CN105709797B - A kind of hydrocracking catalyst and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of hydrocracking catalyst and preparation method thereof.The catalyst, as predominant cracking component, suitably as the hydrocracking catalyst for flexibly producing high-quality heavy naphtha, boat coal and diesel oil, has higher activity and selectivity using the Modified Zeolite Y that a kind of big crystal grain, high silicon, effective pore sife distribution are concentrated.

Description

A kind of hydrocracking catalyst and preparation method thereof

Technical field

The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, particularly a kind of flexibly production heavy naphtha, Hydrocracking catalyst of jet fuel and diesel oil and preparation method thereof.

Background technology

Hydrocracking technology be mainly characterized by adaptability to raw material is strong, products scheme flexibly, purpose product selectivity is high, production Quality is good and added value height etc., can directly produce a variety of high-quality oil products（Such as gasoline, jet fuel, diesel oil, oil base is lubricated Plinth oil etc.）With high-quality industrial chemicals（Such as raw materials for production of benzene,toluene,xylene, ethene）.Therefore, with crude quality by The phase of the sustainable growth and new environmental regulation of year variation and market to high quality oil product and high-quality chemical industry raw materials requirement amount It is also increasingly extensive after appearance, the importance day aobvious protrusion of hydrocracking technology, application, it has also become rationally to be provided using limited oil Source, to greatest extent production cleaning oil product and the optimum oil Refining Technologies of high-quality industrial chemicals, it is modern oil refining and oil Oil, change, the fine core combined in work enterprise.

For hydrocracking catalyst, while catalyst activity is paid attention to, it is necessary to consider the selectivity of purpose product, Therefore a relatively reasonable balance must be found in active this contradiction with the selectivity of purpose product of catalyst, with more The performance of catalyst is played well.

US4036739 discloses a kind of method of cracking hydrocarbons raw material production low boiling point hydrocarbon, wherein Y type molecular sieve used Preparation method, when one section is handled at a temperature of 315~899 DEG C, and under conditions of being contacted with least 0.5Psi vapor Between, the cell parameter for making Y type molecular sieve after processing is 2.440~2.464nm；Molecular sieve after processing is subjected to ammonium exchange, obtained It is less than 1wt% product to sodium content；Then it is calcined again once at 315~899 DEG C, obtains cell parameter less than 2.440nm's Y type molecular sieve.The acid site of the Y type molecular sieve obtained using the above method is reduced, and crystallinity declines, containing big in molecular sieve The non-framework aluminum of amount, so that the activity of the hydrocracking catalyst containing this Y type molecular sieve is not high.

US6174429 discloses a kind of hydrocracking catalyst, the catalyst contain at least one acidifying containing aluminium without fixed Shape matrix, a kind of cell parameter are 2.438nm, SiO₂/Al₂O₃Chemical mol ratio is about 8, SiO₂/Al₂O₃Framework mole ratio is 20 The Y type molecular sieve of left and right, at least one metal component of group VIII, at least one metal component of group VIB, auxiliary agent and at least one VIIth A races element.The catalyst has preferably activity and stability, but jet fuel and diesel yield be not high.

Hydrocracking catalyst in the above method uses conventional die size（1μm）Modified Zeolite Y, this is Due to the influence of method of modifying and zeolite crystal size, cause the property of Y type molecular sieve different, so that catalyst performance is deposited In very big difference.

In the prior art, direct synthesis technique refers to without post processing, the Y type molecular sieve that directly prepares of single sintering, one As be NaY type molecular sieves.Conventional method is to use directing agent method, the chemical ratio of Al to Si of the Y type molecular sieve of synthesis at present（SiO₂/ Al₂O₃）For 3.5 ~ 5.5, and the high Y type molecular sieve of chemical ratio of Al to Si is obtained, it is necessary to add expensive and strong toxicity crown ether It is only possible to realize Deng organic material.In addition when preparing Y type molecular sieve, silica alumina ratio is lower, and easier preparation, silica alumina ratio is higher, bar Part is harsher, is more difficult to prepare.When preparing the molecular sieve of high silica alumina ratio, its influence factor is more, such as the group of reactant mixture Into, preparation method, reactant source, the preparation of directed agents, gel acid-base value, crystallization condition etc..

US3671191 and US3639099 is using directing agent method synthesis Y type molecular sieve, prepares directed agents first, then makes Standby silica-alumina gel, the directed agents added after ageing, then carries out crystallization at high temperature.Be respectively adopted in the above method inorganic acid and Aluminium salt is to reduce the basicity of reaction system, so as to improve the silica alumina ratio of product molecule sieve.But what is prepared as stated above is general Logical Y type molecular sieve, need first to synthesize directed agents during preparation, preparation process is longer, and cost is higher.

From the molecular sieve with cracking function from the point of view of the application during Industrial Catalysis, its performance depends primarily on following Two aspects：Selective absorption and reaction.When reactant molecule size is less than molecular sieve aperture and overcomes molecular sieve crystal surface It energy barrier, can just diffuse into molecular sieve pore passage, specific catalytic reaction occurs, at this moment be adsorbed molecule and pass through molecular sieve crystal Hole and cage diffusion serve it is conclusive.And compared with conventional die molecular sieve, larger crystal molecular sieve has more Internal surface area, be more suitable for the pore passage structure of macromolecular reaction, using the teaching of the invention it is possible to provide more two secondary fissures of the macromolecular in molecular sieve Transforming machine meeting is solved, therefore larger crystal molecular sieve can handle the heavier raw material of the bigger oil product of molecule, improve macromolecular conversion probability Etc. show more superior performance.But for larger crystal molecular sieve, particle diameter is bigger, and duct is longer, not only influences The diffusion of reactant, and multiple cracking reaction easily occurs in molecular sieve pore passage for reactant, reduces the selectivity of catalyst.

The content of the invention

In order to overcome weak point of the prior art, the invention provides a kind of hydrocracking catalyst and its preparation side Method.The Modified Zeolite Y conduct that the hydrocracking catalyst is more concentrated using a kind of big crystal grain, high silicon, effective pore sife distribution Predominant cracking component, for flexibly producing high-quality heavy naphtha, boat coal and diesel oil, there is good activity and selectivity.

The hydrocracking catalyst of the present invention, including hydrogenation active metal component and carrier, carrier include modified Y type molecules Sieve, aluminum oxide and amorphous silica-alumina, wherein described Modified Zeolite Y, its property is as follows：Average grain diameter be 2.0 ~ 5.0 μm, preferably 2.0 ~ 4.5 μm, more preferably 3.0 ~ 4.5 μm, relative crystallinity 110% ~ 150%, SiO₂/Al₂O₃Mol ratio For 60 ~ 120, cell parameter is 2.425 ~ 2.435nm, preferably 2.427 ~ 2.434nm, and bore dia is shared by 3nm ~ 7nm hole Pore volume be total pore volume 70% ~ 95%, preferably 75% ~ 90%.

In Modified Zeolite Y of the present invention, non-framework aluminum accounts for the 0.1% ~ 1.0% of total aluminium, preferably 0.1% ~ 0.5%.

In hydrocracking catalyst of the present invention, the pore volume of described Modified Zeolite Y is 0.35cm³/g~0.50cm³/ g, Specific surface area is 800m²/g~980m²/g。

In hydrocracking catalyst of the present invention, infrared 0.1 ~ 0.5mmol/g of total acid of described Modified Zeolite Y.

In hydrocracking catalyst of the present invention, in described Modified Zeolite Y, Na₂O weight content is 0.15wt% Below.

In described hydrocracking catalyst, described carrier, in terms of the weight of carrier, including Modified Zeolite Y Content is 10%~50%, preferably 15%~45%, and the content of aluminum oxide is 20%~85%, preferably 30% ~ 75%, amorphous silica-alumina Content be 5%~30%, preferably 10%~25%.

For described hydrogenation active metals typically using vib and the metal of group VIII, vib metals are preferably molybdenum He ∕ or tungsten, group VIII metal are preferably Gu He ∕ or nickel.In catalyst of the present invention, on the basis of the weight of catalyst, VI B Race's metal（In terms of oxide）Content be 10.0% ~ 30.0%, group VIII metal（In terms of oxide）Content for 4.0% ~ 8.0%。

The specific surface area of hydrocracking catalyst of the present invention is 250~450m²/ g, pore volume are 0.30~0.50ml/g.

The preparation method of hydrocracking catalyst of the present invention, include preparation and the load hydrogenation active metal component of carrier, The preparation process of wherein carrier is as follows：By Modified Zeolite Y, amorphous silica-alumina, aluminum oxide mix, shaping, then dry and Roasting, is made the preparation method of catalyst carrier, wherein Modified Zeolite Y, comprises the following steps：

（1）The preparation of big crystal grain NaY type molecular sieves；

（2）By step（1）The big crystal grain NaY type molecular sieves of gained are prepared into big crystal grain NH₄NaY；

（3）To step（2）Gained Y type molecular sieve carries out hydro-thermal process；Wherein hydrothermal conditions：Gauge pressure be 0.28 ~ 0.50MPa, temperature are 550 ~ 700 DEG C, and processing time is 0.5 ~ 5.0 hour；

（4）With（NH₄）₂SiF₆The aqueous solution and step（3）The material of gained is contacted, then filtered and dry, is made Modified Zeolite Y.

In the preparation process of Modified Zeolite Y used in the present invention, step（1）Described big crystal grain NaY type molecular sieves Property is as follows：

Average grain diameter is 2.0 ~ 5.0 μm, preferably 2.0 ~ 4.5 μm, more preferably 3.0 ~ 4.5 μm, and bore dia is Pore volume shared by 1nm ~ 10nm hole accounts for the 70% ~ 90% of total pore volume, preferably 70% ~ 85%, and relative crystallinity is 110% ~ 150%, Cell parameter 2.460nm ~ 2.465nm.

The NaY type molecular sieves of the present invention, preferable property are as follows：It is 800m than surface²/g~1000m²/ g, total pore volume are 0.30mL/g ~ 0.40mL/g, external surface area 60m²/g~100m²/g。

The NaY type molecular sieves of the present invention, preferable property are as follows：SiO₂/Al₂O₃Mol ratio 3.5 ~ 6.5, preferably 4.0 ~ 6.0。

In the preparation process of Modified Zeolite Y used in the present invention, step（2）The big crystal grain NH of preparation₄Sodium oxide molybdena in NaY Weight content be 2.5% ~ 5.0%.

In the preparation process of Modified Zeolite Y used in the present invention, step（3）Hydro-thermal process be with saturated steam Manage step（2）In obtained molecular sieve, treatment conditions：0.28 ~ 0.50MPa of gauge pressure, preferably 0.3 ~ 0.5MPa, temperature 550 ~ 700 DEG C, preferably 600 ~ 700 DEG C, preferably 0.5 ~ 5.0 hour processing time, 1.0 ~ 3.0 hours.

In the inventive method, step（4）It is by step（3）In obtained material with（NH₄）₂SiF₆The aqueous solution contact, mistake Journey is as follows：Step（3）In obtained molecular sieve be beaten in aqueous, solvent and solute weight ratio 8：1~15：1, temperature is 95 ~ 130 ℃；Added into slurry（NH₄）₂SiF₆The aqueous solution, 35 ~ 80 grams are added according to every 100 grams of Y molecular sieves（NH₄）₂SiF₆Amount add Enter（NH₄）₂SiF₆The aqueous solution, 3 ~ 30 grams can be added per 100gY types molecular sieve per hour（NH₄）₂SiF₆, add（NH₄）₂SiF₆Water Solution using disposed slurry in temperature as at 80 ~ 120 DEG C, stir 0.5 ~ 5.0 hour, then filtration drying, obtains product.

In the preparation process of Modified Zeolite Y used in the present invention, step（1）The preparation method of middle NaY types molecular sieve, bag Include following steps：

I, gel is directly prepared：At a temperature of 20 DEG C ~ 40 DEG C, at a temperature of preferably 25 DEG C ~ 35 DEG C, according to Na₂O：Al₂O₃： SiO₂：H₂O=10~15：1：10~20：500 ~ 600 molar ratio, height is slowly added under conditions of stirring by waterglass It is well mixed in alkali sodium aluminate solution, afterwards, aluminum sulfate solution and low alkali aluminium acid sodium solution is sequentially added, in said temperature Under stir；Then constant temperature aging in confined conditions, obtains gel；

II, crystallization：By step（2）Hydrothermal crystallizing 12 ~ 24 is small at 80 DEG C ~ 120 DEG C and under conditions of stirring for obtained gel When, through filtering, washing, drying after crystallization, obtain big crystal grain NaY type molecular sieves.

In the preparation process of NaY types molecular sieve used in the present invention, step I feeds intake according to following mol ratio, Na₂O： Al₂O₃：SiO₂：H₂O=10~15：1：10~20：500 ~ 600, its reclaimed water can be individually added into, and can also together be added with solution.

In the preparation process of NaY types molecular sieve used in the present invention, in step I, aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali are inclined The ratio of the addition of sodium aluminate, 1 is calculated as with aluminum oxide：（0.5~0.7）：（0.6~0.8）.

In the preparation process of NaY types molecular sieve used in the present invention, step I is added without directed agents, template in reaction system The additives such as agent, surfactant are big using a hydrothermal crystallizing synthesis by selecting suitable raw material and optimization preparation process The utilization ratio of crystal NaY type molecular sieve, silicon source and silicon source is high, and technological process is simple, and cost is low.NaY types prepared by this method The granularity of molecular sieve reaches 2.0 ~ 5.0 μm, and silica alumina ratio is high, effective pore sife distribution is more concentrated, heat endurance and hydrothermally stable Property is good.

The Y type molecular sieve that catalyst of the present invention is more concentrated using big crystal grain, high silicon, effective pore sife distribution is as cracking group Point.Because the larger crystal molecular sieve not only has larger crystal grain so that structure cell quantity increases to 1000 ~ 2000 in each dimension It is individual, be advantageous to macromolecular and cracked, but also with more preferably pore size distribution range, splitting for reactant can be efficiently controlled Solution degree, and be advantageous to product and be diffused in duct, so in cracking reaction, can relative increase activated centre, and can Heavy oil macromolecular is carried out the cracking reaction of suitable degree, both improved the cracking capability of heavy oil, while reduce coke yield, urge Agent can show good cracking activity and product selectivity.The hydrocracking catalyst is especially suitable as flexibly producing excellent Matter heavy naphtha, boat coal and diesel oil, have higher catalyst activity and selectivity.

Catalyst of the present invention is hydrocracked flexibly production industrial chemicals and transportation fuel especially suitable for heavy wax oil, Used hydrocracking operation condition is as follows：Using one-stage serial technological process, 12.0 ~ 20.0MPa of stagnation pressure is reacted, body during liquid 0.5 ~ 2.0h of product air speed^-1, hydrogen to oil volume ratio 1000：1~2000：1,370 ~ 435 DEG C of reaction temperature.

Brief description of the drawings

Fig. 1 is the gained LY-1 of embodiment 1 SEM electromicroscopic photographs；

Fig. 2 is the gained DLY-1 of comparative example 1 SEM electromicroscopic photographs；

Fig. 3 is the gained LY-1 of embodiment 1 XRD diffraction patterns.

Embodiment

Aluminum oxide can use oxygen used in conventional hydrocracking catalyst in carrier of hydrocracking catalyst of the present invention Change aluminium, such as macroporous aluminium oxide and ∕ or small porous aluminum oxide.

Adhesive therefor of the present invention is made up of small porous aluminum oxide and inorganic acid and/or organic acid.Aperture oxidation used Aluminium pore volume is 0.3~0.5mL/g, and specific surface area is 200~400m²/g。

Amorphous silica-alumina used can be prepared by coprecipitation or grafting copolymerization process in catalyst carrier of the present invention, by document It is prepared by middle conventional method.SiO in obtained amorphous silica-alumina₂Weight content be 30%~70%, preferably 35%~65%, The pore volume of amorphous silica-alumina is 0.6~1.1mL/g, preferably 0.8~1.0mL/g, and specific surface area is 300~500m²/ g, preferably For 350~500m²/g。

In the preparation process of Modified Zeolite Y used in the present invention, step（1）Big crystal grain NaY type molecular sieves preparation In method, Na in high alkali deflection aluminium acid sodium solution₂O content is 260 ~ 320g/L, Al₂O₃Content is 30 ~ 50g/L, can use routine side Method is prepared.Na in low alkali aluminium acid sodium solution₂O content is 100 ~ 130g/L, Al₂O₃Content is 60 ~ 90g/L, can use routine side Method is prepared.Al in aluminum sulfate solution₂O₃Content be 80 ~ 100g/L.SiO in waterglass₂Content be 200 ~ 300g/L, modulus For 2.8 ~ 3.5.

In the preparation process of Modified Zeolite Y used in the present invention, step（1）Big crystal grain NaY type molecular sieves preparation Method, specifically comprise the following steps：

I, according to Na₂O：Al₂O₃：SiO₂：H₂O=10~15：1：10~20：500 ~ 600 molar ratio, at 20 DEG C ~ 40 DEG C At a temperature of, at a temperature of preferably 25 ~ 35 DEG C, waterglass is slowly added into high alkali deflection aluminium acid sodium solution under conditions of stirring It is well mixed, afterwards, aluminum sulfate solution and low alkali aluminium acid sodium solution are added, is stirred at the temperature disclosed above, generally 0.5 ~ 1.0 hours；Then mixed liquor is enclosed in synthesis reactor, static constant temperature aging, preferably ageing time are 1.0 ~ 2.0 hours；

II, by synthesis mother liquid in confined conditions, using the method for a thermostatic crystallization.A described thermostatic crystallization is Refer to crystallization under agitation.Under agitation, first by the slower speed of gel（Typically at 2 ~ 4 DEG C/minute）It is warming up to Under the conditions of 90 DEG C ~ 110 DEG C, and thermostatic crystallization 12 ~ 24 hours at this temperature.After crystallization terminates, quickly synthesis reactor is cooled down Cooling, filtered, washing and drying, obtain big crystal grain NaY type molecular sieves.

In the preparation process of Modified Zeolite Y used in the present invention, step（2）Can using ammonium concentration as 0.1mol/L ~ 1.0mol/L ammonium salt solution, one or more of the described ammonium salt in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate, It is 50 ~ 100 DEG C in temperature, solvent and solute weight ratio 8：1~15：Under conditions of 1, constant temperature processing big crystal grain NaY, the time is 0.5 ~ 1.5 Hour, it is filtered, then repeat ammonium exchange under these conditions, obtained product is filtered, stand-by after drying.Wherein The weight content for seeking sodium oxide molybdena in the larger crystal molecular sieve after controlling ammonium exchange is 2.5% ~ 5.0%.

In the preparation process of Modified Zeolite Y used in the present invention, step（3）It is by step（2）In obtained product water It is heat-treated and obtains.With saturated steam processing step（2）In obtained molecular sieve, add step in pipe type water heat-treatment furnace （2）In obtained molecular sieve, treatment conditions：0.28 ~ 0.50MPa of gauge pressure, preferably 0.3 ~ 0.5MPa, 550 ~ 700 DEG C of temperature are excellent Elect 600 ~ 700 DEG C as, 0.5 ~ 5 hour processing time, preferably 1 ~ 3 hour.

In the inventive method, step（4）It is by step（3）In obtained material with（NH₄）₂SiF₆The aqueous solution contact, mistake Journey is as follows：Step（3）In obtained molecular sieve be beaten in aqueous, solvent and solute weight ratio 8：1~15：1, temperature is 95 ~ 130 ℃；Added into slurry（NH₄）₂SiF₆The aqueous solution, 35 ~ 80 grams are added according to every 100 grams of Y molecular sieves（NH₄）₂SiF₆Amount add Enter（NH₄）₂SiF₆The aqueous solution, 3 ~ 30 grams can be added per 100gY types molecular sieve per hour（NH₄）₂SiF₆, add（NH₄）₂SiF₆Water Solution using disposed slurry in temperature as at 80 ~ 120 DEG C, stir 0.5 ~ 5.0 hour, then filtration drying, obtains product.

Stirring described in the inventive method is using conventional stirring means, typically using mechanical agitation.

Detailed process prepared by catalyst carrier for hydrgenating of the present invention is as follows：By Modified Zeolite Y, aluminum oxide, amorphous Sial and adhesive mixing, extruded moulding, then dry and are calcined, be prepared into carrier；Drying can be in 80 DEG C ~ 150 DEG C of temperature Degree is lower to be dried 3~6 hours, and roasting is calcined 2.5~6.0 hours at 500 DEG C~600 DEG C.

Carrier of hydrocracking catalyst of the present invention loads hydrogenation active metal component by conventional methods（Vib and Group VIII metal component such as Co, Ni, Mo, W etc.）, it is prepared into hydrocracking catalyst.Using load side conventional in the prior art Method, preferably infusion process, can be saturation leaching, excessive leaching or complexing leaching, i.e., with the solution impregnation catalyst containing required active component Agent carrier, carrier after dipping are then small in 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 in 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour When, final catalyst is made.

The following examples are used to technical scheme be described in more detail, but the scope of the present invention is not limited solely to this The scope of a little embodiments.

Analysis method of the present invention：Specific surface area, pore volume and external surface area, pore size distribution use low temperature liquid nitrogen physisorphtion Measuring, relative crystallinity and cell parameter are measured using X-ray diffraction method, and silica alumina ratio is measured using chemical analysis, point The grain size of son sieve uses SEM（SEM）Mode determine.

The preparation big crystal grain NaY molecular sieve of the embodiment of the present invention 1 and comparative example 1 prepare feed stock used in DLY-3 molecular sieves Matter is as follows：

High alkali deflection aluminium acid sodium solution：Na₂O content 291g/L, Al₂O₃Content 42g/L；

Low alkali aluminium acid sodium solution：Na₂O content 117g/L, Al₂O₃Content 77g/L；

Aluminum sulfate solution：Al₂O₃Content 90g/L；

Waterglass：SiO₂Content 250g/L, modulus 3.2.

Embodiment 1

The present embodiment is to prepare big crystal grain NaY molecular sieve using the inventive method.

Y-1 preparation

（1）The preparation of gel：Temperature is 25 DEG C, under stirring condition, is slowly added into 63mL high alkali deflection aluminium acid sodium solution Enter 165mL waterglass, after being well mixed, sequentially add 42.5mL aluminum sulfate solution and 35.6mL low alkali aluminium acid sodium solutions, Constant temperature stirs 0.5 hour, then by obtained Synthesis liquid static aging 1 hour at the temperature disclosed above, obtains gel；

（2）Crystallization：Under agitation, the gel in synthesis reactor is raised to 100 DEG C with 2.5 DEG C/minute of heating rate, perseverance Temperature stirring crystallization 16 hours, after crystallization terminates, is quickly cooled with cold water, and is opened synthesis reactor and taken out synthetic molecular sieve, warp It is filtered, washed and dried, obtains product LY-1, product property is shown in Table 1.

LY-2 preparation：

（1）The preparation of gel：Temperature is 35 DEG C, under stirring condition, is slowly added into 48mL high alkali deflection aluminium acid sodium solution Enter 156mL waterglass, after being well mixed, sequentially add 39.6mL aluminum sulfate solution and 28.5mL low alkali aluminium acid sodium solutions, Constant temperature constant speed stirs 1 hour, then by obtained Synthesis liquid static aging 2 hours at the temperature disclosed above, obtains gel；

（2）Crystallization：Under agitation, the gel in synthesis reactor is raised to 110 DEG C with 3 DEG C/minute of heating rate, constant temperature Stir crystallization 24 hours, after crystallization terminates, quickly cooled with cold water, and open synthesis reactor and take out synthetic molecular sieve, pass through Filter, wash and dry, obtain product LY-2, product property is shown in Table 1.

Comparative example 1

This comparative example is to prepare big crystal grain NaY molecular sieve raw material using art methods.

DLY-1：

Using USP 3639099, molecular sieve is prepared using directing agent method.Specifically preparation process is：The preparation of directed agents, will 26g aluminium hydroxides are dissolved in 153g sodium hydroxides and 279mL water, form A raw materials；Then 525g water glass is added into A raw materials Glass（Modulus 3.3）, after above-mentioned gel quickly stirring, aging 24 hours, stand-by at room temperature；

At 37.8 DEG C, to 2223g waterglass（Modulus 3.3）Middle addition aluminum sulfate solution containing 601g（Sulfuric acid aluminium content with Al₂O₃Count=16.9 wt%）, then 392g directed agents are added in above-mentioned solution, stirred, then add 191g aluminic acids Sodium solution（Contain 126g aluminium hydroxides and 96.5g sodium hydroxides）, above-mentioned solution is quickly stirred and then in 98.8 DEG C of hydro-thermal crystalline substances Change 10 hours and obtain NaY molecular sieve, sample number into spectrum DLY-1, product property is shown in Table 1.

DLY-2：

Molecular sieve is prepared using CN101481120A method.By 0.699g Ludox（40wt%）, 0.156g hydroxides Sodium, 0.212g sodium aluminates and 2.94mL water purification are stirred at room temperature uniformly, obtain white gels, and then 2.4g OP10,1.6g be just Butanol, 1.8mL hexamethylenes, stir, and 100 DEG C of hydrothermal crystallizings 24 hours, obtain product DLY-2, product property is shown in Table 1.

DLY-3：

The preparation of directed agents, take 153g sodium hydrate solids to be dissolved in 279mL deionized waters, after being cooled to room temperature, add Enter 22.5g sodium metaaluminates and high alkali deflection aluminium acid sodium solution is made.Then high alkali deflection aluminium acid sodium solution is added in 525g waterglass, is mixed Aging 24 hours at room temperature after closing uniformly, it is stand-by.

In 1547g waterglass stir under sequentially add 720g deionized waters, 222.5g low alkali aluminium acid sodium solutions and 242g directed agents, after being well mixed, it is fitted into stainless steel cauldron, it is then filtered, wash in 100 DEG C of static crystallization 24 hours Wash and dry, obtain product DLY-3, product property is shown in Table 1.

Embodiment 2

Ammonium exchange is carried out to raw material big crystal grain NaY molecular sieve LY-1 first.Compound concentration is that 0.5mol/L ammonium nitrate is water-soluble 10 liters of liquid.2000 grams of small crystal grain NaY molecular sieve is weighed, is dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, speed of agitator is 300rpm, constant temperature stirs 1 hour at 90 DEG C, and then filtering molecular sieves, and stays sample, analyzes Na₂O content；Repeat above-mentioned behaviour Make, until Na in molecular sieve₂O content reaches 2.5~5.0wt%, and it is LYN-1 to obtain dried sample number into spectrum.

Embodiment 3

Change the big crystal grain NaY molecular sieve LY-1 in embodiment 2 into LY-2, repeat the process of embodiment 2, obtained sample Product, numbering LYN-2.

Embodiment 4

Weigh 200g LYN-1 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 590 DEG C, in gauge pressure Handle 2.0 hours under 0.30MPa, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 100 DEG C, speed of agitator 300rpm.Within the time of 2 hours, 386mL ammonium hexafluorosilicates are added at the uniform velocity into molecular sieve slurry The aqueous solution, 38.6 grams of ammonium hexafluorosilicates are added altogether, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member LYNS-1, property are listed in table 2

Embodiment 5

Weigh 200g LYN-1 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 650 DEG C, in gauge pressure 0.4MPa Lower processing 1.0 hours, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, and be rapidly heated stirring, and temperature is 120 DEG C, is stirred Mix rotating speed is 300rpm.Within the time of 2 hours, 676mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, altogether 67.6 grams of ammonium hexafluorosilicates are added, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member LYNS-2, property It is listed in table 2.

Embodiment 6

Weigh 200g LYN-2 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 600 DEG C, in gauge pressure Handle 3.0 hours under 0.45MPa, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 110 DEG C, speed of agitator 300rpm.Within the time of 2 hours, 435mL ammonium hexafluorosilicates are added at the uniform velocity into molecular sieve slurry The aqueous solution, 43.5 grams of ammonium hexafluorosilicates are added altogether, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member LYNS-3, property are listed in table 2.

Embodiment 7

Weigh 200g LYN-2 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 680 DEG C, in gauge pressure 0.3MPa Lower processing 1.5 hours, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, and be rapidly heated stirring, and temperature is 100 DEG C, is stirred Mix rotating speed is 300rpm.Within the time of 2 hours, 723mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, altogether 72.3 grams of ammonium hexafluorosilicates are added, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member LYNS-4, property It is listed in table 2.

Comparative example 2 ~ 4

Change the big crystal grain NaY molecular sieve LY-1 in embodiment 2 into DLY-1, DLY-2 and DLY-3 respectively, repeat embodiment 2 process, obtained sample, numbering DLYN-1, DLYN-2 and DLYN-3.

Comparative example 5 ~ 7

Change the LYN-1 in embodiment 5 into DLYN-1, DLYN-2 and DLYN-3 respectively, repeat the process of embodiment 5, system The sample obtained, numbering DYNS-1, DYNS-2, DYNS-3, property are listed in table 2.

The property of the NaY type molecular sieves of table 1

Production code member	LY-1	LY-2
			Specific surface area, m2/g	897	956
Pore volume, cm3/g	0.35	0.37
			External surface area, m2/g	80	82
Lattice constant, nm	2.465	2.463
			Relative crystallinity, %	118	128
Average crystallite size, μm	3.0	2.5
			SiO2/Al2O3Mol ratio	5.68	5.32
The pore volume that bore dia 1nm ~ 10nm is accounted for accounts for total pore volume, %	78	87
			Relative crystallinity * after roasting, %	95	92
Relative crystallinity * after hydro-thermal process, %	108	115

Continued 1

Production code member	DLY-1	DLY-2	DLY-3
				Specific surface area, m2/g	840	820	738
Pore volume, cm3/g	0.32	0.32	0.30
				External surface area, m2/g	150	132	121
Lattice constant, nm	2.468	2.468	2.472
				Relative crystallinity, %	96	146.7	92
Average crystallite size, μm	0.95	1.80	1.10
				SiO2/Al2O3Mol ratio	4.21	4.35	5.10
The pore volume that bore dia 1nm ~ 10nm is accounted for accounts for total pore volume, %	51	56	43
				Relative crystallinity * after roasting, %	69	81	44
Relative crystallinity * after hydro-thermal process, %	70	70	76

Note：In table 1, * roasting conditions are as follows：It is calcined 3 hours in 600 DEG C of air；

* the condition of hydro-thermal process is as follows：650 DEG C of steam treatments 1 hour.

The property of the Y type molecular sieve of table 2

Production code member	LYNS-1	LYNS-2	LYNS-3	LYNS-4
					Specific surface area, m2/g	965	947	936	926
Pore volume, cm3/g	0.46	0.47	0.46	0.48
					Lattice constant, nm	2.433	2.428	2.430	2.426
Relative crystallinity, %	136	143	140	146
					Average crystallite size, μm	3.0	3.0	3.0	3.0
SiO2/Al2O3Mol ratio	69.8	105.6	88.1	113.6
					The pore volume that bore dia 3nm ~ 7nm is accounted for is total pore volume, %	83	91	89	93
Non-framework aluminum accounts for total aluminium content, %	0.2	0.1	0.2	0.1
					Infrared total acid content, mmol/g	0.42	0.28	0.35	0.24
Na2O, wt%	0.10	0.09	0.10	0.08

Continued 2

Production code member	DYNS-1	DYNS-2	DYNS-3
				Specific surface area, m2/g	569	585	546
Pore volume, cm3/g	0.37	0.36	0.35
				Lattice constant, nm	2.429	2.431	2.430
Relative crystallinity, %	79	81	59
				Average crystallite size, μm	0.95	0.95	1.10
SiO2/Al2O3Mol ratio	23.5	16.9	22.4
				The pore volume that bore dia 3nm ~ 7nm is accounted for is total pore volume, %	36	33	32
Non-framework aluminum accounts for total aluminium content, %	1.8	2.1	4.5
				Infrared total acid content, mmol/g	0.29	0.38	0.77
Na2O, wt%	0.16	0.18	0.22

Embodiment 8

By 100 grams of LYNS-1 molecular sieves（Butt 90wt%）, 64.3 grams of amorphous silica-aluminas（SiO₂Content 20wt%, pore volume 0.85ml/g, specific surface area 370m²/ g, butt 70wt%）, 150 grams of macroporous aluminium oxides（Pore volume 1.0ml/g, specific surface area 400m²/ G, butt 70wt%）, 200 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into roller Mixed grind, add water, be rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, obtains carrier ZS-1。

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst HC-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Embodiment 9

By 50 grams of LYNS-2 molecular sieves（Butt 90wt%）, 50 grams of amorphous silica-aluminas（SiO₂Content 20wt%, pore volume 0.85ml/g, specific surface area 370m²/ g, butt 70wt%）, 214.3 grams of macroporous aluminium oxides（Pore volume 1.0ml/g, specific surface area 400m²/ g, butt 70wt%）, 200 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into stone roller Mixed grind in press, adds water, is rolled into paste, extrusion, and extrusion bar is dried 4 hours at 110 DEG C, is then calcined 4 hours at 550 DEG C, Obtain carrier ZS-2.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst HC-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Embodiment 10 ~ 11

As described in Example 8, change LYNS-1 into LYNS-3, LYNS-4 respectively, carrier ZS-3, ZS-4 is made and urges Agent HC-3 and HC-4, carrier and catalyst composition are shown in Table 3.

Comparative example 8 ~ 10

As described in Example 8, change LYNS-1 into DYNS-1, DYNS-2, DYNS-3 respectively, be made carrier DZS-1, DZS-2, DZS-3 and catalyst DHC-1, DHC-2 and DHC-3, carrier and catalyst composition are shown in Table 3.

Embodiment 12 ~ 15

This embodiment describes by catalyst HC-1, HC-2, HC-3 and HC-4 Activity evaluation of the present invention.In fixed bed Evaluated on hydrogenation test apparatus, appreciation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity during liquid 1.30h^-1, using vacuum distillate as feedstock oil, feedstock property is listed in table 3, and evaluation result is listed in table 4.

Comparative example 11 ~ 13

This comparative example describes catalyst DHC-1, DHC-2 and DHC-3 activity prepared by comparative example carrier of the present invention Evaluation result.Evaluated on fixed bed hydrogenation experimental rig, appreciation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.30h during liquid^-1, using vacuum distillate as feedstock oil, feedstock property is listed in table 4, and evaluation result is listed in Table 5.

The physico-chemical property of the catalyst carrier of table 3 and catalyst

Carrier forms and property
					Numbering	ZS-1	ZS-2	ZS-3	ZS-4
Modified Zeolite Y, wt%	30.0	15.0	30.0	30.0
					Amorphous silica-alumina, wt%	15.0	15.0	15.0	15.0
Macroporous aluminium oxide, wt%	35.0	50.0	35.0	35.0
					Adhesive, wt%	Surplus	Surplus	Surplus	Surplus
Pore volume, mL/g	0.64	0.69	0.66	0.67
					Specific surface area, m2/g	523	440	533	529
Catalyst forms and property
					Numbering	HC-1	HC-2	HC-3	HC-4
WO3, wt%	22.56	23.50	21.92	23.18
					NiO, wt%	5.73	5.96	5.89	5.86
Pore volume, mL/g	0.39	0.44	0.40	0.41
					Specific surface area, m2/g	421	380	423	430

Continued 3

Carrier forms and property
				Numbering	DZS-1	DZS-2	DZS-3
Modified Zeolite Y, wt%	30.0	30.0	30.0
				Amorphous silica-alumina, wt%	15.0	15.0	15.0
Macroporous aluminium oxide, wt%	35.0	35.0	35.0
				Adhesive, wt%	Surplus	Surplus	Surplus
Pore volume, mL/g	0.57	0.59	0.55
				Specific surface area, m2/g	461	464	423
Catalyst forms and property
				Numbering	DHC-1	DHC-2	HC-2
WO3, wt%	22.42	22.53	22.52
				NiO, wt%	5.79	5.69	5.74
Pore volume, mL/g	0.31	0.32	0.29
				Specific surface area, m2/g	336	358	312

The feedstock oil main character of table 4

The comparative evaluation's result of table 5

Catalyst	HC-1	HC-2	HC-3	HC-4
					Feedstock oil	Vacuum distillate	Vacuum distillate	Vacuum distillate	Vacuum distillate
Volume space velocity during liquid, h-1	1.30	1.30	1.30	1.30
					Hydrogen to oil volume ratio	1200:1	1200:1	1200:1	1200:1
React stagnation pressure, MPa	14.7	14.7	14.7	14.7
					Reaction temperature, DEG C	370	374	368	365
Product yield and property
					Heavy naphtha
Yield, wt%	23.1	24.6	23.0	24.3
					Virtue is latent, wt%	61.3	60.3	62.4	63.2
Jet fuel
					Yield, wt%	21.2	20.6	20.7	21.5
Smoke point, mm	28	29	28	28
					Aromatic hydrocarbons, v%	6.3	5.9	6.4	6.2
Diesel oil
					Yield, wt%	19.4	19.9	20.5	18.6
Cetane number	60.3	62.0	60.0	61.1
					Tail oil
Yield, wt%	29.1	29.0	29.9	29.5
					BMCI values	9.7	9.2	9.5	10.3
Chemical hydrogen consumption, wt%	2.35	2.36	2.31	2.21
					Liquid is received, wt%	96.7	96.5	97.3	97.5

Continued 5

Catalyst	DHC-1	DHC-2	DHC-3
				Feedstock oil	Vacuum distillate	Vacuum distillate	Vacuum distillate
Volume space velocity during liquid, h-1	1.30	1.30	1.30
				Hydrogen to oil volume ratio	1200:1	1200:1	1200:1
React stagnation pressure, MPa	14.7	14.7	14.7
				Reaction temperature, DEG C	375	377	380
Product yield and property
				Heavy naphtha
Yield, wt%	22.3	22.8	21.5
				Virtue is latent, wt%	60.0	55.4	52.3
Jet fuel
				Yield, wt%	21.2	21.3	21.5
Smoke point, mm	26	24	23
				Aromatic hydrocarbons, v%	7.7	8.5	10.3
Diesel oil
				Yield, wt%	17.6	19.2	18.5
Cetane number	59.1	58.3	59.3
				Tail oil
Yield, wt%	29.6	28.0	28.5
				BMCI values	12.0	11.0	10.6
Chemical hydrogen consumption, wt%	2.44	2.47	2.52
				Liquid is received, wt%	95.8	95.1	94.6

It can be seen from the evaluation result of table 5 under identical process conditions, during using catalyst of the present invention, scheelite brain The yield and quality of oil, jet fuel and diesel oil are superior to reference catalyst.

Claims (28)

1. a kind of hydrocracking catalyst, including hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y, oxygen Change aluminium and amorphous silica-alumina, wherein described Modified Zeolite Y, its property is as follows：Average grain diameter is 2.0 ~ 5.0 μm, Relative crystallinity 110% ~ 150%, SiO₂/Al₂O₃Mol ratio is 60 ~ 120, and cell parameter is 2.425 ~ 2.435nm, and bore dia is Pore volume shared by 3nm ~ 7nm hole is the 70% ~ 95% of total pore volume.

2. according to the catalyst carrier described in claim 1, it is characterised in that：The crystal grain of the Modified Zeolite Y is averagely straight Footpath is 2.0 ~ 4.5 μm.

3. according to the catalyst carrier described in claim 2, it is characterised in that：The crystal grain of the Modified Zeolite Y is averagely straight Footpath is 3.0 ~ 4.5 μm.

4. according to the catalyst carrier described in claim 1, it is characterised in that：The bore dia of the Modified Zeolite Y is 3nm Pore volume shared by ~ 7nm hole is the 75% ~ 90% of total pore volume.

5. according to the catalyst carrier described in claim 1, it is characterised in that：The Modified Zeolite Y, non-framework aluminum account for always The 0.1% ~ 1.0% of aluminium.

6. according to the catalyst carrier described in claim 5, it is characterised in that：The Modified Zeolite Y, non-framework aluminum account for always The 0.1% ~ 0.5% of aluminium.

7. according to the catalyst described in claim 1, it is characterised in that：The pore volume of the Modified Zeolite Y is 0.35cm³/g~ 0.50cm³/ g, specific surface area 800m²/g~980m²/g。

8. according to the catalyst described in claim 1, it is characterised in that：The infrared total acid 0.1 of the Modified Zeolite Y ~ 0.5mmol/g。

9. according to the catalyst described in claim 1, it is characterised in that：In the Modified Zeolite Y, Na₂O weight content For below 0.15wt%.

10. according to the catalyst described in claim 1, it is characterised in that：Described carrier, in terms of the weight of carrier, including change Property Y type molecular sieve content be 10%~50%, the content of aluminum oxide is 20%~85%, and the content of amorphous silica-alumina is 5%~30%.

11. according to the catalyst described in claim 10, it is characterised in that：Described carrier, in terms of the weight of carrier, including change Property Y type molecular sieve content be 15%~45%, the content of aluminum oxide is 30%~75%, the content of amorphous silica-alumina for 10%~ 25%。

12. according to the catalyst described in claim 1, it is characterised in that：Described hydrogenation active metals are using vib and the The metal of VIII, vib metals be Mu He ∕ or tungsten, group VIII metal is Gu He ∕ or nickel, using the weight of catalyst as Benchmark, using the content that oxide is counted as 10.0% ~ 30.0%, content of the group VIII metal in terms of oxide is vib metals 4.0%~8.0%。

13. according to the catalyst described in claim 1, it is characterised in that：SiO in amorphous silica-alumina used₂Weight content be 30%~70%, the pore volume of amorphous silica-alumina is 0.6~1.1mL/g, and specific surface area is 300~500m²/g。

14. the preparation method of any catalyst of claim 1 ~ 13, include preparation and the load hydrogenation active metals of carrier The preparation process of component, wherein carrier is as follows：Modified Zeolite Y, amorphous silica-alumina, aluminum oxide are mixed, shaping, Ran Hougan Dry and roasting, is made the preparation method of catalyst carrier, wherein Modified Zeolite Y, comprises the following steps：

（1）The preparation of big crystal grain NaY type molecular sieves；

（2）By step（1）The big crystal grain NaY type molecular sieves of gained are prepared into big crystal grain NH₄NaY；

（3）To step（2）Gained Y type molecular sieve carries out hydro-thermal process；Wherein hydrothermal conditions：Gauge pressure be 0.28 ~ 0.50MPa, temperature are 550 ~ 700 DEG C, and processing time is 0.5 ~ 5.0 hour；

（4）With（NH₄）₂SiF₆The aqueous solution and step（3）The material of gained is contacted, then filtered and dry, is made and is modified Y type molecular sieve.

15. in accordance with the method for claim 14, it is characterised in that：Step（1）The property of described big crystal grain NaY type molecular sieves Matter is as follows：

Average grain diameter is 2.0 ~ 5.0 μm, and bore dia is that the pore volume shared by 1nm ~ 10nm hole accounts for the 70% ~ 90% of total pore volume, Relative crystallinity is 110% ~ 150%, cell parameter 2.460nm ~ 2.465nm.

16. in accordance with the method for claim 15, it is characterised in that：Step（1）The crystalline substance of described big crystal grain NaY type molecular sieves Grain average diameter is 2.0 ~ 4.5 μm.

17. in accordance with the method for claim 16, it is characterised in that：Step（1）The crystalline substance of described big crystal grain NaY type molecular sieves Grain average diameter is 3.0 ~ 4.5 μm.

18. in accordance with the method for claim 15, it is characterised in that：Step（1）The hole of described big crystal grain NaY type molecular sieves Pore volume shared by a diameter of 1nm ~ 10nm hole accounts for the 70% ~ 85% of total pore volume.

19. in accordance with the method for claim 14, it is characterised in that：Step（1）The property of the NaY types molecular sieve is as follows： SiO₂/Al₂O₃Mol ratio 3.5 ~ 6.5.

20. in accordance with the method for claim 19, it is characterised in that：Step（1）The property of the NaY types molecular sieve is as follows： SiO₂/Al₂O₃Mol ratio is 4.0 ~ 6.0.

21. according to the method described in claim 14,15 or 19, it is characterised in that：Step（1）The property of the NaY types molecular sieve Matter is as follows：It is 800m than surface²/g~1000m²/ g, total pore volume are 0.30mL/g ~ 0.40mL/g, external surface area 60m²/g~ 100m²/g。

22. in accordance with the method for claim 14, it is characterised in that：Step（2）The big crystal grain NH of preparation₄Sodium oxide molybdena in NaY Weight content is 2.5% ~ 5.0%.

23. in accordance with the method for claim 14, it is characterised in that：Step（3）Hydrothermal conditions it is as follows：Gauge pressure is 0.30 ~ 0.50MPa, temperature are 600 ~ 700 DEG C, and processing time is 1.0 ~ 3.0 hours.

24. in accordance with the method for claim 14, it is characterised in that：Step（4）It is by step（3）In obtained material with （NH₄）₂SiF₆The aqueous solution contact, solvent and solute weight ratio 8：1~15：1, temperature is 95 ~ 130 DEG C, is added by every 100 grams of Y molecular sieves Enter 35 ~ 80 grams（NH₄）₂SiF₆Amount add（NH₄）₂SiF₆The aqueous solution, add 3 ~ 30 grams per 100gY types molecular sieve per hour （NH₄）₂SiF₆, add（NH₄）₂SiF₆The aqueous solution using disposed slurry in temperature as at 80 ~ 120 DEG C, stir 0.5 ~ 5.0 hour.

25. in accordance with the method for claim 14, it is characterised in that：Step（1）The preparation side of middle big crystal grain NaY type molecular sieves Method, comprise the following steps：

I, at a temperature of 20 DEG C ~ 40 DEG C, according to Na₂O：Al₂O₃：SiO₂：H₂O=10~15：1：10~20：500 ~ 600 feed intake mole Than waterglass is slowly added into high alkali deflection aluminium acid sodium solution under conditions of stirring and is well mixed, afterwards, sequentially adds sulphur Sour aluminum solutions and low alkali aluminium acid sodium solution, stir at the temperature disclosed above；Then constant temperature aging in confined conditions, is obtained Gel；

II, hydrothermal crystallizing 12 ~ 24 hours by the gel that step I is obtained at 80 DEG C ~ 120 DEG C and under conditions of stirring, are passed through after crystallization Filtering, washing, dry, obtain big crystal grain NaY type molecular sieves.

26. in accordance with the method for claim 25, it is characterised in that：In step I, aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali The ratio of the addition of sodium metaaluminate, 1 is calculated as with aluminum oxide：（0.5~0.7）：（0.6~0.8）.

27. in accordance with the method for claim 25, it is characterised in that：In step I, in described high alkali deflection aluminium acid sodium solution Na₂O content is 260 ~ 320g/L, Al₂O₃Content is 30 ~ 50g/L；Na in described low alkali aluminium acid sodium solution₂O content is 100 ~ 130g/L, Al₂O₃Content is 60 ~ 90g/L, Al in described aluminum sulfate solution₂O₃Content be 80 ~ 100g/L；Described water SiO in glass₂Content be 200 ~ 300g/L, modulus is 2.8 ~ 3.5.

28. in accordance with the method for claim 25, it is characterised in that：In step II, under agitation, by temperature with 2 ~ 4 DEG C/minute it is warming up to crystallization temperature i.e. 80 DEG C ~ 120 DEG C.