CN102049283B - Hydro-cracking catalyst and preparation method thereof - Google Patents
Hydro-cracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydro-cracking catalyst and a preparation method thereof. The catalyst comprises hydrogenated active metal ingredients and carriers containing small grain Y molecular sieves, amorphous silica-alumina and alumina, wherein the small grain Y molecular sieves are obtained by treating hydrothermally treated Y molecular sieves by using mixed aqueous solution of aluminum salt and acid. The Y molecular sieves have small grains, high crystallization degree, high silica-alumina ratio and proper total acid amount and acid distribution; the Y molecular sieves and the amorphous silica-alumina are used as acid components of the catalyst together; and the prepared catalyst can treat heavier and/or poor-quality raw materials, and has the characteristics of high catalytic activity, good selectivity of intermediate fraction oil and the like.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, particularly a kind of high activity fecund intermediate oil hydrocracking catalyst and preparation method thereof.
Background technology
The sustainable development of World Economics, make international oil product market to the demand of high-quality middle cut oil product (comprising that mainly sea-lanes of communication and agricultural and major impetus fuel--power fuel of diesel oil, the aircraft industry--jet fuel of engineering machinery and family's warming are with oily) always in continuous increase.China is because economic development is rapid, and this demand is more vigorous.In addition, the ecological environment for to protect mankind is depended on for existence has also proposed more and more high requirement to fuel oil quality, and production and use clean fuel become the main flow of world today's development.Meanwhile, World's Oil and Gas Resources constantly reduces, and crude quality is variation year by year, and the situation of China is all the more so.Based on the exclusive characteristics and advantages of hydrocracking technology, this technology has become rationally utilizes limited crude resources, to greatest extent production cleaning intermediate oil and the optimum oil Refining Technologies of high-quality industrial chemicals, and is obtaining increasingly extensive application.
Hydrocracking catalyst is a kind of bifunctional catalyst, and it has cracking activity and hydrogenation activity simultaneously, namely contains simultaneously acidic components and hydrogenation activity component.Wherein acidity mainly is to be provided by various molecular sieves and/or the heat-resistant inorganic oxide that consists of carrier, and the character of acidic components selectively has a very important impact to the activity of hydrocracking catalyst and intermediate oil.The hydrogenation activity component generally is selected from metal, metal oxide and/or the metal sulfide of group vib and VIII family in the periodic table of elements.The key component that plays cracking in the hydrocracking catalyst mostly is molecular sieve, and the quality of molecular sieve performance will directly affect catalyst performance and oil quality.
US4401556 discloses a kind of hydrocracking catalyst for the production of intermediate oil.This catalyst be take through the Y zeolite of dealuminzation as the cracking activity component, its silica alumina ratio is 4.5～35, cell parameter 2.420～2.445nm, the BET surface area is not less than 350m
2/ g.This catalyst is during take a kind of VGO as raw material, and its activity is relatively poor, and middle distillates oil selectivity is not high yet.
US4894142 discloses a kind of hydrocracking catalyst, is mainly used in the technique of voluminous intermediate oil.This catalyst contains the Y zeolite of amorphous aluminum silicide and a kind of low acidity, and the characteristics of this molecular sieve are at high temperature to process the raw molecule sieve, comprise 680～780 ℃ hydrothermal treatment consists or are higher than 700 ℃ the dry type heat treatment that passes into inert gas.Because this molecular sieve acidity is lower, makes the activity of catalyst too on the low side, this just requires to improve the hydrocracking reaction temperature, the thermal cracking trend of molecular sieve strengthens, but suppressed hydrogenation reaction, made the middle distillates oil selectivity raising of catalyst not obvious, product quality also is adversely affected.
Hydrocracking catalyst in the above-mentioned patent adopts the modified Y molecular sieve of conventional crystallite dimension, because different method of modifying and crystallite dimension are very large to the performance impact of hydrocracking catalyst, used molecular sieve crystal diffusional resistance is large, large molecule is difficult to enter inside, duct and reacts, the reaction afterproduct also difficulty diffuse out, so its cracking activity and purpose product selectively be subject to restriction.
Introduced a kind of small-grain Y-type zeolite and preparation method thereof among the CN1382632A, the lattice constant of molecular sieve is 2.425～2.45nm, and crystallization reservation degree is greater than 75%, and adopts the silicon tetrachloride gaseous state to contact the modification small crystal grain Y-shaped molecular sieve with prepared molecular sieve.Its prepared raw material small crystal grain Y-shaped molecular sieve crystallization reservation degree is low, the method for modifying that adopts, and preparation cost is high, industrial difficult the realization.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of hydrocracking catalyst and preparation method thereof.This hydrocracking catalyst adopts that little crystal grain, degree of crystallinity are high, silica alumina ratio is large, total acid content and acid distribute suitable small-grain Y molecular sieve as acidic components, is conducive to improve the selective of the activity of hydrocracking catalyst and intermediate oil.
Hydrocracking catalyst of the present invention comprises hydrogenation active metals component and the carrier that contains small-grain Y molecular sieve, amorphous aluminum silicide and aluminium oxide, wherein said small-grain Y molecular sieve, and its character is as follows: SiO
2/ Al
2O
3Mol ratio is 30.0～150.0, is preferably 40.0～80.0, and average grain diameter is 100～700nm, is preferably 300～500nm; Cell parameter is 2.425～2.433nm, and relative crystallinity is 90%～130%, is preferably 100%～130%, and crystallization reservation degree generally below 120%, is preferably 98%～120% greater than 95%, and specific surface is 850～950m
2/ g, pore volume 0.30ml/g～0.50ml/g, meleic acid amount 0.1～0.4mmol/g, B acid/L acid is more than 7.0, is preferably more than 8.0, sodium oxide content≤0.05wt% is preferably≤0.01wt%.
Hydrocracking catalyst character of the present invention is as follows: specific area is 200～350m
2/ g, pore volume are 0.40～0.65ml/g.
Described hydrogenation active metals is the metal of group vib and/or group VIII, and the group vib metal is preferably molybdenum and/or tungsten, and the metal of group VIII is preferably cobalt and/or nickel.With the weighing scale of catalyst, the content of group vib metal (take oxide) is 10.0%～30.0%, and the content of group VIII metal (take oxide) is 4.0%～8.0%, and the content of carrier is 62.0%～86.0%.
Described carrier of hydrocracking catalyst with the weighing scale of carrier, comprises 10%～70% amorphous aluminum silicide, 3%～20% small-grain Y molecular sieve, 15%～70% aluminium oxide.
The preparation method of hydrocracking catalyst of the present invention comprises the steps:
With small-grain Y molecular sieve, amorphous aluminum silicide, aluminium oxide, adhesive mechanical mixture, moulding, then catalyst carrier is made in drying and roasting; Supported active metal component on the catalyst carrier of gained, catalyst is made in drying and roasting;
Wherein said small-grain Y molecular sieve comprises being prepared as follows step:
(1) preparation of fine grain NaY type molecular sieve;
(2) the fine grain NaY type molecular sieve with step (1) gained becomes little crystal grain NH
4NaY;
(3) with little crystal grain NH
4The NaY molecular sieve is raw material, carries out dealumination complement silicon with the hexafluorosilicic acid aqueous ammonium and processes;
(4) Y zeolite that step (3) is obtained carries out hydrothermal treatment consists;
(5) with the Y zeolite of aluminium salt and inorganic acid or organic acid mixed aqueous solution treatment step (4) gained, then filter, wash and drying, obtain the used small crystal grain Y-shaped molecular sieve of carrier of the present invention.
The preparation method of fine grain NaY type molecular sieve is as follows in the step in the inventive method (1):
A, preparation directed agents: more than 0 ℃ and under less than 15 ℃ temperature, be preferably under 4～10 ℃ the temperature, high alkali deflection aluminium acid sodium solution and waterglass are mixed, then more than 0 ℃ and under less than 15 ℃ temperature, be preferably under 4～10 ℃ the temperature static aging 10～14 hours, make directed agents;
B, preparation gel: under 0 ℃～10 ℃ temperature, the prepared directed agents of waterglass, aluminum sulfate solution, low alkali aluminium acid sodium solution and steps A is mixed, the synthetic liquid that then will obtain is static wearing out 5～10 hours under said temperature, obtains gel; The Al in the directed agents wherein
2O
3Weight accounts for the middle Al that always feeds intake
2O
33wt%～the 10wt% of weight;
C, crystallization: the gel that step B is obtained was 50 ℃～90 ℃ and the Water Under thermal crystallisation that stirs 5～10 hours, then heat up, hydrothermal crystallizing 5～10 hours again under 80 ℃～120 ℃ and the condition that stirs, crystallization obtains fine grain NaY type molecular sieve by filtration, washing, drying.
Steps A and step B can feed intake according to the raw material proportioning that routine prepares NaY type molecular sieve in the inventive method, and the inventive method is recommended as follows: the described high alkali deflection aluminium acid sodium solution of steps A and waterglass are pressed Na
2O: Al
2O
3: SiO
2: H
2The mol ratio of O=10～20: 1: 10～20: 300～400 feeds intake; The described waterglass of step B, aluminum sulfate solution, low alkali aluminium acid sodium solution and the prepared directed agents of steps A are pressed Na
2O: Al
2O
3: SiO
2: H
2The mol ratio of O=2～4: 1: 6～12: 150～300 feeds intake; Wherein water can add separately, also can together add with solution.
In the step (5), in described aluminium salt and inorganic acid or the organic acid mixed aqueous solution, the aluminium salinity is (with Al
3+Meter) 0.2～4.0mol/L, preferred 1.0～2.0mol/L, inorganic acid or organic acid concentration are (with H
+Meter) 0.2～2.0mol/L, preferred 0.4～1.0mol/L.Aluminium salt is (with Al
3+Meter) with inorganic acid or organic acid (with H
+Meter) mol ratio is 0.2～20, preferred 2～5.The weight ratio of aluminium salt and inorganic acid or organic acid mixed solution and molecular sieve is 3: 1～50: 1.Described treatment conditions: 40～120 ℃ of temperature, be preferably 70～100 ℃, the time is 0.5～8 hour, preferred 1～3 hour.Described wash conditions: until cleaning solution pH value is near neutrality, then under 100～120 ℃ condition dry 3～6 hours.
Treatment conditions described in the step (4): gauge pressure 0.05～0.40MPa is preferably 0.1～0.2MPa, 630～750 ℃ of temperature, preferred 630～700 ℃, 0.5～5.0 hour processing time, preferred 1.0～3.0 hours.
Hydrocracking catalyst of the present invention can be used in the conventional hydrocracking process, be specially adapted to take the hydrocracking process of voluminous intermediate oil as the purpose product, its hydrocracking operating condition is as follows: reaction temperature is 350～420 ℃, stagnation pressure 8～17MPa, hydrogen to oil volume ratio 600～1500, volume space velocity 0.6～2.0h during liquid
-1
Small-grain Y molecular sieve of the present invention is the Y zeolite that adopts after aluminium salt and sour mixed aqueous solution are processed hydrothermal treatment consists, in the situation that does not remove framework aluminum, not only can remove the non-framework aluminum fragment that almost all is deposited in the secondary pore, and can also remove the non-framework aluminum fragment that is filled in a large number in the micropore, in the situation that keeps the molecular sieve high-crystallinity, improved after the hydrothermal treatment consists amount of removing of non-framework aluminum in the molecular sieve, improved the silica alumina ratio of molecular sieve, increased the specific surface of molecular sieve, adopt simultaneously suitable hydrothermal treatment consists condition, the acidity and the acid that have improved molecular sieve distribute, especially the distribution of B acid and L acid, and make the secondary pore duct that forms after the hydrothermal treatment consists become very " unobstructed ".
Adopting small crystal grain molecular sieve in the carrier of the present invention in addition is the cracking component, prepared catalyst can be processed heavier charging, as the oil of the generation after the deep drawing of reducing pressure, wherein containing restructuring divides many, utilize the huge outer surface of small crystal grain molecular sieve, make large molecule have the space of reaction, make simultaneously that product is easier to be diffused out, in addition, sodium oxide content in the small-grain Y molecular sieve can drop to below 0.05%, even below 0.01%, can make by this molecular sieve is the activity increase of the hydrocracking catalyst of active component, can promote better the performance of catalyst hydrogenation performance simultaneously.Catalyst of the present invention adopts this small crystal grain Y-shaped molecular sieve and amorphous aluminum silicide as acidic components, oil type hydrocracking catalyst in the suitable conduct, activity and the middle distillates oil selectivity of raising catalyst.
In the mixed aqueous solution of the aluminium salt that the present invention adopts and acid, the concentration of aluminium salt and acid and ratio are suitable, not only can avoid because acid concentration is crossed strong infringement to framework of molecular sieve, and the molecular sieve after the hydrothermal treatment consists is being kept in the situation of high-crystallinity, remove to greatest extent non-framework aluminum, make the duct unimpeded, specific surface increases, and suitable acidity is arranged.The little crystal grain high-crystallinity high silica alumina ratio Y zeolite of gained of the present invention is as the cracking component, can relatively increase the activated centre, and can make the large molecule of heavy oil easier of the activated centre, crackate is easier to be diffused out from chain carrier, both improved the cracking ability of heavy oil, reduced again the secondary response of intermediate oil, gas yield is descended, coke yield reduces, and therefore catalyst shows good cracking activity and product selectivity.
The inventive method preparation process is simple, and production cost is low, and the pollution to environment in the production process is little.
The specific embodiment
Used amorphous aluminum silicide can be by coprecipitation or grafting copolymerization process preparation in the catalyst of the present invention, press in the document conventional method and prepares and get final product.SiO in the amorphous aluminum silicide that makes
2Weight content be 30%～70%, be preferably 35%～65%, the pore volume of amorphous aluminum silicide is 0.6～1.1ml/g, is preferably 0.8～1.0ml/g, specific area is 300～500m
2/ g is preferably 350～500m
2/ g.The weight content of described amorphous aluminum silicide in carrier is preferably 25%～55%.
Aluminium oxide can adopt aluminium oxide used in the conventional hydrocracking catalyst in the hydrocracking catalyst of the present invention, such as macroporous aluminium oxide and/or little porous aluminum oxide.
Adhesive therefor of the present invention is to be made by little porous aluminum oxide and inorganic acid and/or organic acid.Used aperture aluminium oxide pore volume is 0.3～0.5ml/g, and specific area is 200～400m
2/ g.
In the inventive method step (1), Na in the described high alkali deflection aluminium acid sodium solution
2O content is 260～320g/L, Al
2O
3Content is 30～50g/L, and solution does not contain floccule or precipitation for the clarification shape, can adopt the conventional method preparation.Na in the described low alkali aluminium acid sodium solution
2O content is 100～130g/L, Al
2O
3Content is 60～90g/L, and solution does not contain floccule or precipitation for the clarification shape, can adopt the conventional method preparation.Al in the described aluminum sulfate solution
2O
3Content be 80～100g/L.SiO in the described waterglass
2Content be 200～300g/L, modulus is 2.8～3.5.
The preparation method of fine grain NaY type molecular sieve of the present invention specifically comprises the steps:
A, low temperature prepare directed agents.
According to Na
2O: Al
2O
3: SiO
2: H
2The molar ratio of O=10～20: 1: 10～20: 300～400, more than 0 ℃ and under less than 15 ℃ of temperature, be preferably under 0～10 ℃ of temperature, under the condition that stirs, waterglass slowly joined in the high alkali deflection aluminium acid sodium solution and mix, afterwards, the constant temperature constant speed stirred 0.5～2 hour under said temperature; Then mixed liquor is enclosed in the synthesis reactor, aging 10～14 hours of static constant temperature makes directed agents; This directed agents preferably adds the water purification that accounts for directed agents weight 20%～40% before use.
B, low temperature prepare gel.
Under 0 ℃～10 ℃ and stirring condition, the directed agents of waterglass, aluminum sulfate solution, low alkali sodium metaaluminate and steps A gained is evenly mixed, then the constant temperature constant speed stirred 0.5～2 hour under said temperature; To synthesize liquid after stirring finishes and wear out 5～10 hours under 0 ℃～10 ℃ conditions of temperature, the synthetic liquid that then will obtain is static wearing out 5～10 hours under said temperature, gets gel; Wherein the molar ratio of gel is Na
2O: Al
2O
3: SiO
2: H
2O=2～4: 1: 6～12: 150～300, the wherein Al in the directed agents
2O
3Weight accounts for the middle Al that always feeds intake
2O
33wt%～the 10wt% of weight; The feeding sequence of the waterglass described in the step B, aluminum sulfate solution, low alkali aluminium acid sodium solution and steps A gained directed agents can adopt conventional feeding sequence, and preferably the order according to waterglass, aluminum sulfate solution, low alkali aluminium acid sodium solution and steps A gained directed agents adds.
The method Hydrothermal Synthesis fine grain NaY type molecular sieve of C, employing variable temperature crystallization.
The gel that step B is obtained adopts two sections alternating temperature dynamic crystallization methods in confined conditions.Describedly dynamically refer to crystallization under stirring condition.Under stirring condition, at first gel quick (generally at 3～8 ℃/minutes) is warmed up under 50 ℃～90 ℃ conditions, and under this temperature thermostatic crystallization 5～10 hours, the low temperature crystallized method of this elder generation can make the quantity of small crystal nucleus in the synthetic system increase, and guarantee that the crystal growth is unlikely to too fast, excessive, and can fully consume raw material in the synthetic system, and improve the output of molecular sieve, reduce synthetic cost.Improve crystallization temperature after the low temperature crystallized end, fast (generally at 3～8 ℃/minutes) are warmed up under 80 ℃～120 ℃ conditions incubation water heating crystallization 5～10 hours again, make molecular sieve Fast Growth in the synthetic system to the granule size that is fit to.Simultaneously the variable temperature crystallization method can make molecular sieve crystal framework silicon, Distribution of Al more even, is conducive to improve the hydrothermal stability of molecular sieve.Two sections crystallization cool synthesis reactor after finishing fast, after filtration, washing and dry, obtain fine grain NaY type molecular sieve.
The used raw material small crystal grain NaY molecular sieve character of the present invention is as follows: SiO
2/ Al
2O
3Mol ratio 4.0～6.0, average grain diameter are 100～700nm, specific surface 800m
2/ g～950m
2/ g, pore volume 0.30ml/g～0.40ml/g, relative crystallinity are 90%～130%, cell parameter is 2.462～2.470nm, Na
2O content is 8～10wt%.
The inventive method step (2), (3), (4) all can adopt the method for conventional Modified Zeolite Y to carry out.
Step in the inventive method (2) can be take ammonium concentration as 0.1mol/L～1.0mol/L ammonium salt solution, described ammonium salt is selected from one or more in ammonium nitrate, ammonium sulfate, ammonium chloride and the ammonium acetate, it is 50～100 ℃ in temperature, solvent and solute weight ratio is under 8: 1～15: 1 the condition, constant temperature is processed fine grain NaY, and the time is 0.5～1.5 hour, after filtration, then repeat under these conditions ammonium exchange, the product that obtains after filtration, stand-by after dry.Wherein requiring the weight content of sodium oxide molybdena in the small crystal grain molecular sieve after the control ammonium exchanges is 2.5%～5.0%.
Step in the inventive method (3) is the product (NH that will obtain in the step (2)
4)
2SiF
6The aqueous solution process, in the molecular sieve dealumination complement silicon, remove to greatest extent the sodium ion of equilibrium electronegativities in the molecular sieve.At first the molecular sieve that obtains in the step (2) is pulled an oar in the aqueous solution, solvent and solute weight ratio is 3: 1～10: 1, and temperature is 80～120 ℃, and speed of agitator is 200～400rpm; Secondly, after temperature reaches to fixed temperature, in slurry, add (NH with certain speed
4)
2SiF
6The aqueous solution adds 10～60 gram (NH according to per 100 gram Y molecular sieves
4)
2SiF
6Amount add (NH
4)
2SiF
6The aqueous solution, the speed that adds simultaneously is too not fast, and requires at the uniform velocity to add, and general warranty per hour every 100gY type molecular sieve can add 3～30 gram (NH
4)
2SiF
6, add (NH
4)
2SiF
6The aqueous solution take disposed slurry temperature as 80～120 ℃ under, the constant temperature constant speed stirred 0.5～5 hour, then filtration drying obtains product.
Step of the present invention (4) is the product water heat treatment that will obtain in the step (3) and obtaining.With the molecular sieve that obtains in the saturated steam treatment step (3), in the pipe type water heat-treatment furnace, add the molecular sieve that obtains in the step (3), treatment conditions: gauge pressure 0.05～0.4MPa, be preferably 0.1～0.2MPa, 630～750 ℃ of temperature, preferred 630～700 ℃, 0.5～5.0 hour processing time, preferred 1～3 hour;
The detailed process of the molecular sieve that obtains in the mixed aqueous solution treatment step (4) with aluminium salt and acid in the step of the present invention (5) is as follows: add the mixed solution of aluminium salt and acid in return-flow system and airtight container, wherein the aluminium salinity is (with Al
3+Meter) 0.2～4.0mol/L, preferred 1.0～2.0mol/L, inorganic acid or organic acid concentration are (with H
+Meter) 0.2～2.0mol/L, preferred 0.4～1.0mol/L stirs and is warmed up to 40～120 ℃, is preferably 70～100 ℃, then be 3: 1～50: 1 by aluminium salt with the mixed solution of acid and the weight ratio of molecular sieve, add the molecular sieve that step (2) obtains, constant temperature stirred 0.5～8 hour, preferred 1～3 hour, filter, wash, the washing until cleaning solution pH value near neutrality, and under 100～120 ℃ condition the drying 3～6 hours, obtain Y zeolite of the present invention.Wherein aluminium salt can be in alchlor, aluminum nitrate, the aluminum sulfate one or more in the mixed aqueous solution of aluminium salt and acid; Inorganic acid or organic acid can be one or more in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, the citric acid.
Stirring described in the inventive method is to adopt conventional stirring means, generally adopts mechanical agitation.
The detailed process of hydrogenation catalyst preparation of the present invention is:
Small-grain Y molecular sieve, amorphous aluminum silicide, aluminium oxide and adhesive are mixed, then extruded moulding carries out drying and roasting, is prepared into carrier, described drying can be carried out under 80 ℃ to 150 ℃ temperature 3～6 hours, and roasting is 500 ℃～700 ℃ roastings 2.5～6 hours.
The load of catalyst activity metal of the present invention, can adopt carrying method conventional in the prior art, preferred infusion process, can be saturatedly soak, excessive soak or complexing is soaked, namely with the solution impregnated catalyst carrier that contains required active component, then carrier behind the dipping 450 ℃～550 ℃ roastings 2.5～6.0 hours, makes final catalyst 100 ℃～150 ℃ dryings 1～12 hour.
The following examples are used for illustrating in greater detail the preparation method of catalyst of the present invention, but scope of the present invention is not only limited to the scope of these embodiment.
Among the present invention, specific surface and pore volume adopt the low temperature liquid nitrogen physisorphtion, relative crystallinity and cell parameter adopt x-ray diffraction method, silica alumina ratio adopts chemical method, meleic acid amount, B acid amount and L acid amount adopt the pyridine adsorption infra-red sepectrometry, wherein the summation of B acid amount and L acid amount is the meleic acid amount, and sodium content adopts plasma emission spectrometry.
Crystallization reservation degree definition: the peak height of 5 characteristic peaks and as foundation in the X-ray diffracting spectrum of Y zeolite, with through the peak height of 5 characteristic peaks of Y zeolite after the modification and divided by the peak height of 5 characteristic peaks of raw materials used NaY type molecular sieve and percentage; 5 characteristic peaks of the X-ray diffracting spectrum of Y zeolite are as follows respectively: 2 θ are the corresponding characteristic peaks of 15.8,20.7,24.0,27.4 and 31.8 peak positions.
Embodiment 1
Present embodiment is the raw materials small crystal grain NaY molecular sieve.
Used feedstock property is as follows:
High alkali deflection aluminium acid sodium: Na
2O content 291g/L, Al
2O
3Content 42g/L; Low alkali sodium metaaluminate: Na
2O content 117g/L, Al
2O
3Content 77g/L; Waterglass: SiO
2Content 250g/L, modulus 3.2; Aluminum sulfate: Al
2O
3Content 90g/L.
The preparation of LY-1:
The preparation of A, directed agents: under 10 ℃ of temperature, under stirring condition, the waterglass of 1200ml is slowly joined in the 800ml high alkali deflection aluminium acid sodium, after waterglass added, constant temperature stirred 40 minutes.Stop stirring mixed liquor is enclosed within the container, under 5 ℃ of temperature, constant temperature burin-in process 12 hours.Constant temperature finishes to add in the backward mixed liquor water purification of 667ml, and is stand-by as directed agents.
The preparation of B, gel: temperature is under 5 ℃, stirring condition, the low sodium metaaluminate and the 42.2ml directed agents that add successively 59.4ml aluminum sulfate, 62.7ml in the waterglass of 208ml, then the constant temperature constant speed stirred 1.5 hours, the synthetic liquid that then will obtain is static wearing out 8 hours under said temperature, obtains gel.
C, crystallization: under stirring condition, in 20 minutes the gel in the synthesis reactor is raised to 70 ℃, constant temperature stirred crystallization 7 hours; After the low temperature crystallized end, in 20 minutes the temperature in the synthesis reactor is brought up to 110 ℃, then constant temperature stirred 6 hours.After the high temperature crystallization finishes, fast with the cold water cooling, and open synthesis reactor and take out synthetic molecular sieve, after filtration, washing and dry, obtain product LY-1.
The preparation of LY-2:
The preparation of A, directed agents: under 8 ℃ of temperature, under stirring condition, the waterglass of 1200ml is slowly joined in the 800ml high alkali deflection aluminium acid sodium, after waterglass added, the constant temperature constant speed stirred 40 minutes.Stop stirring mixed liquor is enclosed within the container, under 8 ℃ of temperature conditions, constant temperature burin-in process 12 hours.After finishing, constant temperature in mixed liquor, adds the water purification of 667ml, and stand-by as directed agents.
The preparation of B, gel: temperature is under 2 ℃, stirring condition, in the waterglass of 208ml, add successively the low sodium metaaluminate of 59.4ml aluminum sulfate, 62.7ml and the directed agents of 56.3ml, then the constant temperature constant speed stirred 1.5 hours, the synthetic liquid that then will obtain is static wearing out 8 hours under said temperature, obtains gel.
C, crystallization: under stirring condition, in 20 minutes with synthesis reactor in the temperature of gel be raised to 80 ℃, constant temperature stirred crystallization 6 hours; After the low temperature crystallized end, in 20 minutes the temperature in the synthesis reactor is brought up to 120 ℃, then constant temperature stirred 5 hours.After the high temperature crystallization finishes, fast with the cold water cooling, and open synthesis reactor and take out synthetic molecular sieve, after filtration, washing and dry, obtain product LY-2.
Embodiment 2
At first raw material small crystal grain NaY molecular sieve LY-1 is carried out the ammonium exchange.Compound concentration is 10 liters of 0.5mol/l aqueous ammonium nitrate solutions.Take by weighing small crystal grain NaY molecular sieve 2000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions that prepare, speed of agitator is 300rpm, stirs 1 hour at 90 ℃ of lower constant temperature, then filters molecular sieve, and stays sample, analyzes Na
2O content; Repeat aforesaid operations, until Na in the molecular sieve
2O content reach 2.5～5wt%, obtaining dried sample number into spectrum is LNY-1.
Measure 1 liter of water purification and with 1000 the gram LNY-1 be dissolved in the water purification, the stirring that is rapidly heated, temperature is 95 ℃, speed of agitator is 300rpm.Within 2 hours time, at the uniform velocity in the molecular sieve slurry, add the hexafluorosilicic acid aqueous ammonium, add altogether 50 gram ammonium hexafluorosilicate, then the constant temperature constant speed stirred 2 hours, filtered, and drying obtains production code member LNY-2.
Embodiment 3
At first raw material small crystal grain NaY molecular sieve LY-2 is carried out the ammonium exchange.Compound concentration is 10 liters of 0.7mol/l aqueous ammonium nitrate solutions.Take by weighing small crystal grain NaY molecular sieve 1000 grams, be dissolved in 10 liters of aqueous ammonium nitrate solutions that prepare, speed of agitator is 300rpm, stirs 1 hour at 90 ℃ of lower constant temperature, then filters molecular sieve, and stays sample, analyzes Na
2O content; Repeat aforesaid operations, until Na in the molecular sieve
2O content reach 2.5～5wt%, obtaining dried sample number into spectrum is LNY-3.
Measure 1 liter of water purification and with 200 the gram LNY-3 be dissolved in the water purification, the stirring that is rapidly heated, temperature is 95 ℃, speed of agitator is 300rpm.Within 2 hours time, at the uniform velocity in the molecular sieve slurry, add the hexafluorosilicic acid aqueous ammonium, add altogether 50 gram ammonium hexafluorosilicate, then the constant temperature constant speed stirred 2 hours, filtered, and drying obtains production code member LNY-4.
Embodiment 4
Take by weighing 100g LNY-2 molecular sieve and put into the pipe type water heat-treatment furnace, temperature programming to 650 ℃, under gauge pressure 0.2MPa, processed 2.0 hours, after hydrothermal treatment consists finishes, take out molecular sieve and put into reflux and flask that can be airtight, add and contain concentration 1.0mol/L aluminum sulfate and concentration is the mixed aqueous solution 2000ml of 0.8mol/L sulfuric acid, stirred 1.0 hours at 100 ℃ of lower constant temperature, filter, and use the hot deionized water washing leaching cake, stop to wash after 7 with the pH value of cleaning solution.Filter cake 120 ℃ of dryings 5 hours in baking oven obtain Y zeolite of the present invention, and it numbers LNYH-1, and molecular sieve character sees Table 1.
Embodiment 5
Take by weighing 100g LNY-2 molecular sieve and put into the pipe type water heat-treatment furnace, temperature programming to 680 ℃, under gauge pressure 0.2MPa, processed 2.5 hours, then put into reflux and flask that can be airtight, adding contains concentration 1.0mol/L aluminum nitrate and concentration is the mixed aqueous solution 900ml of 0.5mol/L nitric acid, stirs 2 hours at 90 ℃ of lower constant temperature, filters, and use the hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 ℃ of dryings 5 hours in baking oven.Numbering LNYH-2, molecular sieve character sees Table 1.
Embodiment 6
Take by weighing 100g LNY-4 molecular sieve and put into the pipe type water heat-treatment furnace, temperature programming to 700 ℃, under gauge pressure 0.1MPa, processed 1.5 hours, then put into reflux and flask that can be airtight, adding contains concentration 0.6mol/L aluminum sulfate and concentration is the mixed aqueous solution 800ml of 0.4mol/L sulfuric acid, stirs 2.0 hours at 90 ℃ of lower constant temperature, filters, and use the hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 ℃ of dryings 5 hours in baking oven.Numbering LNYH-3, molecular sieve character sees Table 1.
Comparative Examples 1
Adopt method preparation among the patent CN1382632A, preparation small-grain Y zeolite, the method for modifying of employing this patent, advanced ammonium exchange, then the ammonium hexafluorosilicate dealumination complement silicon obtains the DL-1 molecular sieve, and character is listed in table 1.Claim DL-1 molecular sieve 200g to put into the pipe type water heat-treatment furnace, temperature programming to 650 ℃, under gauge pressure 0.1MPa, processed 1.5 hours, then put into reflux and flask that can be airtight, add and contain concentration 0.6mol/L aluminum sulfate aqueous solution 800ml, stirred 2 hours at 95 ℃ of lower constant temperature, filter, and use the hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 ℃ of dryings 5 hours in baking oven.Numbering DLY-1, molecular sieve character sees Table 1.
Embodiment 7
With 25.3 gram LNYH-1 sieves (butt 95wt%), 71.4 gram amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 122.9 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier FES-1.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst FEC-1, and carrier and corresponding catalyst character see Table 2.
Embodiment 8
With 14.7 gram LNYH-2 molecular sieves (butt 95wt%), 151.4 gram amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 57.1 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier FES-2.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst FEC-2, and carrier and corresponding catalyst character see Table 2.
Embodiment 9
With 8.4 gram LNYH-3 molecular sieves (butt 95wt%), 85.7 gram amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 131.42 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier FES-3.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst FEC-3, and carrier and corresponding catalyst character see Table 2.
Embodiment 10
With 31.6 gram LNYH-1 molecular sieves (butt 95wt%), 142.9 gram amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 42.9 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier FES-4.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst FEC-4, and carrier and corresponding catalyst character see Table 2.
Comparative Examples 2
With 21.1 gram DLY-1 molecular sieves (butt 95wt%), 128.6 gram amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 71.4 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier DES-1.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst DEC-1, and carrier and corresponding catalyst character see Table 2.
Comparative Examples 3
With 14.7 gram DLY-1 molecular sieves (butt 95wt%), 151.4 gram amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 57.1 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier DES-2.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, and 500 ℃ of roastings of temperature programming 4 hours get catalyst DEC-2, and carrier and corresponding catalyst character see Table 2.
Embodiment 11
Present embodiment has been introduced the catalyst activity evaluation result by the present invention's preparation.Estimate at the fixed bed hydrogenation experimental rig, appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.0h
-1, use vacuum distillate (VGO) as feedstock oil, feedstock oil character is listed in table 3.The catalyst for preparing in above-mentioned each example is estimated under above-mentioned process conditions, and the evaluation result that obtains is listed in table 4.
The physico-chemical property of table 1 embodiment gained molecular sieve
| Production code member | LY-1 | LY-2 | LNYH-1 | LNYH-2 | LNYH-3 | DL-1 | DLY-1 |
| Specific area, m 2/g | 878 | 899 | 921 | 918 | 916 | 742 | 784 |
| Pore volume, cm 3/g | 0.37 | 0.35 | 0.48 | 0.46 | 0.49 | 0.34 | 0.37 |
| External surface area, m 2/g | 153 | 167 | 189 | 182 | 179 | 123 | 142 |
| Lattice constant, nm | 2.465 | 2.463 | 2.432 | 2.430 | 2.429 | 2.447 | 2.433 |
| Relative crystallinity, % | 103 | 98 | 116 | 112 | 115 | 90 | 71 |
| The average crystal grain granularity, nm | 400 | 350 | 400 | 400 | 350 | 150 | 150 |
| SiO 2/Al 2O 3Mol ratio | 5.13 | 5.22 | 43.86 | 65.12 | 77.39 | 8.30 | 11.56 |
| Na 2O，wt％ | 8.31 | 8.26 | 0.03 | 0.02 | 0.04 | 0.15 | 0.10 |
| Crystallization reservation degree, % | - | - | 113.6 | 109.8 | 113.6 | 87 | 78.9 |
| The meleic acid amount, mmol/g | - | - | 0.308 | 0.267 | 0.238 | - | 0.852 |
| B acid/L acid | - | - | 9.66 | 11.62 | 13.81 | - | 6.79 |
The physico-chemical property of table 2 catalyst carrier and catalyst
| Carrier forms and character | ||||||
| Numbering | FES-1 | FES-2 | FES-3 | FES-4 | DES-1 | DES-2 |
| The small-grain Y molecular sieve, wt% | 12.0 | 7.0 | 4.0 | 15.0 | 10.0 | 7.0 |
| Amorphous aluminum silicide, wt% | 25.0 | 53.0 | 30.0 | 50.0 | 45.0 | 53.0 |
| Macroporous aluminium oxide, wt% | 43.0 | 20.0 | 46.0 | 15.0 | 25.0 | 20.0 |
| Adhesive, wt% | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 |
| Pore volume, ml/g | 0.73 | 0.76 | 0.78 | 0.70 | 0.69 | 0.68 |
| Specific area, m 2/g | 425 | 392 | 383 | 448 | 361 | 348 |
| Catalyst forms and character | ||||||
| Numbering | FEC-1 | FEC-2 | FEC-3 | FEC-4 | DEC-1 | DEC-2 |
| WO 3，wt％ | 16.58 | 22.82 | 23.27 | 27.49 | 21.49 | 22.45 |
| NiO，wt％ | 4.36 | 5.73 | 5.81 | 7.18 | 5.86 | 5.48 |
| Pore volume, ml/g | 0.56 | 0.53 | 0.55 | 0.41 | 0.47 | 0.47 |
| Specific area, m 2/g | 324 | 279 | 281 | 269 | 251 | 246 |
Table 3 feedstock oil main character
| Feedstock oil | Vacuum distillate |
| Density (20 ℃), kg/m 3 | 920.6 |
| Boiling range, ℃ | |
| IBP/10％ | 328/413 |
| 30％/50％ | 450/471 |
| 70％/90％ | 493/522 |
| 95％/EBP | 534/545 |
| Nitrogen, μ g/g | 1575 |
| Carbon, wt% | 85.25 |
| Hydrogen, wt% | 11.96 |
| Carbon residue, wt% | 0.35 |
Table 4 catalyst comparative evaluation result of the present invention
Claims (26)
1. the preparation method of a hydrocracking catalyst comprises the steps:
With small crystal grain Y-shaped molecular sieve, amorphous aluminum silicide, aluminium oxide and adhesive mechanical mixture, moulding, then catalyst carrier is made in drying and roasting; Supported active metal component on the catalyst carrier of gained, catalyst is made in drying and roasting;
(1) preparation of fine grain NaY type molecular sieve;
(2) the fine grain NaY type molecular sieve with step (1) gained becomes little crystal grain NH
4NaY;
(3) with (NH
4)
2SiF
6In the aqueous solution to the little crystal grain NH of step (2) gained
4NaY carries out dealumination complement silicon to be processed;
(4) step (3) gained Y zeolite is carried out hydrothermal treatment consists;
(5) with the molecular sieve of aluminium salt and inorganic acid or aqueous solutions of organic acids treatment step (4) gained, then through washing, after the drying, obtain small crystal grain Y-shaped molecular sieve; In described aluminium salt and inorganic acid or the organic acid mixed aqueous solution, the aluminium salinity is with Al
3+Count 0.2～4.0mol/L, inorganic acid or organic acid concentration are with H
+Count 0.2～2.0mol/L; Aluminium salt is with Al
3+Meter and inorganic acid or organic acid are with H
+The mol ratio of meter is 0.2～20;
Wherein the preparation method of fine grain NaY type molecular sieve is as follows in the step (1):
A, preparation directed agents: more than 0 ℃ and under less than 15 ℃ temperature, high alkali deflection aluminium acid sodium solution and waterglass are mixed, then at more than 0 ℃ and under less than 15 ℃ temperature static aging 10～14 hours, make directed agents;
B, preparation gel: under 0 ℃～10 ℃ temperature, the prepared directed agents of waterglass, aluminum sulfate solution, low alkali aluminium acid sodium solution and steps A is mixed, the synthetic liquid that then will obtain is static wearing out 5～10 hours under said temperature, obtains gel; The Al in the directed agents wherein
2O
3Weight accounts for the middle Al that always feeds intake
2O
33wt%～the 10wt% of weight;
C, crystallization: the gel that step B is obtained was 50 ℃～90 ℃ and the Water Under thermal crystallisation that stirs 5～10 hours, then heat up, hydrothermal crystallizing 5～10 hours again under 80 ℃～120 ℃ and the condition that stirs, crystallization obtains fine grain NaY type molecular sieve by filtration, washing, drying.
2. according to preparation method claimed in claim 1, it is characterized in that the described high alkali deflection aluminium acid sodium solution of steps A and waterglass are by Na
2O: Al
2O
3: SiO
2: H
2The mol ratio of O=10～20: 1: 10～20: 300～400 feeds intake; The described waterglass of step B, aluminum sulfate solution, low alkali aluminium acid sodium solution and the prepared directed agents of steps A are pressed Na
2O: Al
2O
3: SiO
2: H
2The mol ratio of O=2～4: 1: 6～12: 150～300 feeds intake.
3. according to preparation method claimed in claim 1, after it is characterized in that in the steps A waterglass and high alkali deflection aluminium acid sodium solution mixed, under mixing temperature, constant temperature stirred 0.5～2 hour, then wore out.
4. according to preparation method claimed in claim 1, after it is characterized in that among the step B that directed agents with waterglass, aluminum sulfate solution, low alkali aluminium acid sodium solution and steps A gained mixes, under mixing temperature, constant temperature stirred 0.5～2 hour, then wore out.
5. according to preparation method claimed in claim 1, when it is characterized in that the described preparation directed agents of steps A, the raw material mixing temperature is 0 ℃～10 ℃, and aging temperature is 0 ℃～10 ℃.
6. according to preparation method claimed in claim 1, it is characterized in that Na in the described high alkali deflection aluminium acid sodium solution of steps A
2O content is 260～320g/L, Al
2O
3Content is 30～50g/L; SiO in steps A and the described waterglass of step B
2Content be 200～300g/L, modulus is 2.8～3.5; Na in the described low alkali aluminium acid sodium solution of step B
2O content is 100～130g/L, Al
2O
3Content is 60～90g/L; Al in the described aluminum sulfate solution of step B
2O
3Content be 80～100g/L.
7. according to preparation method claimed in claim 1, it is characterized in that steps A gained directed agents adds the water purification that accounts for directed agents weight 20%～40% before use.
8. according to preparation method claimed in claim 1, the feeding sequence that it is characterized in that the waterglass described in the step B, aluminum sulfate solution, low alkali aluminium acid sodium solution and steps A gained directed agents is the order adding according to waterglass, aluminum sulfate solution, low alkali aluminium acid sodium solution and steps A gained directed agents.
9. according to preparation method claimed in claim 1, it is characterized in that step B gained gel was warmed up to 50 ℃～90 ℃ with 3～8 ℃/minutes, after the first paragraph crystallization, be warmed up to 80 ℃～120 ℃ with 3～8 ℃/minutes and carry out the second segment crystallization.
10. according to preparation method claimed in claim 1, it is characterized in that step (2) process is as follows: adopting ammonium concentration is the ammonium salt solution of 0.1mol/L～1.0mol/L, it is 50～100 ℃ in temperature, solvent and solute weight ratio is under 8: 1～15: 1 the condition, constant temperature is processed fine grain NaY, time is 0.5～1.5 hour, after filtration, then repeat under these conditions the ammonium exchange, the product that obtains after filtration, stand-by after dry, wherein requiring the weight content of sodium oxide molybdena in the small crystal grain molecular sieve after the exchange of control ammonium is 2.5%～5.0%; Described ammonium salt is one or more in ammonium nitrate, ammonium sulfate, ammonium chloride and the ammonium acetate.
11. according to preparation method claimed in claim 1, it is characterized in that step (3) process is as follows: first the molecular sieve that obtains in the step (2) is pulled an oar in the aqueous solution, solvent and solute weight ratio is 3: 1～10: 1, and temperature is 80～120 ℃, and speed of agitator is 200～400rpm; After temperature reaches to fixed temperature, add 10～60 gram (NH according to per 100 gram Y zeolites
4)
2SiF
6Amount, add 3～30 gram (NH with every 100gY type molecular sieve per hour
4)
2SiF
6Speed add (NH in the slurry
4)
2SiF
6The aqueous solution, add take disposed slurry temperature as 80～120 ℃ under, the constant temperature constant speed stirred 0.5～5 hour, then filtration drying.
12. according to preparation method claimed in claim 1, it is characterized in that the described hydrothermal treatment consists condition of step (4) is as follows: gauge pressure 0.05～0.4MPa, 630～750 ℃ of temperature, 0.5～5 hour processing time.
13. according to preparation method claimed in claim 1, it is characterized in that in the step (5), the weight ratio of aluminium salt and inorganic acid or organic acid mixed solution and molecular sieve is 3: 1～50: 1; Described treatment conditions: 40～120 ℃ of temperature, the time is 0.5～8 hour.
14. according to preparation method claimed in claim 1, it is characterized in that in the step (5), in described aluminium salt and inorganic acid or the organic acid mixed aqueous solution, the aluminium salinity is with Al
3+Count 1.0～2.0mol/L, inorganic acid or organic acid concentration are with H
+Count 0.4～1.0mol/L.
15. according to preparation method claimed in claim 1, it is characterized in that in the step (5), described washing until cleaning solution pH value near neutrality, then under 100～120 ℃ condition dry 3～6 hours.
16., it is characterized in that in the step (5) that described aluminium salt is one or more in alchlor, aluminum nitrate, the aluminum sulfate according to preparation method claimed in claim 1; Inorganic acid or organic acid are one or more in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, the citric acid.
17. according to preparation method claimed in claim 1, it is characterized in that described carrier drying condition is as follows: under 80～150 ℃, carried out 3.0～6.0 hours, roasting condition was as follows: 500 ℃～700 ℃ roastings 2.5～6.0 hours, described catalyst drying condition is as follows: 100 ℃～150 ℃ dryings 1.0～12.0 hours, roasting condition was as follows: 450 ℃～550 ℃ roastings 2.5～6.0 hours.
18. a hydrocracking catalyst comprises hydrogenation active metals component and the carrier that contains small crystal grain Y-shaped molecular sieve, amorphous aluminum silicide, aluminium oxide, wherein said small crystal grain Y-shaped molecular sieve, and its character is as follows: SiO
2/ Al
2O
3Mol ratio is 30.0～150.0, and average grain diameter is 100～700nm; Cell parameter is 2.425～2.433nm, and relative crystallinity is 90%～130%, and crystallization reservation degree is greater than 95%, and specific area is 850～950m
2/ g, pore volume 0.30ml/g～0.50ml/g, meleic acid amount 0.1～0.4mmol/g, B acid/L acid is more than 7.0, sodium oxide content≤0.05wt%; Described crystallization reservation degree is the peak height of 5 characteristic peaks in the X-ray diffracting spectrum of Y zeolite and as foundation, with the peak height of 5 characteristic peaks of small crystal grain Y-shaped molecular sieve and divided by the peak height of 5 characteristic peaks of raw materials used fine grain NaY type molecular sieve and percentage; 5 characteristic peaks of the X-ray diffracting spectrum of Y zeolite are as follows respectively: 2 θ are the corresponding characteristic peaks of 15.8,20.7,24.0,27.4 and 31.8 peak positions.
19. according to the described hydrocracking catalyst of claim 18, it is characterized in that the crystallization reservation degree 98%～120% of described small crystal grain Y-shaped molecular sieve.
20. according to the described hydrocracking catalyst of claim 18, it is characterized in that sodium oxide content≤0.01wt% in the described small crystal grain Y-shaped molecular sieve.
21. according to the described hydrocracking catalyst of claim 18, it is characterized in that described small crystal grain Y-shaped molecular sieve character is as follows: SiO
2/ Al
2O
3Mol ratio 40.0～80.0, relative crystallinity are that 100%～130%, B acid/L acid is more than 8.0, and average grain diameter is 300～500nm, and B acid/L acid is more than 8.0.
22. according to the described hydrocracking catalyst of claim 18, the specific area that it is characterized in that described hydrocracking catalyst is 200～350m
2/ g, pore volume are 0.40～0.65ml/g.
23. according to the described hydrocracking catalyst of claim 18, it is characterized in that described hydrogenation active metals is the metal of group vib and group VIII, the group vib metal is molybdenum and/or tungsten, the metal of group VIII is cobalt and/or nickel; With the weighing scale of catalyst, the group vib metal is take the content of oxide as 10.0%～30.0%, and the group VIII metal is take the content of oxide as 4.0%～8.0%, and the content of carrier is 62%～86%.
24. according to claim 18 or 23 described hydrocracking catalysts, it is characterized in that described carrier of hydrocracking catalyst, with the weighing scale of carrier, comprise 10%～70% amorphous aluminum silicide, 3%～20% small crystal grain Y-shaped molecular sieve and 15%～70% aluminium oxide.
25. according to claim 18 or 24 described hydrocracking catalysts, it is characterized in that SiO in the amorphous aluminum silicide of described carrier
2Weight content be 30%～70%, pore volume is 0.6～1.1ml/g, specific area is 300～500m
2/ g, the weight content of described amorphous aluminum silicide in carrier is 25%～55%.
26. the application of the arbitrary described hydrocracking catalyst of claim 18～25 in hydrocracking process, be used for take the hydrocracking process of voluminous intermediate oil as the purpose product, its hydrocracking operating condition is as follows: reaction temperature is 350～420 ℃, stagnation pressure 8～17MPa, hydrogen to oil volume ratio 600～1500, volume space velocity 0.6～2.0h during liquid
-1
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| CN107304375A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of catalytic diesel oil conversion process catalyst grade matches somebody with somebody process |
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