CN105709820A - Hydrocracking catalyst, and preparation method thereof - Google Patents
Hydrocracking catalyst, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrocracking catalyst. The hydrocracking catalyst comprises, by weight, 25 to 75% of alumina, 5 to 45% of a hydrogen type USY-Y composite molecular sieve and 15 to 50% of active metal (in terms of oxide), wherein the catalyst has a specific surface area of 200 to 300 m<2>/g, an outer specific surface area of 150 to 200 m<2>/g and a pore volume of 0.35 to 0.46 ml/g. The hydrogen type USY-Y composite molecular sieve uses a USY type molecular sieve as a core and a Y type molecular sieve as a shell. The catalyst can effectively convert 2-3 cyclic aromatic hydrocarbons in the raw materials; and the BMCI value of a tail oil product of hydrocracking is low.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, particularly highly active hydrocracking catalyst that can process heavy distillate and preparation method thereof.
Background technology
The features such as hydrocracking technology has that adaptability to raw material is strong, production operation and big, the good product quality of products scheme motility, various heavy inferior chargings can be converted into the high-quality jet fuel of market in urgent need, diesel oil, lube basestocks and chemical industry Petroleum and tail oil preparing ethylene by steam cracking raw material, become one of modern oil refining and the most important heavy oil deep processing technique of petro chemical industry, at home and abroad obtain increasingly extensive application.
Along with crude quality is deteriorated year by year, the sour crude of import increases considerably and refinery is for increasing economic efficiency, start commonly used crude oil deep vacuum distillation technology, doing of vacuum distillate is made to have been brought up to about 600 DEG C by original 520 DEG C, the impurity contents such as its density is increasing, boiling range is more and more higher, the molecular weight of contained hydrocarbon molecule is increasing, structure also becomes increasingly complex, sulfur nitrogen also get more and more, considerably increasing the difficulty of hydrogenation cracking, hydrocracking technology and hydrocracking catalyst are proposed higher requirement by these.The demand of product quality upgrading simultaneously and device capacity expansion revamping promotes increasingly, and the performance of hydrocracking catalyst is proposed increasingly higher requirement by refinery.Hydrocracking catalyst is the core of hydrocracking technology.The bifunctional catalyst that hydrocracking catalyst is made up of hydrogenating function and cracking function, wherein hydrogenating function is to be provided by hydrogenation active metals, improves the Hydrogenation of hydrocracking catalyst, is conducive to the saturated of aromatic hydrocarbons；Cracking function is provided by amorphous silicon aluminium or molecular sieve, it can crack the macromole of long-chain and make the further open loop of saturated rear polycyclic aromatic hydrocarbon convert, this Hydrocracking Raw Oil not only contributing to process more heavy, poor quality, improve liquid product yield and produce high-quality hydrocracked product, the ability that the anti-organic nitrogen of catalyst is poisoning can also be improved further, reduce green coke, carbon deposit, extend the service life of catalyst.
The patent such as CN103007999, CN103041482, CN103100400, CN103100427, CN103100430, CN103100412, CN103191772, CN103191773 and CN103191774 is respectively adopted the catalyst of the different different catalytic performances of method of modifying preparation, especially alumina powder has first been carried out the modified hydrocracking catalyst that is prepared for by patent CN103191773 and CN103191774 respectively, and catalytic performance is improved.
Patent CN101343559, CN101343560 and CN10134356 all describe the hydrocracking catalyst and preparation method that adopt composite molecular screen to prepare.The hydrocracking catalyst of preparation shows the catalytic performance of excellence.
Modified molecular sieve is as the component providing lytic activity in hydrocracking catalyst, and its performance is most important to the performance of hydrocracking catalyst, adopts the modified molecular screen of excellent performance to be conducive to improving further the catalytic performance of hydrocracking catalyst.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of high-activity hydrocracking catalyst and preparation method thereof.Catalyst prepared by the method has the advantages that hydrogenation cracking activity is high and 2-3 PAH cracking ability is strong.Can effectively converting the 2-3 PAH in raw material, the BMCI value of the tail oil product of hydrogenation cracking is relatively low.
Hydrocracking catalyst of the present invention, according to catalyst weight percent meter, including following component: aluminium oxide 25wt% ~ 75wt%, it is preferable that 35wt% ~ 65wt%；Hydrogen USY-Y composite molecular screen 5wt% ~ 45wt%, it is preferable that 15wt% ~ 40wt%；Active metal 15wt% ~ 50wt% (in oxide), it is preferable that 20wt% ~ 45wt%；Wherein group vib tenor is 10wt% ~ 40wt%, it is preferable that 15wt% ~ 35wt%；Group VIII metal content is 2wt% ~ 18wt%, it is preferable that 4wt% ~ 15wt%, the specific surface area 200 ~ 300m of described catalyst2/ g, external surface area 150 ~ 200m2/ g, pore volume 0.35 ~ 0.46ml/g；Described Hydrogen USY-Y composite molecular screen is with USY type molecular sieve for core, and with Y type sub-sieve for shell, in composite molecular screen, the weight content of Y type molecular sieve is 10wt% ~ 90wt%, it is preferable that 30wt% ~ 70wt%；Composite molecular screen has mesoporous-microporous structure, and mesoporous shared pore volume accounts for the 15% ~ 50% of the total pore volume of molecular sieve, it is preferable that 20% ~ 40%, and in composite molecular screen, silica/alumina molar ratio is 4.2 ~ 25, and specific surface area is 450 ~ 900m2/ g, pore volume is 0.33 ~ 0.62ml/g, and average pore size is 1.5 ~ 4.0nm；Preferential oxidation silicon/alumina molar ratio is 6 ~ 15, and specific surface area is 550 ~ 800m2/ g, pore volume is 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 steps:
(1) aluminium oxide, Hydrogen USY-Y composite molecular screen, binding agent, sesbania powder and water fully being rolled aftershaping, then dry, roasting, obtains catalyst carrier；
(2) catalyst carrier obtained by the dipping solution impregnation steps (1) containing active metal component, then dry, roasting, obtains hydrocracking catalyst.
In said method, acidic catalyst material Hydrogen USY-Y composite molecular screen described in step (1) is obtained through modified by sodium form USY-Y composite molecular screen, concrete method of modifying is as follows: be at least 2 times initially with ammonium salt exchange times, and exchange temperature is 60 ~ 110 DEG C, it is preferable that 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, it is preferable that ammonium salt is ammonium nitrate, it is preferable that concentration is 1 ~ 2mol/L.The liquid-solid ratio (ml/g) of exchange process is 5 ~ 30, it is preferable that 10 ~ 20；Each swap time is 0.5 ~ 2.0 hour, it is preferable that 1 ~ 1.5 hour.Then carrying out hydrothermal treatment consists, water vapour pressure is at 0.05 ~ 0.5MPa, it is preferable that 0.1 ~ 0.3MPa；Steam temperature is between 500 ~ 800 DEG C, it is preferable that 550 ~ 700 DEG C；The process time is between 0.5 ~ 10 hour, it is preferable that 1 ~ 6 hour.
In said method, the preparation method of sodium form USY-Y composite molecular screen, comprises the steps:
A USY molecular sieve is adopted ammonium salt to swap by ()；
B () is according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=15 ~ 20:1:15 ~ 22:320 ~ 420, are configured to mixed liquor by aluminum source, water, sodium hydroxide and waterglass, then ageing 0.5 ~ 2 day at 20 ~ 50 DEG C, prepare directed agents；
C () according to the mol ratio of (USY molecular sieve that removing adds) each material in gel isn(NaOH):n(Al2O3):n(SiO2):n(H2O)=14 ~ 18:1:9 ~ 20:320 ~ 760, it is preferable thatn(NaOH):n(Al2O3):n(SiO2):n(H2O)=14.5 ~ 16.5:1:11 ~ 18:400 ~ 650, by aluminum source, sodium hydroxide, water and waterglass are configured to mixed liquor, it is subsequently adding the USY molecular sieve after step (a) ammonium salt swaps and the prepared directed agents of step (b), by gel thermostatic crystallization 12 ~ 72 hours under 85 ~ 120 DEG C of conditions after stirring, preferably in thermostatic crystallization 24 ~ 60 hours under 90 ~ 110 DEG C of conditions, then cooled, washing, sucking filtration, obtain after drying with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added accounts for 4 ~ 30wt% of gel rubber system gross mass, preferably 6 ~ 15wt%, the quality of the directed agents added accounts for 2 ~ 20wt% of gel rubber system gross mass, preferably 4 ~ 10wt%.
USY molecular sieve described in the inventive method step (a) is through modified Y type molecular sieve, is obtained by physics or chemical method dealuminzation, desiliconization or dealumination complement silicon.Wherein representative method of modifying is hydrothermal treatment consists dealuminzation and chemical method desiliconization, dealumination complement silicon.Modified Y type molecular sieve can be Hydrogen can also be sodium form.The silica/alumina molar ratio of USY molecular sieve is 4.2 ~ 35, and specific surface area is 450 ~ 850m2/ g；Preferential oxidation silicon/alumina molar ratio is 6 ~ 15, and specific surface area is 550 ~ 800m2/g。
The inventive method step (a) adopt ammonium salt to swap process as follows: to be added to the water by ammonium salt, be subsequently adding molecular sieve, after being stirred continuously 1 ~ 2 hour, sucking filtration, dry；The concentration of ammonium salt solution is 0.15mol/L ~ 0.5mol/L, it is preferable that 0.2mol/L ~ 0.3mol/L；The mass ratio of solution and molecular sieve is 6:1 ~ 20:1, it is preferable that 9:1 ~ 15:1.
Ammonium salt in the inventive method step (a) refers to various organic quaternary ammonium salt and long-chain organic cation type surfactant.The preferred tetraethyl ammonium radical ion of quaternary ammonium salt and tetrapropyl ammonium radical ion, the long-chain organic cation preferred cetyl trimethylammonium bromide of type surfactant, P123 and F127 etc..
In the inventive method step (b) and (c), described aluminum source includes aluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate etc., it is preferable that sodium aluminate.
In the inventive method, the specific surface area of the alumina powder described in step (1) is 300 ~ 820m2/ g, it is preferable that 350 ~ 750m2/ g, pore volume is 0.45 ~ 1.45ml/g, it is preferable that 0.55 ~ 1.15ml/g.
In the inventive method, binding agent described in step (1) is to be prepared from by little porous aluminum oxide, organic acid and/or mineral acid, and preparation process is known for those skilled in the art, and wherein aperture aluminium oxide pore volume used is 0.25 ~ 0.55ml/g, preferably 0.31 ~ 0.48ml/g, specific surface is 160 ~ 420m2/ g, it is preferable that 190 ~ 390m2/g。
In the inventive method, the baking temperature described in step (1) is 50 ~ 120 DEG C, and the time is 6 ~ 12 hours；Sintering temperature is 450 ~ 650 DEG C, and the time is 2 ~ 12 hours.
In the inventive method, containing active metal component in the metallic solution described in step (2) is group vib metal and group VIII metal；The preferred tungsten of group vib metal (W) and molybdenum (Mo), the preferred cobalt of group VIII metal (Co) and nickel (Ni), the those skilled in the art that are formulated as of dipping solution know；Dipping method adopts supersaturation dipping.
In the inventive method, described baking temperature is 50 ~ 150 DEG C, it is preferable that 100 ~ 120 DEG C, and drying time is 6 ~ 12 hours；Sintering temperature is 450 ~ 650 DEG C, and the time is 2 ~ 12 hours.
Catalyst prepared by the inventive method has high catalysis activity and 2-3 PAH cracking ability is suitable for treatment of heavy hydrocarbon material, the heavy hydrocarbon material of especially high arene content.The boiling range of heavy hydrocarbon material is 300 ~ 600 DEG C.Catalyst of the present invention process VGO time, reaction condition all under hydrogen existence condition, reaction pressure 10 ~ 20MPa, reaction temperature 360 ~ 420 DEG C, hydrogen to oil volume ratio 500 ~ 2000, volume space velocity 0.5 ~ 7.0h during liquid-1。
The inventive method is compared to prior art, have the advantage that USY-Y composite molecular screen has obvious mesoporous-microporous structure, improve active center accessibility and the interaction with hydrogenation metal in the catalyst of preparation, make cracking component and hydrogenation component carry out the collocation more optimized.The diffusion velocity of reactant and product can also be improved simultaneously, reduce the chance of molecule generation second pyrolysis.The reaction existing for macromole especially aromatic hydrocarbons macromole of a large amount of meso-hole structures provides condition, makes catalyst of the present invention not only have suitable lytic activity, also has efficient 2-3 PAH conversion capability simultaneously.
Detailed description of the invention
Further illustrate the preparation process of the present invention below in conjunction with embodiment, but following example do not constitute the restriction to the inventive method.Preparation process all adopts and adds aluminium oxide and the binding agent with following character.The character of alumina powder is as follows: specific surface area is 425m2/ g, pore volume is 0.82ml/g.Binding agent is to be prepared from by little porous aluminum oxide, organic acid and/or mineral acid, and preparation process is known for those skilled in the art, and wherein aperture Properties of Alumina used is as follows: specific surface is 298m2/ g, pore volume is 0.46ml/g.
The preparation of composite molecular screen and modified
Embodiment 1
(1) adopt 4-propyl bromide to swap USY molecular sieve, make molecular sieve structure stable.4-propyl bromide is added to the water, then adds USY and enter molecular sieve, after being stirred continuously 1 hour, sucking filtration, dry.The concentration of ammonium salt solution is 0.35mol/L, and the mass ratio of 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, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 1.5 days at 40 DEG C, prepare directed agents.
(3) according to the mol ratio of (USY molecular sieve that removing adds) each material in gel it isn(NaOH):
n(Al2O3):n(SiO2):n(H2The condition of O)=16:1:16:480.When stirring, sodium aluminate, sodium hydroxide, water and waterglass are added sequentially in beaker and form mixed liquor, it is subsequently adding the directed agents that step (1) USY molecular sieve and step (2) prepare, by gel thermostatic crystallization 48 hours under 95 DEG C of conditions after stirring, then cooled, washing, sucking filtration, after drying obtain with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added accounts for the 8wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 6wt% of gel rubber system gross mass.
(4) adopting the ammonium chloride solution of 1mol/L to carry out 2 ammonium exchanges, exchange temperature is 80 DEG C.Liquid-solid ratio (ml/g) in exchange process is 15；Each swap time is 1.0 hours.Sucking filtration after end, then carries out hydrothermal treatment consists, controls water vapour pressure at 0.2MPa；Steam temperature processes 5 hours at 600 DEG C of constant temperature.The Hydrogen USY-Y composite molecular screen of preparation is with USY type molecular sieve for core, and with Y type sub-sieve for shell, in composite molecular screen, the weight content of Y type molecular sieve is 48wt%；Composite molecular screen has mesoporous-microporous structure, and mesoporous shared pore volume accounts for the 28% of the total pore volume of molecular sieve, and in composite molecular screen, silica/alumina molar ratio is 7, and specific surface area is 720m2/ g, pore volume is 0.38ml/g, and average pore size is 2.0nm.
Embodiment 2
(1) adopting tetraethylammonium bromide to swap USY molecular sieve, the pore passage structure making USY molecular sieve is stable.Concrete exchange process is as follows: be added to the water by tetraethylammonium bromide, then adds USY and enters molecular sieve, after being stirred continuously 1.5 hours, and sucking filtration, 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, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 2 days at 25 DEG C, prepare directed agents.
(3) according to the mol ratio of (USY molecular sieve that removing adds) each material in gel it isn(NaOH):
n(Al2O3):n(SiO2):n(H2The condition of O)=15:1:16:450.When stirring, sodium aluminate, sodium hydroxide, water and waterglass are added sequentially in beaker and form mixed liquor, it is subsequently adding the directed agents that step (1) USY molecular sieve and step (2) prepare, by gel thermostatic crystallization 60 hours under 90 DEG C of conditions after stirring, then cooled, washing, sucking filtration, after drying obtain with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added accounts for the 8wt% 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) adopting the ammonium chloride of 1.5mol/L, ammonium sulfate or ammonium nitrate ammonium salt solution to carry out 2 ammonium exchanges, exchange temperature is 90 DEG C.Liquid-solid ratio (ml/g) in exchange process is 8；Each swap time is 1.5 hours.Sucking filtration after end, then carries out hydrothermal treatment consists, controls water vapour pressure at 0.1MPa；Steam temperature processes 2 hours at 650 DEG C of constant temperature.
The Hydrogen USY-Y composite molecular screen of preparation is with USY type molecular sieve for core, and with Y type sub-sieve for shell, in composite molecular screen, the weight content of Y type molecular sieve is 60wt%；Composite molecular screen has mesoporous-microporous structure, and mesoporous shared pore volume accounts for the 25% of the total pore volume of molecular sieve, and in composite molecular screen, silica/alumina molar ratio is 6, and specific surface area is 800m2/ g, pore volume is 0.41ml/g, and average pore size is 1.9nm.
Embodiment 3
(1) adopt cetyl trimethylammonium bromide to swap USY molecular sieve, make molecular sieve structure stable.Cetyl trimethylammonium bromide is added to the water, then adds USY and enter molecular sieve, after being stirred continuously 1.5 hours, sucking filtration, dry.The concentration of ammonium salt 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, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 1 day at 35 DEG C, prepare directed agents.
(3) according to the mol ratio of (USY molecular sieve that removing adds) each material in gel it isn(NaOH):
n(Al2O3):n(SiO2):n(H2The condition of O)=15.5:1:14:550.When stirring, aluminum sulfate, sodium hydroxide, water and waterglass are added sequentially in beaker and form mixed liquor, it is subsequently adding the directed agents that step (1) USY molecular sieve and step (2) prepare, by gel thermostatic crystallization 48 hours under 100 DEG C of conditions after stirring, then cooled, washing, sucking filtration, after drying obtain with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added 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) adopting the ammonium chloride of 2mol/L, ammonium sulfate or ammonium nitrate ammonium salt solution to carry out 2 ammonium exchanges, exchange temperature is 70 DEG C.Liquid-solid ratio (ml/g) in exchange process is 20；Each swap time is 1 hour.Sucking filtration after end, then carries out hydrothermal treatment consists, controls water vapour pressure at 0.2MPa；Steam temperature processes 1 hour at 550 DEG C of constant temperature.
The Hydrogen USY-Y composite molecular screen of preparation is with USY type molecular sieve for core, and with Y type sub-sieve for 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 32% of the total pore volume of molecular sieve, and in composite molecular screen, silica/alumina molar ratio is 11, and specific surface area is 700m2/ g, pore volume is 0.45ml/g, and average pore size is 2.3nm.
Embodiment 4
(1) adopt cetyl trimethylammonium bromide to swap USY molecular sieve, make molecular sieve structure stable.Cetyl trimethylammonium bromide is added to the water, then adds USY and enter molecular sieve, after being stirred continuously 2 hours, sucking filtration, dry.The concentration of ammonium salt solution 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, under stirring, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 1 day at 35 DEG C, prepare directed agents.
(3) according to the mol ratio of (USY molecular sieve that removing adds) each material in gel it isn(NaOH):
n(Al2O3):n(SiO2):n(H2The condition of O)=16:1:17:450.When stirring, aluminum nitrate, sodium hydroxide, water and waterglass are added sequentially in beaker and form mixed liquor, it is subsequently adding the directed agents that step (1) USY molecular sieve and step (2) prepare, by gel thermostatic crystallization 24 hours under 110 DEG C of conditions after stirring, then cooled, washing, sucking filtration, after drying obtain with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added 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) adopting the ammonium chloride of 1.5mol/L, ammonium sulfate or ammonium nitrate ammonium salt solution to carry out 2 ammonium exchanges, exchange temperature is 70 DEG C.Liquid-solid ratio (ml/g) in exchange process is 12；Each swap time is 2 hours.Sucking filtration after end, then carries out hydrothermal treatment consists, controls water vapour pressure at 0.15MPa；Steam temperature processes 3 hours at 640 DEG C of constant temperature.
The Hydrogen USY-Y composite molecular screen of preparation is with USY type molecular sieve for core, and with Y type sub-sieve for 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 38% of the total pore volume of molecular sieve, and in composite molecular screen, silica/alumina molar ratio is 13, and specific surface area is 680m2/ g, pore volume is 0.52ml/g, and average pore size is 2.5nm.
Catalyst preparing
Embodiment 5
Hydrogen USY-Y composite molecular screen, binding agent, sesbania powder and the water aluminium oxide, embodiment 1 prepared fully roll aftershaping, then dry 8 hours when 80 DEG C, finally roasting 4 hours under 550 DEG C of conditions.Obtain catalyst carrier；With the metallic solution impregnated catalyst support containing W and Ni, then drying 12 hours when 120 DEG C, finally roasting 6 hours when 550 DEG C, obtain hydrocracking catalyst HC1.Catalyst property is table 1, table 2 such as.
Embodiment 6
Hydrogen USY-Y composite molecular screen, binding agent, sesbania powder and the water aluminium oxide, embodiment 2 prepared fully roll aftershaping, then dry 8 hours when 100 DEG C, finally roasting 8 hours under 500 DEG C of conditions.Obtain catalyst carrier；With the metallic solution impregnated catalyst support containing W and Co, then drying 8 hours when 110 DEG C, finally roasting 8 hours when 520 DEG C, obtain hydrocracking catalyst HC2.Catalyst property is table 1, table 2 such as.
Embodiment 7
Hydrogen USY-Y composite molecular screen, binding agent, sesbania powder and the water aluminium oxide, embodiment 3 prepared fully roll aftershaping, then dry 9 hours when 90 DEG C, finally roasting 9 hours under 540 DEG C of conditions.Obtain catalyst carrier；With the metallic solution impregnated catalyst support containing Mo and Ni, then drying 7 hours when 110 DEG C, finally roasting 6 hours when 540 DEG C, obtain hydrocracking catalyst HC3.Catalyst property is table 1, table 2 such as.
Embodiment 8
Hydrogen USY-Y composite molecular screen, binding agent, sesbania powder and the water aluminium oxide, embodiment 4 prepared fully roll aftershaping, then dry 12 hours when 60 DEG C, finally roasting 4 hours under 550 DEG C of conditions.Obtain catalyst carrier；With the metallic solution impregnated catalyst support containing W and Ni, then drying 6 hours when 110 DEG C, finally roasting 3 hours when 560 DEG C, obtain hydrocracking catalyst HC4.Catalyst property is table 1, table 2 such as.
Comparative example 1
By aluminium oxide, adopt Y molecular sieve, binding agent, sesbania powder and water that embodiment 4 step (4) method processes fully to roll aftershaping, then dry 12 hours when 60 DEG C, finally roasting 4 hours under 550 DEG C of conditions.Obtain catalyst carrier；With the metallic solution impregnated catalyst support containing W and Ni, then drying 6 hours when 110 DEG C, finally roasting 3 hours when 560 DEG C, obtain hydrocracking catalyst BHC4.Catalyst property is table 1, table 2 such as.
Comparative example 2
By aluminium oxide, adopt USY molecular sieve, binding agent, sesbania powder and water that embodiment 4 step (4) method processes fully to roll aftershaping, then dry 12 hours when 60 DEG C, finally roasting 4 hours under 550 DEG C of conditions.Obtain catalyst carrier；With the metallic solution impregnated catalyst support containing W and Ni, then drying 6 hours when 110 DEG C, finally roasting 3 hours when 560 DEG C, obtain hydrocracking catalyst BHC4.Catalyst property is table 1, table 2 such as.
Catalytic performance test.
Evaluating apparatus adopts 200m1 small hydrogenation device to carry out, and before activity rating, catalyst is carried out presulfurization.Evaluating the raw materials used oil nature of catalyst activity and reaction process condition in Table 3 and table 4, catalyst reaction performance comparison result is in Table 5.When evaluating catalyst, raw oil first passes through Hydrobon catalyst bed and then immediately proceeds to hydrocracking catalyst bed, controls the organic nitrogen content in raw oil lower than 5ppm through Hydrobon catalyst bed.
The composition of table 1 catalyst
The character of table 2 catalyst.
Table 3 process conditions.
Table 4 feedstock property.
Table 5 catalyst reaction performance.
| Catalyst | HC1 | HC2 | HC3 | HC4 | BHC1 | BHC1 |
| Reaction temperature, DEG C | 375 | 370 | 372 | 378 | 385 | 385 |
| BMCI value | 7.6 | 10.5 | 6.5 | 8.0 | 10.5 | 10.2 |
Claims (21)
1. a hydrocracking catalyst, it is characterised in that: according to catalyst weight percent meter, including following component: aluminium oxide 25wt% ~ 75wt%；Hydrogen USY-Y composite molecular screen 5wt% ~ 45wt%；Active metal 15wt% ~ 50wt% (in oxide)；Wherein group vib tenor is 10wt% ~ 40wt%；Group VIII metal content is 2wt% ~ 18wt%, the specific surface area 200 ~ 300m of described catalyst2/ g, external surface area 150 ~ 200m2/ g, pore volume 0.35 ~ 0.46ml/g；Described Hydrogen USY-Y composite molecular screen is with USY type molecular sieve for core, and with Y type sub-sieve for shell, in composite molecular screen, the weight content of Y type molecular sieve is 10wt% ~ 90wt%；Composite molecular screen has mesoporous-microporous structure, and mesoporous shared pore volume accounts for the 15% ~ 50% of the total pore volume of molecular sieve, and in composite molecular screen, silica/alumina molar ratio is 4.2 ~ 25, and specific surface area is 450 ~ 900m2/ g, pore volume is 0.33 ~ 0.62ml/g, and average pore size is 1.5 ~ 4.0nm.
2. catalyst according to claim 1, it is characterised in that: aluminium oxide 35wt% ~ 65wt%；Hydrogen USY-Y composite molecular screen 15wt% ~ 40wt%；Active metal 20wt% ~ 45wt%；Wherein group vib tenor is 15wt% ~ 35wt%；Group VIII metal content is 4wt% ~ 15wt%.
3. catalyst according to claim 1, it is characterised in that: in composite molecular screen, the weight content of Y type molecular sieve is 30wt% ~ 70wt%；Mesoporous shared pore volume accounts for the 20% ~ 40% of the total pore volume of molecular sieve, and composite molecular screen silica/alumina molar ratio is 6 ~ 15, and specific surface area is 550 ~ 800m2/ g, pore volume is 0.35 ~ 0.50ml/g, and average pore size is 1.8 ~ 2.9nm.
4. the preparation method of the described catalyst of one of claim 1-3, it is characterised in that:
(1) aluminium oxide, Hydrogen USY-Y composite molecular screen, binding agent, sesbania powder and water fully being rolled aftershaping, then dry, roasting, obtains catalyst carrier；
(2) catalyst carrier obtained by the dipping solution impregnation steps (1) containing active metal component, then dry, roasting, obtains hydrocracking catalyst.
5. method according to claim 4, it is characterized in that: the Hydrogen USY-Y composite molecular screen described in step (1) is obtained through modified by sodium form USY-Y composite molecular screen, concrete method of modifying is as follows: be at least 2 times initially with ammonium salt exchange times, exchange temperature is 60 ~ 110 DEG C, ammonium salt used is ammonium chloride, ammonium sulfate or ammonium nitrate, the concentration of ammonium salt is 0.5 ~ 3mol/L, and the liquid-solid ratio (ml/g) of exchange process is 5 ~ 30, and each swap time is 0.5 ~ 2.0 hour；Exchange carries out hydrothermal treatment consists after terminating, and water vapour pressure is 0.05 ~ 0.5MPa；Steam temperature is between 500 ~ 800 DEG C；The process time is between 0.5 ~ 10 hour.
6. method according to claim 5, it is characterised in that: exchange temperature is 80 ~ 100 DEG C, and ammonium salt is ammonium nitrate, and concentration is 1 ~ 2mol/L, and the liquid-solid ratio (ml/g) of exchange process is 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；The process time is 1 ~ 6 hour.
7. method according to claim 5, it is characterised in that: the preparation method of sodium form USY-Y composite molecular screen, comprise the steps:
A USY molecular sieve is adopted ammonium salt to swap by ()；
B () is according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=15 ~ 20:1:15 ~ 22:320 ~ 420, are configured to mixed liquor by aluminum source, water, sodium hydroxide and waterglass, then ageing 0.5 ~ 2 day at 20 ~ 50 DEG C, prepare directed agents；
C () according to the mol ratio of (USY molecular sieve that removing adds) each material in gel isn(NaOH):n(Al2O3):n(SiO2):n(H2O)=14 ~ 18:1:9 ~ 20:320 ~ 760, by aluminum source, sodium hydroxide, water and waterglass are configured to mixed liquor, it is subsequently adding the USY molecular sieve after step (a) ammonium salt swaps and the prepared directed agents of step (b), by gel thermostatic crystallization 12 ~ 72 hours under 85 ~ 120 DEG C of conditions after stirring, then cooled, washing, sucking filtration, obtain after drying with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added accounts for 4 ~ 30wt% of gel rubber system gross mass, the quality of the directed agents added accounts for 2 ~ 20wt% of gel rubber system gross mass.
8. method according to claim 7, it is characterized in that: USY molecular sieve described in step (a) is through modified Y type molecular sieve, obtained by physics or chemical method dealuminzation, desiliconization or dealumination complement silicon, the silica/alumina molar ratio of USY molecular sieve is 4.2 ~ 35, and specific surface area is 450 ~ 850m2/g.
Method according to claim 8, it is characterised in that: silica/alumina molar ratio is 6 ~ 15, and specific surface area is 550 ~ 800m2/g。
9. method according to claim 7, it is characterised in that: step (a) adopt ammonium salt to swap process as follows: to be added to the water by ammonium salt, be subsequently adding molecular sieve, after being stirred continuously 1 ~ 2 hour, sucking filtration, dry；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.
10. method according to claim 10, it is characterised in that: the concentration of ammonium salt solution is 0.2mol/L ~ 0.3mol/L；The mass ratio of solution and molecular sieve is 9:1 ~ 15:1.
11. method according to claim 7, it is characterised in that: the ammonium salt in step (a) is organic quaternary ammonium salt or long-chain organic cation type surfactant.
12. method according to claim 12, it is characterised in that: quaternary ammonium salt is tetraethyl ammonium radical ion or tetrapropyl ammonium radical ion, and long-chain organic cation type surfactant is cetyl trimethylammonium bromide, P123 or F127.
13. method according to claim 7, it is characterised in that: step (b) and the aluminum source described in (c) include one or more in aluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate.
14. method according to claim 7, it is characterised in that: step (c) according to the mol ratio of material each in gel isn(NaOH):n(Al2O3):n(SiO2):n(H2O)=14.5 ~ 16.5:1:11 ~ 18:400 ~ 650, aluminum source, sodium hydroxide, water and waterglass are configured to mixed liquor, thermostatic crystallization 24 ~ 60 hours under 90 ~ 110 DEG C of conditions, the quality of the USY molecular sieve added accounts for 6 ~ 15wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for 4 ~ 10wt% of gel rubber system gross mass.
15. method according to claim 4, it is characterised in that: the specific surface area of the alumina powder described in step (1) is 300 ~ 820m2/ g, pore volume is 0.45 ~ 1.45ml/g.
16. method according to claim 16, it is characterised in that: the specific surface area of the alumina powder described in step (1) is 350 ~ 750m2/ g, pore volume is 0.55 ~ 1.15ml/g.
17. method according to claim 4, it is characterized in that: the binding agent described in step (1) is to be prepared from by little porous aluminum oxide, organic acid and/or mineral acid, preparation process is known for those skilled in the art, wherein aperture aluminium oxide pore volume used is 0.25 ~ 0.55ml/g, and specific surface is 160 ~ 420m2/g。
18. method according to claim 4, it is characterised in that: containing active metal component in the metallic solution described in step (2) is group vib metal and group VIII metal；Group vib metal is tungsten (W) or molybdenum (Mo), and group VIII metal is cobalt (Co) or nickel (Ni).
19. method according to claim 4, it is characterised in that: the baking temperature described in step (1) or (2) is 50 ~ 150 DEG C, and drying time is 6 ~ 12 hours；Sintering temperature is 450 ~ 650 DEG C, and the time is 2 ~ 12 hours.
20. the application that the described catalyst of one of claim 1-3 is in treatment of heavy hydrocarbon material, it is characterised in that: the boiling range of heavy hydrocarbon material is 300 ~ 600 DEG C.
21. application according to claim 22, it is characterised in that: heavy hydrocarbon material is VGO, reaction pressure 10 ~ 20MPa, reaction temperature 360 ~ 420 DEG C, hydrogen to oil volume ratio 500 ~ 2000, volume space velocity 0.5 ~ 7.0h during liquid-1。
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| CN110833862A (en) * | 2018-08-16 | 2020-02-25 | 中国石油化工股份有限公司 | Acetal hydrogenation catalyst and preparation method thereof |
| CN112742457A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrocracking catalyst, preparation method and application thereof |
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