CN107344721A

CN107344721A - A kind of Modified Zeolite Y and its preparation method and application

Info

Publication number: CN107344721A
Application number: CN201610290039.0A
Authority: CN
Inventors: 刘昶; 曹均丰; 郝文月; 廖杰锋; 杜艳泽; 黄薇; 王凤来; 关明华
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2016-05-05
Filing date: 2016-05-05
Publication date: 2017-11-14
Anticipated expiration: 2036-05-05
Also published as: CN107344721B

Abstract

The present invention discloses a kind of Modified Zeolite Y and its preparation method and application.Its property of the Y type molecular sieve is as follows：Average grain diameter is 2.0 ~ 5.0 μm, relative crystallinity 100% ~ 140%, SiO₂/Al₂O₃Mol ratio is 30 ~ 100, preferably 40 ~ 100, and cell parameter is 2.428 ~ 2.445nm, and bore dia is that the pore volume shared by 2nm ~ 8nm hole is the 80% ~ 95% of total pore volume, preferably 80% ~ 90%.NH₃TPD 0.2 ~ 1.0mmol/g of total acid content, wherein>Strong acid accounts for more than the 75% of total acid content in 250 DEG C, and the pore volume of described Y type molecular sieve is 0.55cm³/g~0.70cm³/ g, specific surface area 700m²/g~1000m²/g.The molecular sieve has the advantages that crystal grain is big, crystallinity is high, high silicon, effective pore sife distribution are more concentrated, heat endurance and hydrothermal stability are good, is suitable for preparing hydrogenation catalyst.

Description

A kind of Modified Zeolite Y and its preparation method and application

Technical field

It is particularly a kind of big crystal grain, highly crystalline the present invention relates to a kind of Modified Zeolite Y and its preparation method and application Y type molecular sieve that degree, high silicon and pore-size distribution are more concentrated and its preparation method and application.

Background technology

Can there are Y types, β types and ZSM in distillate hydrocracking field as the molecular sieve of active component of cracking catalyst Type molecular sieve etc., wherein Y type molecular sieve application are the most universal.The method of industrial production Y type molecular sieve is essentially all using beautiful The directing agent method that GRACE companies of state propose in USP 3639099 and USP 4166099, the crystalline substance of obtained common Y type molecular sieve Generally 1 μm or so of grain, the structure cell of about 300 ~ 400 in each dimension.The Y types for the typical die size being conventionally synthesized Pore size distribution ratio of the molecular screen primary powder bore dia less than 1nm is 15% ~ 20%, and pore size distribution ratio of the bore dia in 1nm ~ 10nm is 45% ~ 50%, bore dia is in the pore size distribution ratio more than 10nm 30% ~ 40%.For macromolecular cracking reaction, it is adapted to raw material reaction And the preferable pore diameter range of product diffusion is 1nm ~ 10nm, although Y type molecular sieve also can moderately be adjusted by follow-up modification Become preferable pore diameter range distribution, but the pore-size distribution of original molecular sieve directly determines the pore diameter range point of successive modified molecular sieve Cloth, and reaming can influence the skeleton structure of molecular sieve, and then influence the activity and stability of molecular sieve.

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..

CN201210168420.1 discloses a kind of synthetic method of NaY molecular sieve；By waterglass, sodium metaaluminate and go from Sub- water mixing, crystallization director is obtained in 0.5 ~ 48.0 hour in 15 ~ 70 DEG C of agings；By crystallization director, waterglass, acid aluminium salt With the well mixed obtained silica-alumina gel of sodium aluminate solution；By silica-alumina gel at 80 ~ 140 DEG C crystallization, crystallization 0.1 ~ 80.0 hour； Peroxide is added into crystallization silica-alumina gel, makes peroxide and the Al in gel₂O₃Mol ratio be 0.05 ~ 20, be further continued for Crystallization obtains for 5 ~ 20 hours.This method does not add any organic or inorganic template, is modified without multiple post processing yet Journey, can directly prepare the Y type molecular sieve of high silica alumina ratio in the short period of time, and gained molecular sieve has more than 80% knot Brilliant degree, silica alumina ratio are not less than 5.8, and mean grain size is between 200 ~ 300nm.Although this method can the higher Y of synthesizing Si-Al Type molecular sieve, but its preparation method is complicated, and zeolite crystal degree is smaller, and a certain amount of peroxide is added in gel, more Add the severity of Zeolite synthesis.

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.

CN101481120A discloses a kind of method that rapid crystallization prepares Y type molecular sieve.This method is using silicon source, aluminium Alusil is made in source, alkali source, and Alusil, oil, surfactant, cosurfactant then are prepared into W/O emulsion systems, Rapid crystallization in reactor is transferred to again.The process employs expensive surfactant to prepare Y type molecular sieve, makes in addition Standby process is complicated so for preparing cost and greatly increases.

CN201510147788.3 discloses Y molecular sieve that a kind of silica alumina ratio is high and second hole is abundant and preparation method thereof. This method includes：Y type molecular sieve is handled into 1 ~ 5h at 300 DEG C ~ 600 DEG C, dry Y type molecular sieve is obtained, is cooled to 200 ~ 600 ℃；In dried over anhydrous environment, it is passed through into dry Y type molecular sieve by the dry gas of dealumination complement silicon agent saturation, reaction 0.5h ~ 7.0h, or in dried over anhydrous environment, while temperature to be at the uniform velocity warming up to 500 ~ 700 DEG C into dry y-type zeolite It is passed through by the dry gas of dealumination complement silicon agent saturation, reacts 0.5h ~ 7.0h, obtain crude product；By crude product at 30 ~ 100 DEG C Alkali process 10min ~ 5h, the solid-liquid mass ratio of alkali process is 1 ~ 50：1, obtain the Y molecular sieve that silica alumina ratio is high and second hole is abundant.

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, can be formed molecular sieve by successive modified processing and be more beneficial for the preferable pore passage structure of macromolecular reaction, energy Second pyrolysis transforming machine meeting of more macromoleculars in molecular sieve is enough provided, it is naphtha that can make macromolecular charging preferential conversion With boat product of coal, oil product structure is effectively adjusted, provides strong support to reduce diesel and gasoline ratio, therefore larger crystal molecular sieve can be handled The heavier raw material of the bigger oil product of molecule, improve macromolecular conversion probability etc. and show more superior performance.

The content of the invention

In order to overcome weak point of the prior art, the invention provides a kind of big crystal grain, crystallinity is high, high silicon, has Y type molecular sieve that effect pore-size distribution is more concentrated and its preparation method and application.The heat endurance of the big crystal grain Modified Zeolite Y It is good with hydrothermal stability.This method preparation flow is simple, environment-friendly low with cost.

The Modified Zeolite Y of the present invention, its property are as follows：

Average grain diameter is 2.0 ~ 5.0 μm, preferably 2.0 ~ 4.5 μm, more preferably 3.0 ~ 4.5 μm, relative crystallinity 100% ~ 140%, SiO₂/Al₂O₃Mol ratio is 30 ~ 100, preferably 40 ~ 100, and cell parameter is 2.428 ~ 2.445nm, bore dia For the pore volume shared by 2nm ~ 8nm hole is total pore volume 80% ~ 95%, preferably 80% ~ 90%.NH₃- TPD total acid contents 0.2 ~ 1.0mmol/g, wherein>Strong acid accounts for more than the 75% of total acid content, preferably 75 ~ 90%, the pore volume of described Y type molecular sieve in 250 DEG C For 0.55cm³/g~0.70cm³/ g, specific surface area 700m²/g~1000m²/g。

In described Y type molecular sieve, Na₂O weight content is below 0.15wt%.

The preparation method of the Y type molecular sieve of the present invention, 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）With（NH₄）₂SiF₆The aqueous solution and step（2）The material of gained is contacted, then filtered and dry；

（4）Existed using the alcoholic solution even application of organosilicon（3）The material of gained, wherein molecular sieve and organosilicon ratio are 10:1 ~30:1；

（5）To step（4）Gained Y type molecular sieve carries out hydro-thermal process；Wherein hydrothermal conditions：Gauge pressure be 0.10 ~ 0.50MPa, temperature are 500 ~ 700 DEG C, and processing time is 0.5 ~ 5.0 hour.

In the inventive method, step（1）The property of described big crystal grain NaY type molecular sieves 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, bore dia be 1nm ~ Pore volume shared by 10nm hole accounts for the 70% ~ 90% of total pore volume, preferably 70% ~ 85%, and relative crystallinity is 110% ~ 150%, structure cell Parameter 2.460nm ~ 2.465nm.

In the inventive method, step（1）Described big crystal grain NaY type molecular sieves, preferable property are as follows：It is than surface 800m²/g~1000m²/ g, total pore volume are 0.30mL/g ~ 0.40mL/g, external surface area 60m²/g~100m²/g。

In the inventive method, step（1）Described big crystal grain NaY type molecular sieves, preferable property are as follows：SiO₂/Al₂O₃ Mol ratio 3.5 ~ 6.5, preferably 4.0 ~ 6.0.

In the inventive method, step（2）The big crystal grain NH of preparation₄The weight content of sodium oxide molybdena is 2.5% ~ 5.0% in NaY.

In the inventive method, step（3）It is by step（2）In obtained material with（NH₄）₂SiF₆The aqueous solution contact, mistake Journey is as follows：First by step（2）In obtained molecular sieve be beaten in aqueous, solvent and solute weight ratio 3：1~8：1, temperature 70 ~100℃；Then, added into slurry（NH₄）₂SiF₆The aqueous solution, 10 ~ 35 grams are added according to every 100 grams of Y molecular sieves（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, then filtration drying, is produced Product.

In the inventive method, step（4）Using the alcoholic solution even application of organosilicon in step（3）Obtain on molecular sieve, Wherein molecular sieve and organosilicon（Benchmark）Mass ratio be 10:1~30:1, ratio of the organosilicon in alcohol is 20 ~ 45wt%, is had Machine silicon can be the one or more in silicon ether, tetraethyl orthosilicate, methyl-silicone oil, ethyl silicon oil, alcohol can be methanol, ethanol or One or more in propyl alcohol.

In the inventive method, step（5）Hydro-thermal process be to use saturated steam processing step（4）In obtained molecule Sieve, treatment conditions：0.05 ~ 0.25MPa of gauge pressure, preferably 0.10 ~ 0.20MPa, 500 ~ 800 DEG C of temperature, preferably 500 ~ 750 DEG C, 0.5 ~ 5.0 hour processing time, preferably 1.0 ~ 3.0 hours.

Step of the present invention（1）The preparation method of middle big crystal grain NaY type molecular sieves, comprises the 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：Hydrothermal crystallizing 12 ~ 24 hours, crystallization at 80 DEG C ~ 120 DEG C and under conditions of stirring by the gel that step I is obtained By filtering, washing, dry, obtain big crystal grain NaY type molecular sieves.

In the inventive method, step I water can be individually added into, and can also together be added with solution.

In the inventive method, in step I, the ratio of the addition of aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali sodium metaaluminate, with Aluminum oxide is calculated as 1：（0.5~0.7）：（0.6~0.8）Provide benchmark.

Application of the above-mentioned Modified Zeolite Y as acidic components in catalyst is prepared.

A kind of catalyst, the catalyst include active component and carrier, and the carrier contains Modified Zeolite Y, described Modified Zeolite Y, its property are as follows：Average grain diameter is 2.0 ~ 5.0 μm, preferably 2.0 ~ 4.5 μm, is more preferably 3.0 ~ 4.5 μm, relative crystallinity 100% ~ 140%, SiO₂/Al₂O₃Mol ratio is 30 ~ 100, preferably 40 ~ 100, and cell parameter is 2.428 ~ 2.445nm, bore dia are that the pore volume shared by 2nm ~ 8nm hole is the 80% ~ 95% of total pore volume, preferably 80% ~ 90%. NH₃- TPD 0.2 ~ 1.0mmol/g of total acid content, wherein>Strong acid accounts for more than the 75% of total acid content, preferably 75 ~ 90% in 250 DEG C, described The pore volume of Y type molecular sieve be 0.55cm³/g~0.70cm³/ g, specific surface area 700m²/g~1000m²/g。

In above-mentioned catalyst, described hydrogenation active component is the metal of vib and group VIII, vib metals For preferably Mu He ∕ or tungsten, the metal of group VIII is preferably Gu He ∕ or nickel.In terms of the weight of catalyst, vib metals（With Oxide meter）Content be 10.0% ~ 20.0%, group VIII metal（In terms of oxide）Content be 4.0% ~ 8.0%.

In above-mentioned catalyst, further contain aluminum oxide in the carrier, on the basis of the weight of catalyst, modified Y types The content of molecular sieve is 40% ~ 60%, preferably 45% ~ 60%, and the content of aluminum oxide is 10% ~ 50%, preferably 15% ~ 50%.

In above-mentioned catalyst, aluminum oxide and amorphous silicon aluminium are further contained in the carrier, using the weight of carrier as base Standard, the content of Modified Zeolite Y is 10% ~ 30%, preferably 10% ~ 25%, and the content of amorphous silica-alumina is 30% ~ 60%, preferably For 30% ~ 55%, the content of aluminum oxide is 10% ~ 60%, preferably 10% ~ 55%.

Directed agents, template, table are added without in reaction system in the preparation process of big crystal grain NaY type molecular sieves of the present invention The additives such as face activating agent, by selecting suitable raw material and optimization preparation process, big crystal grain Y is synthesized using a hydrothermal crystallizing The utilization ratio of type molecular sieve, silicon source and silicon source is high, and technological process is simple, and cost is low.The crystalline substance of Y type molecular sieve prepared by this method Grain granularity reaches 2.0 ~ 5.0 μm, and silica alumina ratio is high, effective pore sife distribution is more concentrated, heat endurance and hydrothermal stability are good.

The inventive method is modified to specific big crystal grain NaY molecular sieve original powder, using less modification procedure and temperature The treatment conditions of sum, the destruction to the skeleton structure of molecular sieve is so not only avoided that, makes framework of molecular sieve structure more homogeneous Stably, and the Y type molecular sieve of big crystal grain can also be made with higher silica alumina ratio, the effective pore sife distribution more concentrated.

The Modified Zeolite Y that the big crystal grain of the present invention, high silicon, effective pore sife distribution are more concentrated suitably is used 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.

Modified molecular screen of the present invention mends silicon processing using two steps, can keep the very feelings of macromolecule sieve crystallinity and stability Condition obtains the high high-performance Y type molecular sieve of silica alumina ratio.The organosilicon of use can be heated point in zeolite-water heat treatment process Solution, there is good reaming effect to the partial pore structure in molecular sieve, while silicon atom can enter the skeleton of molecular sieve In structure, further molecular sieves stabilized skeleton structure, molecular sieve structure cell, the sour structure of modulation molecular sieve and distribution are shunk.

The suitable acidic components as catalyst for distillate hydro-cracking of the Modified Zeolite Y, the hydrocracking catalyst Agent can be used for flexibly producing the high value added products such as high-quality heavy naphtha, boat coal, diesel oil and low BMCI values hydrogenation tail oil, with compared with High catalyst activity and selectivity.

Method of modifying preparation process of the present invention is simple, and production cost is relatively low, and the pollution in production process to environment is small.

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

In the preparation method of big crystal grain NaY type molecular sieves of the present invention, Na in high alkali deflection aluminium acid sodium solution₂O content is 260 ~ 320g/ L, Al₂O₃Content is 30 ~ 50g/L, conventional method can be used to prepare.Na in low alkali aluminium acid sodium solution₂O content is 100 ~ 130g/ L, Al₂O₃Content is 60 ~ 90g/L, conventional method can be used to prepare.Al in aluminum sulfate solution₂O₃Content be 80 ~ 100g/L.Water SiO in glass₂Content be 200 ~ 300g/L, modulus is 2.8 ~ 3.5.

The preparation method of big crystal grain NaY type molecular sieves of the present invention, specifically comprises the following steps：

I, according to Na₂O：Al₂O₃：SiO₂：H₂O=10~15：1：10~20：500 ~ 600 molar ratio, in 20 DEG C ~ 40 DEG C temperature Under degree, 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 and mixed Close uniformly, afterwards, add aluminum sulfate solution and low alkali aluminium acid sodium solution, stir at the temperature disclosed above, generally 0.5 ~ 1.0 hour；Then mixed liquor is enclosed in synthesis reactor, static constant temperature aging, preferably ageing time are 1 ~ 2 hour；

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

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

Step in the inventive method（2）Ammonium salt solution that can be using ammonium concentration as 0.1mol/L ~ 1.0mol/L, it is described One or more of the ammonium salt in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate, it is 50 ~ 100 DEG C in temperature, the solid weight of liquid Than for 8：1~15：Under conditions of 1, constant temperature processing big crystal grain NaY, the time is 0.5 ~ 1.5 hour, filtered, then in above-mentioned bar Repeat ammonium exchange under part, obtained product is filtered, stand-by after drying.Wherein require the big crystal grain point after control ammonium exchange The weight content of sodium oxide molybdena is 2.5% ~ 5.0% in son sieve.

In the inventive method, step（3）It is by step（2）In obtained material with（NH₄）₂SiF₆The aqueous solution contact, mistake Journey is as follows：First by step（2）In obtained molecular sieve be beaten in aqueous, solvent and solute weight ratio 3：1~8：1, temperature 70 ~90℃；Then, added into slurry（NH₄）₂SiF₆The aqueous solution, 10 ~ 35 grams are added according to every 100 grams of Y molecular sieves（NH₄）₂SiF₆ Amount 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, then filtration drying, obtains product.

In the inventive method, step（4）Figure is uniformly sprayed in step using the alcoholic solution of organosilicon（3）Obtain on molecular sieve. Wherein the ratio of molecular sieve and organosilicon is 10:1~30:1, ratio of the organosilicon in alcohol is 20 ~ 45%.Prepare the alcohol of organosilicon Solution, organosilicon is progressively dissolved in alcohol at normal temperatures, it is stand-by after clarification.It is using sprinkling equipment that the organosilicon measured is molten Liquid uniformly sprays figure in step（3）Molecular sieve on.

Step of the present invention（5）It is by step（4）In obtained product hydro-thermal process and obtain.Handled and walked with saturated steam Suddenly（4）In obtained molecular sieve, add step in pipe type water heat-treatment furnace（4）In obtained molecular sieve, treatment conditions：Gauge pressure 0.05 ~ 0.25MPa, preferably 0.10 ~ 0.20MPa, 500 ~ 800 DEG C of temperature, preferably 500 ~ 750 DEG C, processing time 0.5 ~ 5 is small When, preferably 1 ~ 3 hour.

The following examples are used to the present invention be described in more detail, but the scope of the present invention is not limited solely to these embodiments Scope.

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.

LY-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 165mL waterglass, after being well mixed, 42.5mL aluminum sulfate solution and 35.6mL low alkali aluminium acid sodium solutions are sequentially added, it is permanent Temperature stirring 0.5 hour, then by obtained Synthesis liquid static aging 1 hour at the temperature disclosed above, obtain 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, constant temperature stirs Mix crystallization 16 hours, after crystallization terminates, quickly cooled with cold water, and open the synthetic molecular sieve of synthesis reactor taking-up, filtered, Wash and dry, obtain 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 156mL waterglass, after being well mixed, 39.6mL aluminum sulfate solution and 28.5mL low alkali aluminium acid sodium solutions are sequentially added, it is permanent Warm 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 stirring Crystallization 24 hours, after crystallization terminates, is quickly cooled with cold water, and is opened synthesis reactor and taken out synthetic molecular sieve, filtered, wash 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, by 26g Aluminium hydroxide is dissolved in 153g sodium hydroxides and 279mL water, forms A raw materials；Then 525g waterglass is added into A raw materials （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 is with Al₂O₃Meter =16.9 wt%）, then 392g directed agents are added in above-mentioned solution, stirred, then add 191g sodium aluminate solutions （Contain 126g aluminium hydroxides and 96.5g sodium hydroxides）, by above-mentioned solution, quickly stirring is then small in 98.8 DEG C of hydrothermal crystallizings 10 When obtain NaY molecular sieve, sample number into spectrum DLY-1, physico-chemical property is shown in Table 1.

DLY-2：

Molecular sieve is prepared using CN101481120A method.By 0.699g Ludox（40wt%）, 0.156g sodium hydroxides, 0.212g sodium aluminates and 2.94mL water purification are stirred at room temperature uniformly, obtain white gels, then the positive fourth of 2.4g OP10,1.6g Alcohol, 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 High alkali deflection aluminium acid sodium solution is made in 22.5g sodium metaaluminates.Then high alkali deflection aluminium acid sodium solution, mixing are added in 525g waterglass Aging 24 hours at room temperature after 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 0.5mol/L aqueous ammonium nitrate solutions 10 Rise.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 300rpm, Constant temperature stirs 1 hour at 90 DEG C, and then filtering molecular sieves, and stays sample, analyzes Na₂O content；Aforesaid operations are repeated, until Na in molecular sieve₂O content reaches 2.5~5wt%, 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, compile Number it is LYN-2.

Embodiment 4

Weigh 200g LYN-1 molecular sieves to be dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 90 DEG C, and speed of agitator is 300rpm, within the time of 2 hours, 156mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, add 13.6 altogether Gram ammonium hexafluorosilicate, then constant temperature constant speed stir 2 hours, filter, dry；Using the ethanol solution 28g containing 30% tetraethyl orthosilicate Uniformly on molecular sieve of the spray figure after ammonium hexafluorosilicate processing；Then the molecular sieve for loading organosilicon is placed in hydro-thermal process stove Carry out hydro-thermal process, 550 DEG C for the treatment of temperature, 2 hours processing times, processing pressure 0.1MPa.Obtain production code member LYNG-1, property Matter is listed in table 2.

Embodiment 5

Weigh 200g LYN-2 molecular sieves to be dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 80 DEG C, and speed of agitator is 300rpm, within the time of 2 hours, 198mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, add 27.5 altogether Gram ammonium hexafluorosilicate, then constant temperature constant speed stir 2 hours, filter, dry；It is equal using the propanol solution 48g containing 25% methyl-silicone oil Even spray figure is on the molecular sieve after ammonium hexafluorosilicate processing；Then the molecular sieve for loading organosilicon is placed in hydro-thermal process stove Water-filling is heat-treated, 600 DEG C for the treatment of temperature, 1 hour processing time, processing pressure 0.2MPa.Obtain production code member LYNG-2, property It is listed in table 2.

Embodiment 6

Weigh 200g LYN-1 molecular sieves to be dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 90 DEG C, and speed of agitator is 300rpm, within the time of 2 hours, 156mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, add 13.6 altogether Gram ammonium hexafluorosilicate, then constant temperature constant speed stir 2 hours, filter, dry；Using the ethanol solution 50g containing 30% tetraethyl orthosilicate Uniformly on molecular sieve of the spray figure after ammonium hexafluorosilicate processing；Then the molecular sieve for loading organosilicon is placed in hydro-thermal process stove Carry out hydro-thermal process, 600 DEG C for the treatment of temperature, 2 hours processing times, processing pressure 0.1MPa.Obtain production code member LYNG-3, property Matter is listed in table 2.

Embodiment 7

Weigh 200g LYN-2 molecular sieves to be dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 80 DEG C, and speed of agitator is 300rpm, within the time of 2 hours, 198mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, add 27.5 altogether Gram ammonium hexafluorosilicate, then constant temperature constant speed stir 2 hours, filter, dry；Uniformly sprayed using the ethanol solution 59g containing 30% silicon ether Figure is on the molecular sieve after ammonium hexafluorosilicate processing；Then the molecular sieve for loading organosilicon is placed in hydro-thermal process stove and enters water-filling Heat treatment, 650 DEG C for the treatment of temperature, 2 hours processing times, processing pressure 0.2MPa.Production code member LYNG-4 is obtained, property 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 4 into DLYN-1, DLYN-2 and DLYN-3 respectively, repeat the process of embodiment 4, it is obtained Sample, numbering DYNS-1, DYNS-2 and DYNS-3, property are listed in table 2.

Embodiment 8

By 133.3g LYNG-1 molecular sieves（Butt 90wt%）, 57.2g macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m²/ g, butt 70wt%）, 255mL dust technologies（5g HNO₃/ 100ml solution）Mixed grind in roller is put into, adds water, is rolled into Paste, extrusion, extrusion bar are dried 4 hours at 110 DEG C, are then calcined 4 hours at 550 DEG C, obtain carrier FHS-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 CAT-1 is obtained, carrier and catalyst composition are shown in Table 3.

Embodiment 9 ~ 11

As described in Example 8, change LYNG-1 into LYNG-2, LYNG-3 and LYNG-4 respectively respectively, obtain carrier FHS-2, FHS-3 and FHS-4 and catalyst CAT-2, CAT- 3 and CAT-4, carrier and catalyst composition are shown in Table 3.

Comparative example 8 ~ 10

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

Embodiment 12 ~ 15

Respectively table is listed in CAT-1, CAT-2, CAT-3 and CAT-4 processing charging HLCO and conventional VGO inferior, raw material oil nature 4, comparative evaluation's result of Cracking catalyst is listed in table 5 and table 6.

Comparative example 11 ~ 13

Table 4 is listed in, is split with DCAT-1, DCAT-2 and DCAT-3 processing charging HLCO and conventional VGO inferior, raw material oil nature respectively The comparative evaluation's result for changing catalyst is listed in table 5 and table 6.

The property of the NaY type molecular sieves of table 1

Continued 1

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

Continued 2

The carrier of table 3 and catalyst composition

Continued 3

The raw material oil nature of table 4

The comparative evaluation's result of table 5

The comparative evaluation's result of table 6

Data can be seen that from table 5 and table 6 is better than reference molecules sieve series by the performance of the standby catalyst of system with molecular sieve for preparing of the present invention Standby catalyst.

Claims

A kind of 1. Modified Zeolite Y, it is characterised in that：The property of the Modified Zeolite Y 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, relative crystallinity 100% ~ 140%, SiO₂/Al₂O₃Rub , than being 30 ~ 100, preferably 40 ~ 100, cell parameter is 2.428 ~ 2.445nm for you, and bore dia is the hole shared by 2nm ~ 8nm hole Hold for the 80% ~ 95% of total pore volume, preferably 80% ~ 90%, NH₃- TPD 0.2 ~ 1.0mmol/g of total acid content, wherein>Strong acid in 250 DEG C More than the 75% of total acid content, preferably 75 ~ 90% are accounted for, the pore volume of described Y type molecular sieve is 0.55cm³/g~0.70cm³/ g, compare surface Product is 700m²/g~1000m²/g。
2. molecular sieve according to claim 1, it is characterised in that：In described Modified Zeolite Y, Na₂O weight contains Measure as below 0.15wt%.
3. the preparation method of the molecular sieve described in claim 1, it is characterised in that：Comprise 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）With（NH₄）₂SiF₆The aqueous solution and step（2）The material of gained is contacted, then filtered and dry；

（4）Existed using the alcoholic solution even application of organosilicon（3）The material of gained, wherein molecular sieve and organosilicon（Benchmark）Matter Amount ratio is 10:1~30:1；

（5）To step（4）Gained Y type molecular sieve carries out hydro-thermal process；Wherein hydrothermal conditions：Gauge pressure be 0.10 ~ 0.50MPa, temperature are 500 ~ 700 DEG C, and processing time is 0.5 ~ 5.0 hour.
4. according to the method for claim 3, it is characterised in that：Step（1）The property of described big crystal grain NaY type molecular sieves It 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, bore dia be 1nm ~ Pore volume shared by 10nm hole accounts for the 70% ~ 90% of total pore volume, preferably 70% ~ 85%, and relative crystallinity is 110% ~ 150%, structure cell Parameter 2.460nm ~ 2.465nm.
5. according to the method for claim 3, it is characterised in that：Step（1）Described big crystal grain NaY type molecular sieves, compare table Face is 800m²/g~1000m²/ g, total pore volume are 0.30mL/g ~ 0.40mL/g, external surface area 60m²/g~100m²/g。
6. according to the method for claim 3, it is characterised in that：Step（1）Described big crystal grain NaY type molecular sieves, SiO₂/ Al₂O₃Mol ratio 3.5 ~ 6.5, preferably 4.0 ~ 6.0.
7. according to the method for claim 3, it is characterised in that：Step（2）The big crystal grain NH of preparation₄The weight of sodium oxide molybdena in NaY It is 2.5% ~ 5.0% to measure content.
8. according to the method for claim 3, it is characterised in that：Step（3）It is by step（2）In obtained material with （NH₄）₂SiF₆Aqueous solution contact, process is as follows：First by step（2）In obtained molecular sieve be beaten in aqueous, liquid is solid Weight ratio is 3：1~8：1, temperature is 70 ~ 100 DEG C；Then, added into slurry（NH₄）₂SiF₆The aqueous solution, according to every 100 grams of Y Molecular sieve adds 10 ~ 35 grams（NH₄）₂SiF₆Amount add（NH₄）₂SiF₆The aqueous solution, added per hour per 100gY types molecular sieve 3 ~ 30 grams（NH₄）₂SiF₆, add（NH₄）₂SiF₆The aqueous solution using disposed slurry in temperature as at 80 ~ 120 DEG C, stirring 0.5 ~ 5.0 is small When, then filtration drying.
9. according to the method for claim 3, it is characterised in that：Step（4）Existed using the alcoholic solution even application of organosilicon Step（3）Obtain on molecular sieve, wherein molecular sieve and organosilicon（Benchmark）Mass ratio be 10:1~30:1, organosilicon is in alcohol In ratio be 20 ~ 45wt%, organosilicon is the one or more in silicon ether, tetraethyl orthosilicate, methyl-silicone oil, ethyl silicon oil, alcohol It is the one or more in methanol, ethanol or propyl alcohol.
10. according to the method for claim 3, it is characterised in that：Step（5）Hydro-thermal process be to be handled with saturated steam Step（4）In obtained molecular sieve, treatment conditions：0.05 ~ 0.25MPa of gauge pressure, preferably 0.10 ~ 0.20MPa, temperature 500 ~ 800 DEG C, preferably 500 ~ 750 DEG C, preferably 0.5 ~ 5.0 hour processing time, 1.0 ~ 3.0 hours.
11. according to the method for claim 3, 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, 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, under conditions of stirring by waterglass be slowly added into it is high-alkali partially It is well mixed in sodium aluminate solution, afterwards, sequentially adds aluminum sulfate solution and low alkali aluminium acid sodium solution, stir at the temperature disclosed above Mix uniformly；Then constant temperature aging in confined conditions, obtains gel；

II, crystallization：Hydrothermal crystallizing 12 ~ 24 hours, crystallization at 80 DEG C ~ 120 DEG C and under conditions of stirring by the gel that step I is obtained By filtering, washing, dry, obtain big crystal grain NaY type molecular sieves.
12. according to the method for claim 11, it is characterised in that：Step I reclaimed waters are individually added into, or are together added with solution Enter.
13. according to the method for claim 11, 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）.
14. application of the Modified Zeolite Y as acidic components in catalyst is prepared described in claim 1.
15. a kind of hydrogenation catalyst, the hydrogenation catalyst includes active component and carrier, and the carrier contains modified Y type molecules Sieve, it is characterised in that：The Modified Zeolite Y, its property are 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 100% ~ 140%, SiO₂/Al₂O₃Mol ratio is 30 ~ 100, preferably For 40 ~ 100, cell parameter is 2.428 ~ 2.445nm, bore dia be that pore volume shared by 2nm ~ 8nm hole is total pore volume 80% ~ 95%, preferably 80% ~ 90%, NH₃- TPD 0.2 ~ 1.0mmol/g of total acid content, wherein>In 250 DEG C strong acid account for the 75% of total acid content with On, preferably 75 ~ 90%, the pore volume of described Y type molecular sieve is 0.55cm³/g~0.70cm³/ g, specific surface area 700m²/g~ 1000m²/g。
16. catalyst according to claim 15, it is characterised in that：Described hydrogenation active component is vib and the The metal of VIII, vib metals are preferably Mu He ∕ or tungsten, and the metal of group VIII is preferably Gu He ∕ or nickel, with catalysis The weight meter of agent, vib metals（In terms of oxide）Content be 10.0% ~ 20.0%, group VIII metal（With oxide Meter）Content be 4.0% ~ 8.0%.
17. catalyst according to claim 15, it is characterised in that：Further contain aluminum oxide in the carrier, to urge On the basis of the weight of agent, the content of Modified Zeolite Y is 40% ~ 60%, preferably 45% ~ 60%, and the content of aluminum oxide is 10% ~ 50%, preferably 15% ~ 50%.
18. catalyst according to claim 15, it is characterised in that：Further containing aluminum oxide and without fixed in the carrier Type sial, on the basis of the weight of carrier, the content of Modified Zeolite Y is 10% ~ 30%, preferably 10% ~ 25%, amorphous silicon The content of aluminium is 30% ~ 60%, preferably 30% ~ 55%, and the content of aluminum oxide is 10% ~ 60%, preferably 10% ~ 55%.