CN105709820B - A kind of hydrocracking catalyst and preparation method thereof - Google Patents

A kind of hydrocracking catalyst and preparation method thereof Download PDF

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CN105709820B
CN105709820B CN201410724378.6A CN201410724378A CN105709820B CN 105709820 B CN105709820 B CN 105709820B CN 201410724378 A CN201410724378 A CN 201410724378A CN 105709820 B CN105709820 B CN 105709820B
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usy
molecular sieve
catalyst
ammonium salt
pore volume
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CN105709820A (en
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秦波
杜艳泽
柳伟
张晓萍
王凤来
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The present invention discloses a kind of hydrocracking catalyst, according to catalyst weight percent meter, including following component：Aluminum oxide 25wt% ~ 75wt%；Hydrogen USY Y compound molecular sieves 5wt% ~ 45wt%；Active metal 15wt% ~ 50wt% (in terms of oxide)；The m of specific surface area 200 ~ 300 of the catalyst2/ g, the m of external surface area 150 ~ 2002/ g, 0.35 ~ 0.46ml/g of pore volume；Described Hydrogen USY Y compound molecular sieves are using USY types molecular sieve as core, using Y types sub-sieve as shell.Catalyst can effectively convert 23 PAHs in raw material, and the BMCI values for the tail oil product being hydrocracked are relatively low.

Description

A kind of hydrocracking catalyst and preparation method thereof
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, the height of heavy distillate can be particularly processed Hydrocracking catalyst of activity and preparation method thereof.
Background technology
Hydrocracking technology has strong adaptability to raw material, production operation and the big, good product quality of products scheme flexibility etc. Feature, various heavy inferiors can be fed to high-quality jet fuel, diesel oil, the lube basestocks for being converted into market in urgent need And chemical industry naphtha and tail oil preparing ethylene by steam cracking raw material, it has also become modern times oil refining and petro chemical industry are most important heavy One of oily deep processing technique, at home and abroad obtains increasingly extensive application.
As crude quality is deteriorated year by year, the sour crude of import increases considerably and refinery is increases economic efficiency, Start generally to use crude oil deep vacuum distillation technology so that doing for vacuum distillate has brought up to 600 DEG C of left sides by original 520 DEG C The right side, its density is increasing, boiling range more and more higher, the molecular weight of contained hydrocarbon molecule is increasing, structure also becomes increasingly complex, sulphur The impurity contents such as nitrogen are also more and more, considerably increase the difficulty being hydrocracked, and these split to hydrocracking technology and hydrogenation Change catalyst and be proposed higher requirement.The demand of product quality upgrading simultaneously and device capacity expansion revamping is lifted increasingly, refinery Higher and higher requirement is proposed to the performance of hydrocracking catalyst.Hydrocracking catalyst is the core of hydrocracking technology The heart.The bifunctional catalyst that hydrocracking catalyst is made up of hydrogenating function and cracking function, wherein hydrogenating function are by adding Hydrogen activity metal provides, and improves the Hydrogenation of hydrocracking catalyst, is advantageous to the saturation of aromatic hydrocarbons；Cracking function is by without fixed What type sial or molecular sieve provided, it can crack the macromolecular of long-chain and make polycyclic aromatic hydrocarbon further open loop turn after saturation Change, this not only contributes to handle more heavy, Hydrocracking Raw Oil inferior, improves liquid product yield and produces high quality Hydrocracked product, moreover it is possible to further improve the ability of the anti-organic nitrogen poisoning of catalyst, reduce green coke, carbon deposit, extend catalysis The service life of agent.
CN103007999、CN103041482、CN103100400、CN103100427、CN103100430、 Different modification sides is respectively adopted in the patents such as CN103100412, CN103191772, CN103191773 and CN103191774 Method prepares the catalyst of different catalytic performances, especially patent CN103191773 and CN103191774 respectively first to alumina powder Carried out it is modified be prepared for hydrocracking catalyst, catalytic performance is improved.
Patent CN101343559, CN101343560 and CN10134356 describe to be added using prepared by composite molecular screen Hydrogen Cracking catalyst and preparation method.The hydrocracking catalyst of preparation shows excellent catalytic performance.
Modified molecular sieve is urged being hydrocracked as the component that lytic activity is provided in hydrocracking catalyst, its performance The performance of agent is most important, is advantageous to further improve urging for hydrocracking catalyst using the modified molecular screen of excellent performance Change performance.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of high-activity hydrocracking catalyst and preparation method thereof.Should Catalyst prepared by method has the characteristics of hydrogenation cracking activity height and strong 2-3 PAH cracking abilities.Can effectively it convert 2-3 PAHs in raw material, the BMCI values for the tail oil product being hydrocracked are relatively low.
Hydrocracking catalyst of the present invention, according to catalyst weight percent meter, including following component：Aluminum oxide 25wt% ~ 75wt%, preferably 35wt% ~ 65wt%；Hydrogen USY-Y composite molecular screen 5wt% ~ 45wt%, preferably 15wt% ~ 40wt%；Active metal 15wt% ~ 50wt% (in terms of oxide), preferably 20wt% ~ 45wt%；Wherein group vib tenor is 10wt% ~ 40wt%, preferably 15wt%~35wt%；Group VIII metal content is 2wt% ~ 18wt%, preferably 4wt% ~ 15wt%, the specific surface area 200 of the catalyst ~300 m2/ g, the m of external surface area 150 ~ 2002/ g, 0.35 ~ 0.46ml/g of pore volume；Described Hydrogen USY-Y composite molecular screens Using USY types molecular sieve as core, using Y types sub-sieve as shell, the weight content of Y type molecular sieve is 10wt% ~ 90wt% in composite molecular screen, It is preferred that 30wt% ~ 70wt%；Composite molecular screen has a mesoporous-microporous structure, mesoporous shared pore volume account for molecular sieve total pore volume 15% ~ 50%, preferably 20% ~ 40%, silica/alumina molar ratio is 4.2 ~ 25 in composite molecular screen, and specific surface area is 450 ~ 900m2/ G, pore volume are 0.33 ~ 0.62ml/g, and average pore size is 1.5 ~ 4.0nm；It is preferred that silica/alumina molar ratio is 6 ~ 15, compare table Area is 550 ~ 800 m2/ g, pore volume are 0.35 ~ 0.50ml/g, and average pore size is 1.8 ~ 2.9nm.
The preparation method of hydrocracking catalyst of the present invention, comprises the following steps：
（1）Aluminum oxide, Hydrogen USY-Y composite molecular screens, binding agent, sesbania powder and water are fully rolled into aftershaping, then Dry, roasting, obtain catalyst carrier；
（2）With the dipping solution impregnation steps containing active metal component（1）Obtained catalyst carrier, then dry, Roasting, obtains hydrocracking catalyst.
In the above method, step（1）Described acidic catalyst material Hydrogen USY-Y composite molecular screens are by sodium form USY-Y What composite molecular screen obtained by being modified, specific method of modifying is as follows：It is at least 2 times using ammonium salt exchange times first, is exchanged Temperature is 60 ~ 110 DEG C, preferably 80 ~ 100 DEG C.Ammonium salt used is ammonium chloride, ammonium sulfate or ammonium nitrate, and the concentration of ammonium salt is 0.5 ~ 3mol/L, preferably ammonium salt are ammonium nitrate, and preferred concentration is 1 ~ 2mol/L.The liquid-solid ratio of exchange process（ml/g）For 5 ~ 30, It is preferred that 10 ~ 20；Each swap time is 0.5 ~ 2.0 hour, preferably 1 ~ 1.5 hour.Then hydro-thermal process, water vapour pressure are carried out In 0.05 ~ 0.5MPa, preferably 0.1 ~ 0.3MPa；Steam temperature is between 500 ~ 800 DEG C, preferably 550 ~ 700 DEG C；Processing time Between 0.5 ~ 10 hour, preferably 1 ~ 6 hour.
The preparation method of sodium form USY-Y composite molecular screens, comprises the following steps in the above method：
（a）USY molecular sieve is swapped using ammonium salt；
（b）According to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=15~20:1:15~22:320 ~ 420, by aluminium Source, water, sodium hydroxide and waterglass are configured to mixed liquor, are then aged 0.5 ~ 2 day at 20 ~ 50 DEG C, and directed agents are made；
（c）According in gel（Remove the USY molecular sieve added）The mol ratio of each material isn(NaOH): n(Al2O3):n (SiO2):n(H2O)=14~18:1:9~20:320 ~ 760, preferablyn(NaOH):n(Al2O3):n(SiO2): n(H2O)=14.5~ 16.5:1: 11~18:400 ~ 650, silicon source, sodium hydroxide, water and waterglass are configured to mixed liquor, then add step（a） Ammonium salt swap after USY molecular sieve and step（b）Obtained directed agents, by gel in 85 ~ 120 DEG C of conditions after stirring Lower thermostatic crystallization 12 ~ 72 hours, thermostatic crystallization 24 ~ 60 hours preferably under the conditions of 90 ~ 110 DEG C, then through cooling down, washing, taking out Filter, obtain using USY molecular sieve being core and USY-Y composite molecular screens using Y type molecular sieve as shell after drying, wherein the USY added The quality of molecular sieve accounts for 4 ~ 30wt% of gel rubber system gross mass, preferably 6 ~ 15wt%, and the quality of the directed agents of addition accounts for gelinite It is 2 ~ 20wt% of gross mass, preferably 4 ~ 10wt%.
The inventive method step（a）Described in USY molecular sieve be to pass through modified Y type molecular sieve, by physics or Chemical method dealuminzation, desiliconization or dealumination complement silicon obtain.Wherein representative method of modifying is hydro-thermal process dealuminzation and change Method desiliconization, dealumination complement silicon.Modified Y type molecular sieve can be that Hydrogen can also be sodium form.The oxidation of USY molecular sieve Silicon/alumina molar ratio is 4.2 ~ 35, and specific surface area is 450 ~ 850m2/g；It is preferred that silica/alumina molar ratio is 6 ~ 15, Specific surface area is 550 ~ 800m2/g。
The inventive method step（a）It is as follows that middle use ammonium salt swaps process：Ammonium salt is added to the water, then added Molecular sieve, after being stirred continuously 1 ~ 2 hour, filter, dry；The concentration of ammonium salt solution is 0.15mol/L ~ 0.5mol/L, preferably 0.2mol/L~0.3mol/L；The mass ratio of solution and molecular sieve is 6:1~20:1, preferably 9:1~15:1.
The inventive method step（a）In ammonium salt refer to various organic quaternary ammonium salt and long-chain organic cation type surface-actives Agent.The preferred tetraethyl ammonium radical ion of quaternary ammonium salt and tetrapropyl ammonium radical ion, long-chain organic cation type surfactant preferably ten Six alkyl trimethyl ammonium bromides, P123 and F127 etc..
The inventive method step（b）With（c）In, described silicon source includes aluminium chloride, aluminum sulfate, aluminum nitrate, sodium aluminate etc., It is preferred that sodium aluminate.
In the inventive method, step（1）The specific surface area of described alumina powder is 300 ~ 820m2/ g, preferably 350 ~ 750m2/ g, pore volume are 0.45 ~ 1.45 ml/g, preferably 0.55 ~ 1.15 ml/g.
In the inventive method, step（1）Described binding agent is prepared by small porous aluminum oxide, organic acid and/or inorganic acid Form, preparation process is known to those skilled in the art, wherein aperture aluminum oxide pore volume used is 0.25 ~ 0.55ml/g, preferably 0.31 ~ 0.48ml/g, it is 160 ~ 420m than surface2/ g, preferably 190 ~ 390m2/g。
In the inventive method, step（1）Described drying temperature is 50 ~ 120 DEG C, and the time is 6 ~ 12 hours；Sintering temperature For 450 ~ 650 DEG C, the time is 2 ~ 12 hours.
In the inventive method, step（2）It is group vib metal and VIII to contain active metal component in described metallic solution Race's metal；The preferred tungsten of group vib metal（W）And molybdenum（Mo）, the preferred cobalt of group VIII metal（Co）And nickel（Ni）, the preparation of dipping solution For known to those skilled in the art；Dipping method is impregnated using supersaturation.
In the inventive method, described drying temperature is 50 ~ 150 DEG C, and preferably 100 ~ 120 DEG C, drying time is 6 ~ 12 small When；Sintering temperature is 450 ~ 650 DEG C, and the time is 2 ~ 12 hours.
There is catalyst prepared by the inventive method high catalytic activity and 2-3 PAH cracking abilities to be suitable for processing weight Matter hydrocarbon material, the heavy hydrocarbon material of especially high arene content.The boiling range of heavy hydrocarbon material is 300 ~ 600 DEG C.Present invention catalysis When handling VGO, reaction condition is under hydrogen existence condition, 10 ~ 20MPa of reaction pressure for agent, 360 ~ 420 DEG C of reaction temperature, Hydrogen to oil volume ratio 500 ~ 2000,0.5 ~ 7.0h of volume space velocity during liquid-1。
The inventive method has the following advantages that compared to prior art：USY-Y composite molecular screens have it is obvious be situated between-it is micro- Pore structure, activated centre accessibility and the interaction with hydrogenation metal in the catalyst of preparation are improved, makes cracking group Divide the collocation more optimized with hydrogenation component.The diffusion velocity of reactant and product can also be improved simultaneously, reduced The chance of second pyrolysis occurs for molecule.The reaction for existing for macromolecular especially aromatic hydrocarbons macromolecular of a large amount of meso-hole structures provides bar Part, make catalyst of the present invention that not only there is suitable lytic activity, while also there is efficient 2-3 PAHs conversion capability.
Embodiment
The preparation process of the present invention is further illustrated with reference to embodiment, but following examples are not formed to present invention side The limitation of method.The aluminum oxide and binding agent that there is following property using adding in preparation process.The property of alumina powder is such as Under：Specific surface area is 425m2/ g, pore volume 0.82ml/g.Binding agent is by small porous aluminum oxide, organic acid and/or inorganic acid system Standby to form, preparation process is known to those skilled in the art, wherein aperture Properties of Alumina used is as follows：It is 298m than surface2/ G, pore volume are 0.46 ml/g.
The preparation and modification of composite molecular screen
Embodiment 1
（1）USY molecular sieve is swapped using 4-propyl bromide, makes molecular sieve structure stable.By tetrapropyl bromination Ammonium is added to the water, and then plus USY enters molecular sieve, after being stirred continuously 1 hour, filters, dries.The concentration of ammonium salt solution is The mass ratio of 0.35mol/L, solution and molecular sieve is 10:1.
（2）According to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16:1:16:340, under stirring, Sodium aluminate, water, sodium hydroxide and waterglass are sequentially added into beaker and form mixed liquor, is then aged 1.5 days at 40 DEG C, is made Directed agents.
（3）According in gel（Remove the USY molecular sieve added）The mol ratio of each material isn(NaOH):
n(Al2O3):n(SiO2):n(H2O)=16:1:16:480 condition.Under conditions of stirring, by sodium aluminate, hydrogen-oxygen Change sodium, water and waterglass to be added sequentially to form mixed liquor in beaker, then add step（1）USY molecular sieve and step（2）System Directed agents, after stirring by gel under the conditions of 95 DEG C thermostatic crystallization 48 hours, then through cooling down, washing, filtering, doing It is core and USY-Y composite molecular screens using Y type molecular sieve as shell to be obtained after dry using USY molecular sieve, wherein the USY molecular sieve added Quality account for the 8wt% of gel rubber system gross mass, the quality of the directed agents of addition accounts for the 6wt% of gel rubber system gross mass.
（4）2 ammoniums are carried out using 1mol/L ammonium chloride solution to exchange, exchange temperature is 80 DEG C.Liquid in exchange process Gu ratio（ml/g）For 15；Each swap time is 1.0 hours.Filtered after end, then carry out hydro-thermal process, control water vapor pressure Power is in 0.2MPa；Steam temperature is handled 5 hours in 600 DEG C of constant temperature.The Hydrogen USY-Y composite molecular screens of preparation are with USY types point Son sieve is core, and using Y types sub-sieve as shell, the weight content of Y type molecular sieve is 48wt% in composite molecular screen；Composite molecular screen has Mesoporous-microporous structure, mesoporous shared pore volume account for the 28% of molecular sieve total pore volume, silica/alumina molar ratio in composite molecular screen For 7, specific surface area 720m2/ g, pore volume 0.38ml/g, average pore size 2.0nm.
Embodiment 2
（1）USY molecular sieve is swapped using tetraethylammonium bromide, makes the pore passage structure of USY molecular sieve stable.Specifically Exchange process is as follows：Tetraethylammonium bromide is added to the water, then plus USY enters molecular sieve, after being stirred continuously 1.5 hours, takes out Filter, dry.The concentration of ammonium salt solution is 0.3mol/L, and the mass ratio of solution and molecular sieve is 8:1.
（2）According to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16:1:18:360, under stirring, Sodium aluminate, water, sodium hydroxide and waterglass are sequentially added into beaker and form mixed liquor, is then aged 2 days at 25 DEG C, is made and leads To agent.
（3）According in gel（Remove the USY molecular sieve added）The mol ratio of each material isn(NaOH):
n(Al2O3):n(SiO2):n(H2O)=15:1:16:450 condition.Under conditions of stirring, by sodium aluminate, hydrogen-oxygen Change sodium, water and waterglass to be added sequentially to form mixed liquor in beaker, then add step（1）USY molecular sieve and step（2）System Directed agents, after stirring by gel under the conditions of 90 DEG C thermostatic crystallization 60 hours, then through cooling down, washing, filtering, doing It is core and USY-Y composite molecular screens using Y type molecular sieve as shell to be obtained after dry using USY molecular sieve, wherein the USY molecular sieve added Quality account for the 8wt% of gel rubber system gross mass, the quality of the directed agents of addition accounts for the 5wt% of gel rubber system gross mass.
（4）2 ammoniums are carried out using 1.5mol/L ammonium chloride, ammonium sulfate or ammonium nitrate ammonium salt solution to exchange, and exchange temperature Spend for 90 DEG C.Liquid-solid ratio in exchange process（ml/g）For 8；Each swap time is 1.5 hours.Filtered after end, Ran Houjin Water-filling is heat-treated, and control water vapour pressure is in 0.1MPa；Steam temperature is handled 2 hours in 650 DEG C of constant temperature.
The Hydrogen USY-Y composite molecular screens of preparation are using USY types molecular sieve as core, using Y types sub-sieve as shell, in composite molecular screen The weight content of Y type molecular sieve is 60wt%；Composite molecular screen has mesoporous-microporous structure, and it is total that mesoporous shared pore volume accounts for molecular sieve The 25% of pore volume, silica/alumina molar ratio is 6 in composite molecular screen, specific surface area 800m2/ g, pore volume 0.41ml/ G, average pore size 1.9nm.
Embodiment 3
（1）USY molecular sieve is swapped using cetyl trimethylammonium bromide, makes molecular sieve structure stable.By ten Six alkyl trimethyl ammonium bromides are added to the water, and then plus USY enters molecular sieve, after being stirred continuously 1.5 hours, filter, dry.Ammonium The concentration of solution is 0.2mol/L, and the mass ratio of solution and molecular sieve is 12:1.
（2）According to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=18:1:19:360, under stirring, Sodium aluminate, water, sodium hydroxide and waterglass are sequentially added into beaker and form mixed liquor, is then aged 1 day at 35 DEG C, is made and leads To agent.
（3）According in gel（Remove the USY molecular sieve added）The mol ratio of each material isn(NaOH):
n(Al2O3):n(SiO2):n(H2O)=15.5:1:14:550 condition.Under conditions of stirring, by aluminum sulfate, hydrogen Sodium oxide molybdena, water and waterglass are added sequentially to form mixed liquor in beaker, then add step（1）USY molecular sieve and step（2） Obtained directed agents, after stirring by gel under the conditions of 100 DEG C thermostatic crystallization 48 hours, then through cooling down, washing, taking out Filter, obtain using USY molecular sieve being core and USY-Y composite molecular screens using Y type molecular sieve as shell after drying, wherein the USY added The quality of molecular sieve accounts for the 10wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 8wt% of gel rubber system gross mass.
（4）2 ammoniums are carried out using 2mol/L ammonium chloride, ammonium sulfate or ammonium nitrate ammonium salt solution to exchange, exchange temperature For 70 DEG C.Liquid-solid ratio in exchange process（ml/g）For 20；Each swap time is 1 hour.Filtered after end, then enter water-filling Heat treatment, control water vapour pressure is in 0.2MPa；Steam temperature is handled 1 hour in 550 DEG C of constant temperature.
The Hydrogen USY-Y composite molecular screens of preparation are using USY types molecular sieve as core, using Y types sub-sieve as shell, in composite molecular screen The weight content of Y type molecular sieve is 42%；Composite molecular screen has mesoporous-microporous structure, and mesoporous shared pore volume accounts for the total hole of molecular sieve 32% held, silica/alumina molar ratio is 11 in composite molecular screen, specific surface area 700m2/ g, pore volume 0.45ml/g, Average pore size is 2.3nm.
Embodiment 4
（1）USY molecular sieve is swapped using cetyl trimethylammonium bromide, makes molecular sieve structure stable.By ten Six alkyl trimethyl ammonium bromides are added to the water, and then plus USY enters molecular sieve, after being stirred continuously 2 hours, filter, dry.Ammonium is molten The concentration of liquid is 0.4mol/L, and the mass ratio of solution and molecular sieve is 9:1.
（2）According to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16.5:1:19:330, in stirring Under, sodium aluminate, water, sodium hydroxide and waterglass are sequentially added into beaker and form mixed liquor, is then aged 1 day, makes at 35 DEG C Obtain directed agents.
（3）According in gel（Remove the USY molecular sieve added）The mol ratio of each material isn(NaOH):
n(Al2O3):n(SiO2):n(H2O)=16:1:17:450 condition.Under conditions of stirring, by aluminum nitrate, hydrogen-oxygen Change sodium, water and waterglass to be added sequentially to form mixed liquor in beaker, then add step（1）USY molecular sieve and step（2）System Directed agents, after stirring by gel under the conditions of 110 DEG C thermostatic crystallization 24 hours, then through cooling down, washing, filtering, It is core and USY-Y composite molecular screens using Y type molecular sieve as shell to be obtained after drying using USY molecular sieve, wherein the USY molecules added The quality of sieve accounts for the 7wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 5wt% of gel rubber system gross mass.
（4）2 ammoniums are carried out using 1.5mol/L ammonium chloride, ammonium sulfate or ammonium nitrate ammonium salt solution to exchange, and exchange temperature Spend for 70 DEG C.Liquid-solid ratio in exchange process（ml/g）For 12；Each swap time is 2 hours.Filter after end, then carry out Hydro-thermal process, control water vapour pressure is in 0.15MPa；Steam temperature is handled 3 hours in 640 DEG C of constant temperature.
The Hydrogen USY-Y composite molecular screens of preparation are using USY types molecular sieve as core, using Y types sub-sieve as shell, in composite molecular screen The weight content of Y type molecular sieve is 32%；Composite molecular screen has mesoporous-microporous structure, and mesoporous shared pore volume accounts for the total hole of molecular sieve 38% held, silica/alumina molar ratio is 13 in composite molecular screen, specific surface area 680m2/ g, pore volume 0.52ml/g, Average pore size is 2.5nm.
Catalyst preparation
Embodiment 5
After Hydrogen USY-Y composite molecular screens, binding agent, sesbania powder and water prepared by aluminum oxide, embodiment 1 are fully rolled Shaping, then dry 8 hours under conditions of 80 DEG C, be finally calcined 4 hours under the conditions of 550 DEG C.Obtain catalyst carrier；With Metallic solution impregnated catalyst support containing W and Ni, then dried 12 hours under conditions of 120 DEG C, finally at 550 DEG C Under the conditions of be calcined 6 hours, obtain hydrocracking catalyst HC1.Catalyst property such as table 1, table 2.
Embodiment 6
After Hydrogen USY-Y composite molecular screens, binding agent, sesbania powder and water prepared by aluminum oxide, embodiment 2 are fully rolled Shaping, then dry 8 hours under conditions of 100 DEG C, be finally calcined 8 hours under the conditions of 500 DEG C.Obtain catalyst carrier； With the metallic solution impregnated catalyst support containing W and Co, then dried 8 hours under conditions of 110 DEG C, finally at 520 DEG C Under conditions of be calcined 8 hours, obtain hydrocracking catalyst HC2.Catalyst property such as table 1, table 2.
Embodiment 7
After Hydrogen USY-Y composite molecular screens, binding agent, sesbania powder and water prepared by aluminum oxide, embodiment 3 are fully rolled Shaping, then dry 9 hours under conditions of 90 DEG C, be finally calcined 9 hours under the conditions of 540 DEG C.Obtain catalyst carrier；With Metallic solution impregnated catalyst support containing Mo and Ni, then dried 7 hours under conditions of 110 DEG C, finally at 540 DEG C Under the conditions of be calcined 6 hours, obtain hydrocracking catalyst HC3.Catalyst property such as table 1, table 2.
Embodiment 8
After Hydrogen USY-Y composite molecular screens, binding agent, sesbania powder and water prepared by aluminum oxide, embodiment 4 are fully rolled Shaping, then dry 12 hours under conditions of 60 DEG C, be finally calcined 4 hours under the conditions of 550 DEG C.Obtain catalyst carrier； With the metallic solution impregnated catalyst support containing W and Ni, then dried 6 hours under conditions of 110 DEG C, finally at 560 DEG C Under conditions of be calcined 3 hours, obtain hydrocracking catalyst HC4.Catalyst property such as table 1, table 2.
Comparative example 1
By aluminum oxide, using the step of embodiment 4（4）Y molecular sieve, binding agent, sesbania powder and the water of method processing fully grind Aftershaping is pressed, then dries 12 hours under conditions of 60 DEG C, is finally calcined 4 hours under the conditions of 550 DEG C.Obtain catalyst load Body；With the metallic solution impregnated catalyst support containing W and Ni, then dried 6 hours under conditions of 110 DEG C, finally 560 It is calcined 3 hours under conditions of DEG C, obtains hydrocracking catalyst BHC4.Catalyst property such as table 1, table 2.
Comparative example 2
By aluminum oxide, using the step of embodiment 4（4）USY molecular sieve, binding agent, sesbania powder and the water that method is handled are abundant Aftershaping is rolled, then dries 12 hours under conditions of 60 DEG C, is finally calcined 4 hours under the conditions of 550 DEG C.Obtain catalyst Carrier；With the metallic solution impregnated catalyst support containing W and Ni, then dry 6 hours under conditions of 110 DEG C, finally exist It is calcined 3 hours under conditions of 560 DEG C, obtains hydrocracking catalyst BHC4.Catalyst property such as table 1, table 2.
Catalytic performance test.
Evaluating apparatus is carried out using 200m1 small hydrogenation devices, and presulfurization is carried out to catalyst before activity rating.Evaluation is urged The raw materials used oil nature of agent activity and reaction process condition are shown in Table 3 and table 4, and catalyst reaction performance comparison the results are shown in Table 5.Comment During valency catalyst, feedstock oil first passes through Hydrobon catalyst bed and then immediately proceeds to hydrocracking catalyst bed, passes through The organic nitrogen content in feedstock oil is controlled to be less than 5ppm during Hydrobon catalyst bed.
The composition of the catalyst of table 1
The property of the catalyst of table 2.
The process conditions of table 3.
The feedstock property of table 4.
The catalyst reaction performance of table 5.
Catalyst HC1 HC2 HC3 HC4 BHC1 BHC1
Reaction temperature, DEG C 375 370 372 378 385 385
BMCI values 7.6 10.5 6.5 8.0 10.5 10.2

Claims (22)

  1. A kind of 1. hydrocracking catalyst, it is characterised in that：According to catalyst weight percent meter, including following component：Oxidation Aluminium 25wt% ~ 75wt%；Hydrogen USY-Y composite molecular screens 5wt% ~ 45wt%；Active metal 15wt% ~ 50wt% (in terms of oxide)； Wherein group vib tenor is 10wt% ~ 40wt%；Group VIII metal content is 2wt% ~ 18wt%, the ratio surface of the catalyst 200 ~ 300 m of product2/ g, the m of external surface area 150 ~ 2002/ g, 0.35 ~ 0.46ml/g of pore volume；Described Hydrogen USY-Y is compound Molecular sieve is using USY types molecular sieve as core, using Y types sub-sieve as shell, in composite molecular screen the weight content of Y type molecular sieve be 10wt% ~ 90wt%；Composite molecular screen has a mesoporous-microporous structure, and mesoporous shared pore volume accounts for the 15% ~ 50% of molecular sieve total pore volume, compound point Silica/alumina molar ratio is 4.2 ~ 25 in son sieve, and specific surface area is 450 ~ 900m2/ g, pore volume are 0.33 ~ 0.62ml/g, Average pore size is 1.5 ~ 4.0nm.
  2. 2. catalyst according to claim 1, it is characterised in that：Aluminum oxide 35wt% ~ 65wt%；Compound point of Hydrogen USY-Y Son sieve 15wt% ~ 40wt%；Active metal 20wt% ~ 45wt%；Wherein group vib tenor is 15wt% ~ 35wt%；Group VIII metal Content is 4wt% ~ 15wt%.
  3. 3. catalyst according to claim 1, it is characterised in that：The weight content of Y type molecular sieve is in composite molecular screen 30wt%~70wt%；Mesoporous shared pore volume accounts for the 20% ~ 40% of molecular sieve total pore volume, composite molecular screen silica/alumina mole Than for 6 ~ 15, specific surface area is 550 ~ 800 m2/ g, pore volume are 0.35 ~ 0.50ml/g, and average pore size is 1.8 ~ 2.9nm.
  4. 4. the preparation method of one of the claim 1-3 catalyst, it is characterised in that：
    （1）Aluminum oxide, Hydrogen USY-Y composite molecular screens, binding agent, sesbania powder and water are fully rolled into aftershaping, then dry, Roasting, obtains catalyst carrier；
    （2）With the dipping solution impregnation steps containing active metal component（1）Obtained catalyst carrier, then dry, be calcined, Obtain hydrocracking catalyst.
  5. 5. according to the method for claim 4, it is characterised in that：Step（1）Described Hydrogen USY-Y composite molecular screens be by What sodium form USY-Y composite molecular screens obtained by being modified, specific method of modifying is as follows：It is at least first using ammonium salt exchange times 2 times, exchange temperature is 60 ~ 110 DEG C, and ammonium salt used be ammonium chloride, ammonium sulfate or ammonium nitrate, the concentration of ammonium salt is 0.5 ~ 3mol/L, the liquid-solid ratio of exchange process（ml/g）For 5 ~ 30, each swap time is 0.5 ~ 2.0 hour；Exchange is carried out after terminating Hydro-thermal process, water vapour pressure are 0.05 ~ 0.5MPa；Steam temperature is between 500 ~ 800 DEG C；Processing time is 0.5 ~ 10 small When between.
  6. 6. according to the method for claim 5, it is characterised in that：Exchange temperature is 80 ~ 100 DEG C, and ammonium salt is ammonium nitrate, concentration For 1 ~ 2mol/L, the liquid-solid ratio of exchange process（ml/g）For 10 ~ 20；Each swap time is 1 ~ 1.5 hour, and water vapour pressure is 0.1~0.3MPa；Steam temperature is for 550 ~ 700 DEG C；Processing time is 1 ~ 6 hour.
  7. 7. according to the method for claim 5, it is characterised in that：The preparation method of sodium form USY-Y composite molecular screens, including such as Lower step：
    （a）USY molecular sieve is swapped using ammonium salt；
    （b）According to mol ratio n (Na2O):n(Al2O3):n(SiO2):n(H2O)=15~20:1:15~22:320 ~ 420, by silicon source, Water, sodium hydroxide and waterglass are configured to mixed liquor, are then aged 0.5 ~ 2 day at 20 ~ 50 DEG C, and directed agents are made；
    （c）According in gel（Remove the USY molecular sieve added）The mol ratio of each material is n (NaOH): n(Al2O3):n (SiO2):n(H2O)=14~18:1:9~20:320 ~ 760, silicon source, sodium hydroxide, water and waterglass are configured to mixed liquor, then Add step（a）Ammonium salt swap after USY molecular sieve and step（b）Obtained directed agents, exist gel after stirring Thermostatic crystallization 12 ~ 72 hours under the conditions of 85 ~ 120 DEG C, then through cooling down, wash, filter, dry after obtain using USY molecular sieve as Core and the USY-Y composite molecular screens using Y type molecular sieve as shell, wherein the quality of the USY molecular sieve added accounts for the total matter of gel rubber system 4 ~ 30wt% of amount, the quality of the directed agents of addition account for 2 ~ 20wt% of gel rubber system gross mass.
  8. 8. according to the method for claim 7, it is characterised in that：Step（a）Described in USY molecular sieve be by modified Y type molecular sieve, obtained by physics chemical method dealuminzation, desiliconization or dealumination complement silicon, silica/oxygen of USY molecular sieve It is 4.2 ~ 35 to change al mole ratio, and specific surface area is 450 ~ 850m2/g。
  9. 9. according to the method for claim 8, it is characterised in that：Silica/alumina molar ratio is 6 ~ 15, and specific surface area is 550~800m2/g。
  10. 10. according to the method for claim 7, it is characterised in that：Step（a）It is as follows that middle use ammonium salt swaps process： Ammonium salt is added to the water, then adds molecular sieve, after being stirred continuously 1 ~ 2 hour, filters, dries；The concentration of ammonium salt solution is 0.15mol/L~0.5mol/L；The mass ratio of solution and molecular sieve is 6:1~20:1.
  11. 11. according to the method for claim 10, it is characterised in that：The concentration of ammonium salt solution is 0.2mol/L ~ 0.3mol/L；It is molten The mass ratio of liquid and molecular sieve is 9:1~15:1.
  12. 12. according to the method for claim 7, it is characterised in that：Step（a）In ammonium salt have for organic quaternary ammonium salt or long-chain Machine cationic surface active agent.
  13. 13. according to the method for claim 12, it is characterised in that：Quaternary ammonium salt is tetraethyl ammonium radical ion or tetrapropyl ammonium root Ion, long-chain organic cation type surfactant are cetyl trimethylammonium bromide, P123 or F127.
  14. 14. according to the method for claim 7, it is characterised in that：Step（b）With（c）Described in silicon source include aluminium chloride, One or more in aluminum sulfate, aluminum nitrate, sodium aluminate.
  15. 15. according to the method for claim 7, it is characterised in that：Step（c）According to the mol ratio of each material in gel be n(NaOH):n(Al2O3):n(SiO2): n(H2O)=14.5~16.5:1: 11~18:400 ~ 650, by silicon source, sodium hydroxide, water Mixed liquor is configured to waterglass, thermostatic crystallization 24 ~ 60 hours under the conditions of 90 ~ 110 DEG C, the quality of the USY molecular sieve of addition 6 ~ 15wt% of gel rubber system gross mass is accounted for, the quality of the directed agents of addition accounts for 4 ~ 10wt% of gel rubber system gross mass.
  16. 16. according to the method for claim 4, it is characterised in that：Step（1）The specific surface area of described aluminum oxide be 300 ~ 820m2/ g, pore volume are 0.45 ~ 1.45 ml/g.
  17. 17. according to the method for claim 16, it is characterised in that：Step（1）The specific surface area of described aluminum oxide is 350 ~750m2/ g, pore volume are 0.55 ~ 1.15 ml/g.
  18. 18. according to the method for claim 4, it is characterised in that：Step（1）Described binding agent be by small porous aluminum oxide, Organic acid and/or inorganic acid are prepared, wherein aperture aluminum oxide pore volume used is 0.25 ~ 0.55ml/g, than surface be 160 ~ 420m2/g。
  19. 19. according to the method for claim 4, it is characterised in that：Step（2）Contain active metal in described metallic solution Component is group vib metal and group VIII metal；Group vib metal is tungsten（W）Or molybdenum（Mo）, group VIII metal is cobalt（Co）Or nickel （Ni）.
  20. 20. according to the method for claim 4, it is characterised in that：Step（1）Or（2）Described in drying temperature for 50 ~ 150 DEG C, drying time is 6 ~ 12 hours；Sintering temperature is 450 ~ 650 DEG C, and the time is 2 ~ 12 hours.
  21. 21. application of one of the claim 1-3 catalyst in treatment of heavy hydrocarbon material, it is characterised in that：Heavy hydrocarbon thing The boiling range of material is 300 ~ 600 DEG C.
  22. 22. application according to claim 21, it is characterised in that：Heavy hydrocarbon material is VGO, 10 ~ 20MPa of reaction pressure, 360 ~ 420 DEG C of reaction temperature, hydrogen to oil volume ratio 500 ~ 2000,0.5 ~ 7.0h of volume space velocity during liquid-1。
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CN108246344A (en) * 2016-12-28 2018-07-06 中国石油天然气股份有限公司 A kind of catalytic cracking diesel oil hydrocracking catalyst and preparation method thereof
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