular sieve contain according to mass percent meter
The silica-alumina supports of Y molecular sieve are 70% ~ 92%, and hydrogenation active metals are calculated as 8% ~ 30% with oxide；The hydrocracking catalyst
Specific surface area be 200 ~ 400m20.2 ~ 0.5ml/g of/g, Kong Rongwei；The hydrogenation active metals can be in the periodic table of elements
Group VIII and/or group vi metallic element, wherein group VIII active metal can be Ni and/or Co, group vi activity
Metal is to be W and/or Mo；The group VIII active metallic content is generally 2% ~ 10%, the VIth VI race active metallic content one
As be 5% ~ 20%.The content of the Y molecular sieve in the carrier is generally 30% ~ 90%, preferably 40% ~ 70%, and rest part is nothing
Amorphous silicon-alumina and/or aluminium oxide；The Y molecular sieve property is as follows: 700~900m of specific surface area2/ g, total pore volume 0.35~
0.60ml/g, relative crystallinity 90%~130%, cell parameter 2.437~2.460,0.5~1.5mmol/g of meleic acid amount.
Catalyst of the present invention is that (solid) is granular, rather than the amorphous states such as powder.As described
The shape of grain, can enumerate the conventional use of various shape of this field hydrocracking catalyst, for example can further enumerate ball
Shape and column.As the spherical shape, for example spheroidal and elliposoidal can be enumerated etc.；As the column, for example 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 the minimum dimension side along a catalyst granules
The whole surface of exposure after to the geometric center cutting by its shape.For example, when the catalyst granules is spherical, it is described
Cross section refers to the whole surface of exposure after cutting along the radius or short-axis direction of the ball by its centre of sphere.Alternatively, institute
When to state catalyst granules be column, the cross section refers to that the length dimension direction perpendicular to the column passes through the length dimension
The whole surface of exposure after central point cutting.
In the present invention, the periphery of the exposed surface is known as to the outer most edge of the cross section, by the geometric center (such as
The central point of the centre of sphere or length dimension above-mentioned) it is known as the central point on the cross section.
Present invention simultaneously provides a kind of catalytic diesel oil hydroconversion process, including the following contents:
I, under the conditions of hydrofining technology, the mixed material of catalytic cracking diesel oil and hydrogen be introduced into hydrogenator with
Hydrobon catalyst haptoreaction；
II, under the conditions of hydrocracking process, hydrofining reaction effluent is directly entered urges according to above-mentioned be hydrocracked
The hydrocracking reactor of agent grading method filling, contacts instead with the hydrocracking catalyst bed of grading loading in reactor
It answers；
III, step (II) obtain hydrocracking reaction effluent and are separated and be fractionated acquisition naphtha component and diesel oil group
Point, wherein the straight connecting device of naphtha component can straight connecting device reconciliation as high-knock rating gasoline blend component, diesel component
Diesel oil is also recycled into cracker and further reacts.
Hydrofining technology condition described in step (I) are as follows: 4.0 ~ 10.0MPa of reaction pressure, reaction temperature 320 ~ 420
DEG C, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200:1 ~ 2000:1.
Hydrocracking process condition described in step (I) are as follows: 4.0 ~ 10.0MPa of reaction pressure, reaction temperature 360 ~ 440
DEG C, 1.0 ~ 4.0h of volume space velocity-1, hydrogen to oil volume ratio 200:1 ~ 2000:1.
Commercial product can be used in Hydrobon catalyst described in step (I), can also be according to this field Conventional wisdom
Preparation.Conventional hydrocracking pretreatment catalyst can be used in Hydrobon catalyst used in the present invention, generally with group vib and/
Or group VIII metal is active component, using aluminium oxide or silicon-containing alumina as carrier.Vib metals be generally Mo and/or
W, group VIII metal are generally Co and/or Ni.On the basis of the weight of catalyst, vib metals content is in terms of oxide
For 8wt%~28wt%, group VIII tenor is calculated as 2wt%~15wt% with oxide.
The method of the present invention is by scanning electron microscope, x-ray photoelectron spectroscopy etc. to the phosphorus content and regeneration catalyzing of catalyst
Ji Fei carbon deposit area thickness is measured.
Catalytic reaction process and reaction stream composition have such as in catalytic diesel oil hydrocracking process process cracker
Lower rule: reaction process mainly includes the gasoline of open loop, fracture and the conversion process generation of diesel oil distillate in cracker
The further saturation of component and open loop, react these two types, and open loop, the fracture of diesel oil distillate are conducive to improve diesel product ten
Six alkane values and increasing gasoline yield, and the further reaction for reacting the gasoline component generated is then for yield of gasoline and product quality
Unfavorable.In face of this contradiction, conventional single catalyst system be cannot be considered in terms of.And the present inventor has found through analysis,
Along logistics direction in cracker, the ratio of diesel oil distillate and gasoline fraction is gradually changed, and gasoline component gradually increases
And diesel component gradually decreases, it may be said that reactor top (logistics direction from top to bottom) is with greater need for the higher acid of catalyst
Property, hydrogenation capability meet the open loop of diesel oil distillate, hydrogenation reaction, and lower part diesel component ratio declines, and gasoline proportionality rises, because
This, needs to reduce catalyst activity and the saturation to gasoline component, cracking reaction.
The cracking with higher of fresh hydrocracking catalyst and hydrogenation activity, be conducive to diesel oil distillate abundant plus hydrogen and
Conversion；The present invention uses the hydrocracking catalyst of specific process regeneration treatment, and catalytic inner duct and activated centre are accumulated
Charcoal covering shielding, activated centre is mainly in catalyst surface, therefore, can be considered as outer surface reaction, reactant and catalyst
Speed away catalyst after haptoreaction, advantageously reduces the secondary cracking of the gasoline component of primary first-order equation generation and adds hydrogen full
With reaction process adds hydrogen and selectivity of ring-opening to significantly improve polycyclic/mononuclear aromatics.Cracker catalyst grade of the present invention is matched
In scheme, logistics direction is for from top to bottom, from reactor top to reactor lower part, by the way that regenerative agent is gradually increased mixed
The ratio in catalyst is closed, the technological reaction process diesel oil/gasoline component is improved and adds hydrogen and cracking reaction selectivity, guaranteeing
While diesel product quality, gasoline products octane number and yield are improved.
Specific embodiment
Technical characterstic of the invention is further described by embodiment in next step, but these embodiments cannot limit this hair
It is bright.
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, volume space velocity 1.0 ~
4.0h-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, volume space velocity 1.0 ~
4.0h-1, hydrogen to oil volume ratio 200:1 ~ 2000:1.
It is processed raw material in catalytic diesel oil hydroconversion process described in step (1) as catalytic diesel oil inferior, catalytic diesel oil is close
Degree be 0.90 ~ 1.0g/cm3, boiling range range 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 is replaced to oxygen volume content 2v%, is heated to 500 DEG C；
(2) spent agent is as in the preheated regenerating furnace of step (1) after taking catalytic diesel oil hydro-conversion commercial plant to operate
Roasting 15 minutes；
(3) catalyst after step (2) once roast is taken out, until placing 0.5h at room temperature；
(4) regenerating furnace nitrogen is replaced to oxygen volume content 1v%, is heated to 600 DEG C；
(5) the catalyst addition regeneration of step (3) placement to room temperature the regeneration of embodiment 1 is obtained for kiln roasting 10 minutes to urge
Agent, number Z-1；
Embodiment 2
(1) regenerating furnace nitrogen is replaced to oxygen volume content 2v%, is heated to 550 DEG C；
(2) spent agent is as in the preheated regenerating furnace of step (1) after taking catalytic diesel oil hydro-conversion commercial plant to operate
Roasting 10 minutes；
(3) catalyst after step (2) once roast is taken out, until placing 0.5h at room temperature；
(4) regenerating furnace nitrogen is replaced to oxygen volume content 1v%, is heated to 500 DEG C；
(5) regeneration kiln roasting 15 minutes is added in the catalyst for placing step (3) to room temperature；
(6) catalyst after step (5) after baking is taken out, until placing 1h at room temperature；
(7) regenerating furnace nitrogen is replaced to oxygen volume content 1v%, is heated to 500 DEG C；
(8) the catalyst addition regeneration of step (6) placement to room temperature the regeneration of embodiment 2 is obtained for kiln roasting 15 minutes to urge
Agent, number Z-2；
Embodiment 3
(1) regenerating furnace nitrogen is replaced to oxygen volume content 3v%, is heated to 600；
(2) spent agent is as in the preheated regenerating furnace of step (1) after taking catalytic diesel oil hydro-conversion commercial plant to operate
Roasting 15 minutes；
(3) catalyst after step (2) once roast is taken out, until placing 0.5h at room temperature；
(4) regenerating furnace nitrogen is replaced to oxygen volume content 2v%, is heated to 600 DEG C；
(5) regeneration kiln roasting 10 minutes is added in the catalyst for placing step (3) to room temperature；
(6) catalyst after step (5) after baking is taken out, until placing 1h at room temperature；
(7) regenerating furnace nitrogen is replaced to oxygen volume content 1v%, is heated to 600 DEG C；
(8) the catalyst addition regeneration of step (6) placement to room temperature the regeneration of embodiment 3 is obtained for kiln roasting 10 minutes to urge
Agent, number Z-3；
Embodiment 4
(1) regenerating furnace nitrogen is replaced to oxygen volume content 1.5v%, is heated to 700 DEG C；
(2) spent agent is as in the preheated regenerating furnace of step (1) after taking catalytic diesel oil hydro-conversion commercial plant to operate
Roasting 5 minutes；
(3) catalyst after step (2) once roast is taken out, until placing 0.5h at room temperature；
(4) regenerating furnace nitrogen is replaced to oxygen volume content 1v%, is heated to 550 DEG C；
(5) the catalyst addition regeneration of step (3) placement to room temperature the regeneration of embodiment 4 is obtained for kiln roasting 10 minutes to urge
Agent, number Z-4；
Comparative example 1
(1) the hydrocracking catalyst spent agent after taking catalytic diesel oil hydro-conversion commercial plant to operate is as regenerating furnace
In；
(2) it is passed through air into regenerating furnace, then, is warming up to 550 DEG C with 25 DEG C/h heating rate, constant temperature calcining 4h is obtained
To 1 regenerative agent of comparative example, number B-1；
Embodiment 5
The effect for matching system in order to further illustrate embodiment catalyst grade has carried out midget plant comparative evaluation test.
Using catalytic diesel oil as reaction raw materials oil, the pretreatment once used by process flow, catalyst refining stage using single hop series connection
Catalyst be the widely used FF-36 hydrogenation pretreatment catalyst in this field, cracking zone load respectively A/Z-1, A/Z-2,
A/Z-3, A/B-1, B-2 and several gradation systems of A or more.Evaluation test raw material property, cracking zone subregion, is commented catalyst
Valence condition and evaluation result are listed in table 1 ~ 5.
The new agent of table 1 and industrial operation catalyst physico-chemical property.
2 embodiment of table and comparative example catalyst physico-chemical property.
3 raw material oil nature of table.
4 evaluation condition of table.
5 embodiment of table and comparative example evaluating catalyst result.
Claims (10)
1. a kind of hydrocracking catalyst grading method, it is characterised in that including the following contents: by hydrocracking reactor along object
Direction of flow is divided into 2 ~ 8 reaction zones, mixed packing hydrocracking catalyst and regenerated catalyst in each reaction zone, respectively
The mass ratio of hydrocracking catalyst and regenerated catalyst in reaction zone is 10:1 ~ 1:10, each to react along Flow of Goods and Materials direction
The mass ratio of hydrocracking catalyst and regenerated catalyst in area is gradually reduced；Wherein the regenerated catalyst is after inactivating
By the hydrocracking catalyst of regeneration treatment, regenerated catalyst has the property that specific surface area is 50 ~ 130m2/ g, Kong Rong
For 0.07 ~ 0.15mL/g, carbon content 10wt% ~ 20wt%, 0.08 ~ 0.25mmol/L of total meleic acid amount；Regenerated catalyst presses carbon deposit
Existing position is divided into carbon deposit area and non-carbon deposit area, wherein non-carbon deposit area is any in the outer most edge of regenerated catalyst particles cross section
A little and 25 ~ 250 μ m thick ranges on cross-section center line direction.
2. grading method described in accordance with the claim 1, it is characterised in that: the non-carbon deposit area of the regenerated catalyst is regeneration
Any point and 50 ~ 200 μ m thick ranges on cross-section center line direction in the outer most edge of catalyst granules cross section.
3. grading method described in accordance with the claim 1, it is characterised in that: the preparation process of the regenerated catalyst, comprising:
(1) nitrogen displacement, oxygen 1 ~ 4v% of volume content in adjustment regeneration furnace atmosphere are carried out to regenerating furnace, and is preheated to 400 ~ 800 DEG C；
(2) hydrocracking catalyst inactivated after operating in catalytic diesel oil hydroconversion process is transferred in the regenerating furnace of step (1)
Quickly roasting 5 ~ 30 minutes take out product of roasting, are cooled to room temperature, then repeat above-mentioned quick roasting-taking-up-cooling procedure
1 ~ 4 time, obtain regenerated catalyst.
4. grading method described in accordance with the claim 3, it is characterised in that: the hydrocracking catalyst of step (2) described inactivation,
Have the property that specific surface area is 40 ~ 100m2/ g, Kong Rongwei 0.05 ~ 0.10mL/g, carbon content 12wt% ~ 25wt% are total red
0.05 ~ 0.2mmol/L of outer acid amount.
5. grading method described in accordance with the claim 1, it is characterised in that: the hydrocracking catalyst includes Y molecular sieve
Silica-alumina supports and hydrogenation active metals, according to mass percent meter, the silica-alumina supports containing Y molecular sieve are 70% ~ 92%, add hydrogen living
Property metal is calculated as 8% ~ 30% with oxide；The specific surface area of the hydrocracking catalyst is 200 ~ 400m2/ g, Kong Rongwei 0.2 ~
0.5ml/g；The hydrogenation active metals are group VIII and/or vib metals element in the periodic table of elements, wherein
VIII group active metal is Ni and/or Co, and group VIB active metal is to be W and/or Mo；The group VIII active metal contains
Amount is 2% ~ 10%, and group VIB active metallic content is 5% ~ 20%；The content of the Y molecular sieve in the carrier is 30% ~ 90%,
Rest part is amorphous silica-alumina and/or aluminium oxide.
6. grading method according to claim 5, it is characterised in that: the Y molecular sieve property is as follows: specific surface area 700
~900m2/ g, 0.35~0.60mL/g of total pore volume, relative crystallinity 90%~130%, cell parameter 2.437~2.460 are infrared
0.5~1.5mmol/g of acid amount.
7. a kind of catalytic diesel oil hydroconversion process, it is characterised in that including the following contents: (I) is in hydrofining technology condition
Under, the mixed material of catalytic cracking diesel oil and hydrogen is introduced into hydrogenator and Hydrobon catalyst haptoreaction；(II)
Under the conditions of hydrocracking process, hydrofining reaction effluent is directly entered according to claim 1 ~ 4 any claim institute
The hydrocracking reactor for the hydrocracking catalyst grading method filling stated, is urged with being hydrocracked for grading loading in reactor
Agent bed haptoreaction；(III) step (II) obtains hydrocracking reaction effluent and is separated and be fractionated acquisition naphtha group
Point and diesel component.
8. technique according to claim 7, it is characterised in that: hydrofining technology condition described in step (I) are as follows: reaction
4.0 ~ 10.0MPa of 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. technique according to claim 7, it is characterised in that: hydrocracking process condition described in step (I) are as follows: reaction
4.0 ~ 10.0MPa of 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. technique according to claim 7, it is characterised in that: in catalytic diesel oil hydroconversion process described in step (I)
It processes raw material as catalytic diesel oil inferior, catalytic diesel oil density is 0.90 ~ 1.0g/cm3, boiling range range is at 180 ~ 400 DEG C, nitrogen content
500 ~ 2000ppm, 5000 ~ 15000ppm of sulfur content, 60 ~ 90m% of arene content.
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| CN103773482A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrocracking method used for producing high-quality chemical raw materials |
| CN104611029A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalytic cracking diesel fuel hydroconversion method |
| CN104611050A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalytic cracking diesel fuel conversion method |
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