CN107344721B - A kind of Modified Zeolite Y and its preparation method and application - Google Patents

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

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CN107344721B
CN107344721B CN201610290039.0A CN201610290039A CN107344721B CN 107344721 B CN107344721 B CN 107344721B CN 201610290039 A CN201610290039 A CN 201610290039A CN 107344721 B CN107344721 B CN 107344721B
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molecular sieve
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crystal grain
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organosilicon
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CN107344721A (en
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刘昶
曹均丰
郝文月
廖杰锋
杜艳泽
黄薇
王凤来
关明华
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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    • C01—INORGANIC CHEMISTRY
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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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/Al2O3Molar ratio be 30 ~ 100, preferably 40 ~ 100, cell parameter be 2.428 ~ 2.445nm, bore dia be 2nm ~ 8nm hole shared by Kong Rongwei total pore volume 80% ~ 95%, preferably 80% ~ 90%.NH3- TPD 0.2 ~ 1.0mmol/g of total acid content, wherein strong acid accounts for 75% of total acid content or more in > 250 DEG C, the Kong Rongwei 0.55cm of the Y type molecular sieve3/g~0.70cm3/ g, specific surface area 700m2/g~1000m2/g.The molecular sieve has many advantages, such as that crystal grain is big, crystallinity is high, high silicon, effective pore sife distribution are more concentrated, thermal stability and hydrothermal stability are good, suitable for preparing hydrogenation catalyst.

Description

A kind of Modified Zeolite Y and its preparation method and application
Technical field
It is especially 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 The Y type molecular sieve and its preparation method and application that degree, high silicon and pore-size distribution are more concentrated.
Background technique
Can there are Y type, β type 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 is the most universal.The method of industrial production Y type molecular sieve is essentially all using beauty The directing agent method that GRACE company, state proposes in USP 3639099 and USP 4166099, the crystalline substance of common Y type molecular sieve obtained Generally 1 μm or so of grain, about 300 ~ 400 structure cells in each dimension.The Y type 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 greater than 10nm 30% ~ 40%.For macromolecular cracking reaction, it is suitble to raw material reaction And the ideal pore diameter range of product diffusion is 1nm ~ 10nm, although Y type molecular sieve can also moderately be adjusted by subsequent modification Become ideal 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 will affect 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 sieve.Conventional method is using directing agent method, the chemical ratio of Al to Si (SiO of the Y type molecular sieve of synthesis at present2/ Al2O3) it is 3.5 ~ 5.5, and the high Y type molecular sieve of chemical ratio of Al to Si is obtained, need to add expensive and strong toxicity crown ether Equal organic materials are likely to realize.In addition when preparing Y type molecular sieve, silica alumina ratio is lower, and easier preparation, silica alumina ratio is higher, item Part is harsher, is more difficult to prepare.In the molecular sieve for preparing high silica alumina ratio, its influence factor is more, such as the group of reaction mixture At, preparation method, reactant source, the preparation of directed agents, gel pH 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, obtains crystallization director in aging 0.5 ~ 48.0 hour at 15 ~ 70 DEG C；By crystallization director, waterglass, acid aluminium salt Obtained silica-alumina gel is uniformly mixed with 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 the Al in peroxide and gel2O3Molar ratio be 0.05 ~ 20, be further continued for It obtains within crystallization 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 a relatively short period of time, and gained molecular sieve has 80% or more 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 relatively high Y of synthesizing Si-Al Type molecular sieve, but preparation method is complicated, and zeolite crystal degree is smaller, and a certain amount of peroxide is added in gel, more Increase the severity of Zeolite synthesis.
US3671191 and US3639099 is to synthesize Y type molecular sieve using directing agent method, prepares directed agents first, then makes Standby silica-alumina gel, the directed agents after ageing is added, 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 according to the above method is general Logical Y type molecular sieve, when preparation, need first to synthesize directed agents, and preparation step is longer, higher cost.
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 are then prepared W/O emulsion system, It is transferred to rapid crystallization in reaction kettle again.The process employs expensive surfactants to prepare Y type molecular sieve, in addition make Standby process is complicated, so that preparation cost greatly increases.
CN201510147788.3 discloses that a kind of silica alumina ratio is high and second hole Y molecular sieve abundant and preparation method thereof. This method comprises: obtaining dry Y type molecular sieve, being cooled to 200 ~ 600 Y type molecular sieve in 300 DEG C ~ 600 DEG C 1 ~ 5h of processing ℃；In dried over anhydrous environment, it is passed through the dry gas being saturated by dealumination complement silicon agent into dry Y type molecular sieve, reacts 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 the dry gas being saturated by dealumination complement silicon agent, 0.5h ~ 7.0h is reacted, obtains crude product；By crude product at 30 ~ 100 DEG C Alkali process 10min ~ 5h, the solid-liquid mass ratio of alkali process are 1 ~ 50:1, obtain silica alumina ratio height and second hole Y molecular sieve abundant.
From the point of view of application of the molecular sieve with cracking function during Industrial Catalysis, 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 Energy barrier can just diffuse into molecular sieve pore passage, and specific catalysis reaction occurs, is at this moment adsorbed molecule across molecular sieve crystal Hole and cage diffusion serve it is conclusive.And compared with conventional grain molecular sieve, larger crystal molecular sieve has more Internal surface area, molecular sieve can be made to be formed by successive modified processing and be more advantageous to the ideal cellular structure of macromolecular reaction, energy Second pyrolysis transforming machine meeting of more macromoleculars in molecular sieve is enough provided, macromolecular can be made to feed preferential conversion naphtha With boat product of coal, oil product structure is effectively adjusted, is provided strong support to reduce diesel and gasoline ratio, therefore larger crystal molecular sieve can handle The heavier raw material of the bigger oil product of molecule improves macromolecular conversion probability etc. and shows more superior performance.
Summary of the invention
Place in order to overcome the shortcomings in the prior art the present invention provides a kind of big crystal grain, crystallinity height, high silicon, has The Y type molecular sieve and its preparation method and application that effect pore-size distribution is more concentrated.The thermal stability of the big crystal grain Modified Zeolite Y It is good with hydrothermal stability.This method preparation flow is simple, environmental-friendly and at low cost.
Modified Zeolite Y of the invention, property are as follows:
Average grain diameter is 2.0 ~ 5.0 μm, and preferably 2.0 ~ 4.5 μm, further preferably 3.0 ~ 4.5 μm are opposite to crystallize Spend 100% ~ 140%, SiO2/Al2O3Molar ratio is 30 ~ 100, preferably 40 ~ 100, and cell parameter is 2.428 ~ 2.445nm, Kong Zhi 80% ~ 95% of Kong Rongwei total pore volume shared by hole of the diameter for 2nm ~ 8nm, preferably 80% ~ 90%.NH3- TPD total acid content 0.2 ~ 1.0mmol/g, wherein strong acid accounts for 75% of total acid content or more, preferably 75 ~ 90% in > 250 DEG C, the Kong Rong of the Y type molecular sieve For 0.55cm3/g~0.70cm3/ g, specific surface area 700m2/g~1000m2/g。
In the Y type molecular sieve, Na2The weight content of O is 0.15wt% or less.
The preparation method of Y type molecular sieve of the invention, includes the following steps:
(1) preparation of big crystal grain NaY type molecular sieve；
(2) the resulting big crystal grain NaY type molecular sieve of step (1) is prepared into big crystal grain NH4NaY；
(3) (NH is used4)2SiF6Aqueous solution is contacted with step (2) resulting material, is then filtered and is dried；
(4) using the alcoholic solution even application of organosilicon in (3) resulting material, wherein molecular sieve and organosilicon ratio are 10:1~30:1；
(5) hydro-thermal process is carried out to Y type molecular sieve obtained by step (4)；Wherein hydrothermal conditions: gauge pressure is 0.10 ~ 0.50MPa, temperature are 500 ~ 700 DEG C, and the processing time is 0.5 ~ 5.0 hour.
In the method for the present invention, the property of big crystal grain NaY type molecular sieve described in step (1) is as follows:
Average grain diameter is 2.0 ~ 5.0 μm, preferably 2.0 ~ 4.5 μm, further preferably 3.0 ~ 4.5 μm, and bore dia is Kong Rong shared by the hole of 1nm ~ 10nm accounts for the 70% ~ 90% of total pore volume, preferably 70% ~ 85%, and relative crystallinity is 110% ~ 150%, Cell parameter 2.460nm ~ 2.465nm.
In the method for the present invention, big crystal grain NaY type molecular sieve, preferred property described in step (1) are as follows: specific surface is 800m2/g~1000m2/ g, total pore volume are 0.30mL/g ~ 0.40mL/g, external surface area 60m2/g~100m2/g。
In the method for the present invention, big crystal grain NaY type molecular sieve, preferred property described in step (1) are as follows: SiO2/Al2O3 Molar ratio 3.5 ~ 6.5, preferably 4.0 ~ 6.0.
In the method for the present invention, the big crystal grain NH of step (2) preparation4The weight content of sodium oxide molybdena is 2.5% ~ 5.0% in NaY.
In the method for the present invention, step (3) is by material obtained in step (2) and (NH4)2SiF6Aqueous solution contact, mistake Journey is as follows: being first beaten molecular sieve obtained in step (2) in aqueous solution, solvent and solute weight ratio is 3:1 ~ 8:1, temperature 70 ~100℃；Then, (NH is added into slurry4)2SiF610 ~ 35 grams of (NH are added according to every 100 grams of Y molecular sieves in aqueous solution4)2SiF6Amount be added (NH4)2SiF6Aqueous solution, 3 ~ 30 grams of (NH are added in every 100gY type molecular sieve per hour4)2SiF6, add (NH4)2SiF6Slurry stirs 0.5 ~ 5.0 hour, then filtration drying, is produced in the case where temperature is 80 ~ 120 DEG C after aqueous solution Product.
In the method for the present invention, step (4) is obtained on molecular sieve using the alcoholic solution even application of organosilicon in step (3), Wherein the mass ratio of molecular sieve and organosilicon (benchmark) is 10:1 ~ 30:1, and ratio of the organosilicon in alcohol is 20 ~ 45wt%, is had Machine silicon can be one or more of silicon ether, ethyl orthosilicate, methyl-silicone oil, ethyl silicon oil, alcohol can be methanol, ethyl alcohol or One or more of propyl alcohol.
In the method for the present invention, the hydro-thermal process of step (5) is the molecule obtained in saturated steam processing step (4) 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, it handles the time 0.5 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.
The preparation method of big crystal grain NaY type molecular sieve, includes the following steps: in step (1) of the present invention
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, is slowly added into height for waterglass under stirring conditions It is uniformly mixed in alkali sodium aluminate solution, later, aluminum sulfate solution and low alkali aluminium acid sodium solution is sequentially added, in above-mentioned temperature Under stir evenly；Then constant temperature aging in confined conditions, obtains gel；
II, crystallization: the gel that step I is obtained is at 80 DEG C ~ 120 DEG C and hydrothermal crystallizing 12 ~ 24 hours under conditions of stirring, It is filtered, washed, dried after crystallization, obtain big crystal grain NaY type molecular sieve.
In the method for the present invention, step I water can be individually added into, and can also be added together with solution.
In the method for the present invention, in step I, aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali sodium metaaluminate additional amount ratio, with Aluminium oxide is calculated as 1:(0.5 ~ 0.7): (0.6 ~ 0.8) provides benchmark.
Above-mentioned Modified Zeolite Y is preparing the application in catalyst as acidic components.
A kind of catalyst, the catalyst include active component and carrier, and the carrier contains Modified Zeolite Y, described Modified Zeolite Y, property are as follows: average grain diameter be 2.0 ~ 5.0 μm, preferably 2.0 ~ 4.5 μm, further preferably 3.0 ~ 4.5 μm, relative crystallinity 100% ~ 140%, SiO2/Al2O3Molar ratio is 30 ~ 100, preferably 40 ~ 100, and cell parameter is 2.428 ~ 2.445nm, bore dia be 2nm ~ 8nm hole shared by Kong Rongwei total pore volume 80% ~ 95%, preferably 80% ~ 90%. NH3- TPD 0.2 ~ 1.0mmol/g of total acid content, wherein strong acid accounts for 75% of total acid content or more, preferably 75 ~ 90% in > 250 DEG C, it is described Y type molecular sieve Kong Rongwei 0.55cm3/g~0.70cm3/ g, specific surface area 700m2/g~1000m2/g。
In above-mentioned catalyst, the hydrogenation active component is the metal of group VIB and group VIII, vib metals Preferably Mu is He ∕ or tungsten, the metal of group VIII are preferably Gu He ∕ or nickel.With the poidometer of catalyst, vib metals (with Oxide meter) content be 10.0% ~ 20.0%, the content of group VIII metal (in terms of oxide) is 4.0% ~ 8.0%.
In above-mentioned catalyst, further contain aluminium oxide in the carrier, on the basis of the weight of catalyst, modified Y type The content of molecular sieve is 40% ~ 60%, preferably 45% ~ 60%, and the content of aluminium oxide is 10% ~ 50%, preferably 15% ~ 50%.
In above-mentioned catalyst, aluminium 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 are 10% ~ 30%, preferably 10% ~ 25%, and the content of amorphous silica-alumina is 30% ~ 60%, preferably It is 30% ~ 55%, the content of aluminium oxide is 10% ~ 60%, preferably 10% ~ 55%.
It is added without directed agents, template, table in the reaction system in the preparation process of big crystal grain NaY type molecular sieve of the present invention The additives such as face activating agent synthesize big crystal grain Y using a hydrothermal crystallizing by selecting suitable raw material and optimization preparation process The utilization efficiency of type molecular sieve, silicon source and silicon source is high, and process flow is simple, at low cost.The crystalline substance of the Y type molecular sieve of this method preparation Grain granularity reaches 2.0 ~ 5.0 μm, and silica alumina ratio is high, effective pore sife distribution is more concentrated, thermal stability and hydrothermal stability are good.
The method of the present invention is modified specific big crystal grain NaY molecular sieve original powder, using less modification procedure and temperature The treatment conditions of sum are not only avoided that the destruction to the skeleton structure of molecular sieve in this way, keep framework of molecular sieve structure more uniform And stabilization, and the effective pore sife distribution that the Y type molecular sieve of big crystal grain silica alumina ratio with higher can also be made, more concentrated.
The Modified Zeolite Y that big crystal grain of the invention, high silicon, effective pore sife distribution are more concentrated is suitable for as cracking group Point.Since the larger crystal molecular sieve not only has biggish crystal grain, so that structure cell quantity increases to 1000 ~ 2000 in each dimension It is a, be conducive to macromolecular and cracked, but also there is more preferably pore size distribution range, splitting for reactant can be efficiently controlled Solution degree, and be conducive to product and be diffused in duct, in this way in cracking reaction, can relative increase activated centre, and can So that heavy oil macromolecular is carried out the cracking reaction of suitable degree, had both improved the cracking capability of heavy oil, while reducing coke yield, and urged Agent can show good cracking activity and product selectivity.
Modified molecular screen of the present invention mends silicon processing using two steps, can be in the feelings for keeping very 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 has good reaming to act on the partial pore structure in molecular sieve, while silicon atom is able to enter the skeleton of molecular sieve In structure, further molecular sieves stabilized skeleton structure shrinks molecular sieve structure cell, the sour structure of modulation molecular sieve and distribution.
The Modified Zeolite Y is suitable for the acidic components as catalyst for distillate hydro-cracking, 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 value hydrogenation tail oil, with compared with High catalyst activity and selectivity.
Method of modifying preparation process of the present invention is simple, lower production costs, small pollution of the environment in production process.
Detailed description of the invention
Fig. 1 is the SEM electromicroscopic photograph of 1 gained LY-1 of embodiment；
Fig. 2 is the SEM electromicroscopic photograph of 1 gained DLY-1 of comparative example；
Fig. 3 is the XRD diffraction pattern of 1 gained LY-1 of embodiment.
Specific embodiment
In the preparation method of big crystal grain NaY type molecular sieve of the present invention, Na in high alkali deflection aluminium acid sodium solution2O content be 260 ~ 320g/L, Al2O3Content is 30 ~ 50g/L, and conventional method preparation can be used.Na in low alkali aluminium acid sodium solution2O content be 100 ~ 130g/L, Al2O3Content is 60 ~ 90g/L, and conventional method preparation can be used.Al in aluminum sulfate solution2O3Content be 80 ~ 100g/L.SiO in waterglass2Content be 200 ~ 300g/L, modulus be 2.8 ~ 3.5.
The preparation method of big crystal grain NaY type molecular sieve 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, 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 stirring conditions It is uniformly mixed, later, aluminum sulfate solution and low alkali aluminium acid sodium solution is added, stirs evenly 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 ~ 2 hour；
II, by synthesis mother liquid in confined conditions, using the method for a thermostatic crystallization.Thermostatic crystallization is Refer to crystallization under agitation.Under agitation, the slower speed of gel (generally at 2 ~ 4 DEG C/minute) is warming up to first Under the conditions of 90 DEG C ~ 110 DEG C, and thermostatic crystallization 12 ~ 24 hours at this temperature.It is quickly that synthesis reactor is cooling after crystallization Cooling, is filtered, washed and dried drying, obtains big crystal grain NaY type molecular sieve.
Stirring described in the method for the present invention is generally to use mechanical stirring using conventional stirring means.
Step (2) can be the ammonium salt solution of 0.1mol/L ~ 1.0mol/L with ammonium concentration in the method for the present invention, described Ammonium salt is selected from one of ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate or a variety of, is 50 ~ 100 DEG C in temperature, liquid consolidates weight Under conditions of for 8:1 ~ 15:1, constant temperature handles big crystal grain NaY, and the time is 0.5 ~ 1.5 hour, through filtering, then in above-mentioned item Repeat ammonium exchange under part, obtained product is stand-by after being filtered, being dried.Big crystal grain point after wherein requiring control ammonium exchange The weight content of sodium oxide molybdena is 2.5% ~ 5.0% in son sieve.
In the method for the present invention, step (3) is by material obtained in step (2) and (NH4)2SiF6Aqueous solution contact, mistake Journey is as follows: being first beaten molecular sieve obtained in step (2) in aqueous solution, solvent and solute weight ratio is 3:1 ~ 8:1, temperature 70 ~90℃；Then, (NH is added into slurry4)2SiF610 ~ 35 grams of (NH are added according to every 100 grams of Y molecular sieves in aqueous solution4)2SiF6 Amount be added (NH4)2SiF6Aqueous solution, 3 ~ 30 grams of (NH are added in every 100gY type molecular sieve per hour4)2SiF6, add (NH4)2SiF6Slurry stirs 0.5 ~ 5.0 hour, then filtration drying, obtains product in the case where temperature is 80 ~ 120 DEG C after aqueous solution.
In the method for the present invention, step (4) is uniformly sprayed figure using the alcoholic solution of organosilicon and is obtained on molecular sieve in step (3). Wherein the ratio of molecular sieve and organosilicon is 10:1 ~ 30:1, and ratio of the organosilicon in alcohol is 20 ~ 45%.Prepare the alcohol of organosilicon Organosilicon is gradually dissolved in alcohol by solution at normal temperature, stand-by after clarification.It is using sprinkling equipment that the organosilicon measured is molten Liquid uniformly sprays figure on the molecular sieve of step (3).
Step (5) of the present invention is to obtain product hydro-thermal process obtained in step (4).It is handled and is walked with saturated steam Suddenly molecular sieve obtained in step (4), treatment conditions: gauge pressure are added in molecular sieve obtained in (4) in pipe type water heat-treatment furnace 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 are small When, preferably 1 ~ 3 hour.
Stirring described in the method for the present invention is generally to use mechanical stirring using conventional stirring means.
The following examples are for being described in more detail the present invention, but the scope of the present invention is not limited solely to these embodiments Range.
Analysis method of the present invention: specific surface area, Kong Rong and external surface area, pore size distribution use low temperature liquid nitrogen physisorphtion It measuring, relative crystallinity and cell parameter are measured using X-ray diffraction method, and silica alumina ratio is measured using chemical analysis, point Son sieve grain size using SEM(scanning electron microscope) by the way of measure.
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 sieve 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 method for the present invention.
The preparation of LY-1
(1) preparation of gel: temperature is 25 DEG C, under stirring condition, is slowly added into the high alkali deflection aluminium acid sodium solution of 63mL Enter 165mL waterglass, after mixing, sequentially add the aluminum sulfate solution and 35.6mL low alkali aluminium acid sodium solution of 42.5mL, 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, is quickly cooled down with cold water, and open synthesis reactor and take out synthetic molecular sieve, is passed through It is filtered, washed and dried, obtains product LY-1, product property is shown in Table 1.
The preparation of LY-2:
(1) preparation of gel: temperature is 35 DEG C, under stirring condition, is slowly added into the high alkali deflection aluminium acid sodium solution of 48mL Enter 156mL waterglass, after mixing, sequentially add the aluminum sulfate solution and 28.5mL low alkali aluminium acid sodium solution of 39.6mL, 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 Stirring crystallization 24 hours, after crystallization, is quickly cooled down with cold water, and open synthesis reactor and take out synthetic molecular sieve, is passed through Filter, washing and drying, 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.Specific preparation process are as follows: the preparation of directed agents, it will 26g aluminium hydroxide is dissolved in 153g sodium hydroxide and 279mL water, forms A raw material；Then 525g water glass is added into A raw material Glass (modulus 3.3), after above-mentioned gel is quickly stirred, aging 24 hours at room temperature, for use；
At 37.8 DEG C, to be added in 2223g waterglass (modulus 3.3) aluminum sulfate solution containing 601g (sulfuric acid aluminium content with Al2O3Count=16.9 wt%), then 392g directed agents are added in above-mentioned solution, are stirred evenly, 191g aluminic acid is then added Sodium solution (contains 126g aluminium hydroxide and 96.5g sodium hydroxide), above-mentioned solution is quickly stirred 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, physico-chemical property is shown in Table 1.
DLY-2:
Molecular sieve is prepared using the method for CN101481120A.By 0.699g silica solution (40wt%), 0.156g hydroxide Sodium, 0.212g sodium aluminate 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 hexamethylene, stir evenly, 100 DEG C hydrothermal crystallizing 24 hours, obtain product DLY-2, product property is shown in Table 1.
DLY-3:
The preparation of directed agents takes 153g sodium hydrate solid to be dissolved in 279mL deionized water, after being cooled to room temperature, adds Enter 22.5g sodium metaaluminate and high alkali deflection aluminium acid sodium solution is made.Then high alkali deflection aluminium acid sodium solution is added in 525g waterglass, mixes Aging 24 hours at room temperature after closing uniformly, for use.
In 1547g waterglass stir under sequentially add 720g deionized water, 222.5g low alkali aluminium acid sodium solution and 242g directed agents are fitted into stainless steel cauldron after mixing, 100 DEG C static crystallization 24 hours, then filtered, washed It washs and dries, 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 are weighed, is dissolved in 10 liters of prepared aqueous ammonium nitrate solutions, 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 2.5~5wt%, and the sample number into spectrum after being dried is LYN-1.
Embodiment 3
It changes the big crystal grain NaY molecular sieve LY-1 in embodiment 2 into LY-2, repeats the process of embodiment 2, sample obtained Product, number LYN-2.
Embodiment 4
It weighs 200g LYN-1 molecular sieve to be dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 90 DEG C, speed of agitator 156mL hexafluorosilicic acid aqueous ammonium was added at the uniform velocity into molecular sieve slurry, is added altogether within 2 hours time for 300rpm 13.6 grams of ammonium hexafluorosilicates, then constant temperature constant speed stirs 2 hours, filters, dry；It is molten using the ethyl alcohol containing 30% ethyl orthosilicate Liquid 28g uniformly sprays figure on ammonium hexafluorosilicate treated molecular sieve；Then the molecular sieve for loading organosilicon is placed at hydro-thermal Hydro-thermal process is carried out in reason furnace, 550 DEG C for the treatment of temperature, handles time 2 h, processing pressure 0.1MPa.Obtain product number LYNG-1, property are listed in table 2.
Embodiment 5
It weighs 200g LYN-2 molecular sieve to be dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 80 DEG C, speed of agitator 198mL hexafluorosilicic acid aqueous ammonium was added at the uniform velocity into molecular sieve slurry, is added altogether within 2 hours time for 300rpm 27.5 grams of ammonium hexafluorosilicates, then constant temperature constant speed stirs 2 hours, filters, dry；Using the propanol solution for containing 25% methyl-silicone oil 48g uniformly sprays figure on ammonium hexafluorosilicate treated molecular sieve；Then the molecular sieve for loading organosilicon is placed in hydro-thermal process Hydro-thermal process is carried out in furnace, 600 DEG C for the treatment of temperature, is handled the time 1 hour, processing pressure 0.2MPa.Obtain product number LYNG- 2, property is listed in table 2.
Embodiment 6
It weighs 200g LYN-1 molecular sieve to be dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 90 DEG C, speed of agitator 156mL hexafluorosilicic acid aqueous ammonium was added at the uniform velocity into molecular sieve slurry, is added altogether within 2 hours time for 300rpm 13.6 grams of ammonium hexafluorosilicates, then constant temperature constant speed stirs 2 hours, filters, dry；It is molten using the ethyl alcohol containing 30% ethyl orthosilicate Liquid 50g uniformly sprays figure on ammonium hexafluorosilicate treated molecular sieve；Then the molecular sieve for loading organosilicon is placed at hydro-thermal Hydro-thermal process is carried out in reason furnace, 600 DEG C for the treatment of temperature, handles time 2 h, processing pressure 0.1MPa.Obtain product number LYNG-3, property are listed in table 2.
Embodiment 7
It weighs 200g LYN-2 molecular sieve to be dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 80 DEG C, speed of agitator 198mL hexafluorosilicic acid aqueous ammonium was added at the uniform velocity into molecular sieve slurry, is added altogether within 2 hours time for 300rpm 27.5 grams of ammonium hexafluorosilicates, then constant temperature constant speed stirs 2 hours, filters, dry；It is equal using the ethanol solution 59g containing 30% silicon ether Even spray figure is on ammonium hexafluorosilicate treated molecular sieve；Then by the molecular sieve for loading organosilicon be placed in hydro-thermal process furnace into Row hydro-thermal process, handles time 2 h, processing pressure 0.2MPa by 650 DEG C for the treatment of temperature.Obtain product number LYNG-4, property It is listed in table 2.
Comparative example 2 ~ 4
It changes the big crystal grain NaY molecular sieve LY-1 in embodiment 2 into DLY-1, DLY-2 and DLY-3 respectively, repeats embodiment 2 process, sample obtained, number DLYN-1, DLYN-2 and DLYN-3.
Comparative example 5 ~ 7
It changes the LYN-1 in embodiment 4 into DLYN-1, DLYN-2 and DLYN-3 respectively, repeats the process of embodiment 4, system The sample obtained, number DYNS-1, DYNS-2 and DYNS-3, property are listed in table 2.
Embodiment 8
By 133.3g LYNG-1 molecular sieve (butt 90wt%), 57.2g macroporous aluminium oxide, (hole holds 1.0mL/g, specific surface area 400m2/ g, butt 70wt%), 255mL dust technology (5g HNO3/ 100ml solution) it is put into mixed grind in roller, add water, is rolled into Paste, extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, obtains carrier FHS-1.
Maceration extract room temperature immersion 2 hours of carrier tungstenic and nickel, 120 DEG C drying 4 hours, 500 DEG C of temperature programming roasting 4 Hour, catalyst CAT-1 is obtained, carrier and catalyst composition are shown in Table 3.
Embodiment 9 ~ 11
As described in Example 8, it changes LYNG-1 into LYNG-2, LYNG-3 and LYNG-4 respectively respectively, obtains 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, it changes LYNG-1 into DYNS-1, DYNS-2 and DYNS-3 respectively, carrier DFHS- is made 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 with CAT-1, CAT-2, CAT-3 and CAT-4 processing charging HLCO and routine VGO inferior, raw material oil nature column Table 5 and table 6 are listed in comparative evaluation's result of table 4, Cracking catalyst.
Comparative example 11 ~ 13
Table is listed in DCAT-1, DCAT-2 and DCAT-3 processing charging HLCO inferior and routine VGO, raw material oil nature respectively 4, comparative evaluation's result of Cracking catalyst is listed in table 5 and table 6.
The property of 1 NaY type molecular sieve of table
Continued 1
Note: in table 1, * roasting condition is as follows: roasting 3 hours in 600 DEG C of air；
* the condition of hydro-thermal process is as follows: 650 DEG C steam treatment 1 hour.
The property of 2 Y type molecular sieve of table
Continued 2
3 carrier of table and catalyst composition
Continued 3
4 raw material oil nature of table
5 comparative evaluation's result of table
6 comparative evaluation's result of table
Data can be seen that the performance by the standby catalyst of system with molecular sieve for preparing of the present invention better than reference molecules from table 5 and table 6 Sieve the catalyst of preparation.

Claims (17)

1. a kind of 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, relative crystallinity 100% ~ 140%, SiO2/Al2O3Molar ratio be 30 ~ 100, cell parameter be 2.428 ~ 2.445nm, bore dia are 80% ~ 95%, NH of Kong Rongwei total pore volume shared by the hole of 2nm ~ 8nm3- TPD total acid content 0.2 ~ 1.0mmol/g, wherein strong acid accounts for 75% of total acid content or more in > 250 DEG C, the Kong Rongwei 0.55cm of the Y type molecular sieve3/g~ 0.70cm3/ g, specific surface area 700m2/g~1000m2/g。
2. molecular sieve according to claim 1, it is characterised in that: in the Modified Zeolite Y, Na2The weight of O contains Amount is 0.15wt% or less.
3. the preparation method of molecular sieve described in claim 1, characterized by the following steps:
(1) preparation of big crystal grain NaY type molecular sieve；
(2) the resulting big crystal grain NaY type molecular sieve of step (1) is prepared into big crystal grain NH4NaY；
(3) (NH is used4)2SiF6Aqueous solution is contacted with step (2) resulting material, is then filtered and is dried；
(4) using the alcoholic solution even application of organosilicon in (3) resulting material, wherein molecular sieve and organosilicon are with organosilicon Mass ratio on the basis of quality is 10:1 ~ 30:1；
(5) hydro-thermal process is carried out to Y type molecular sieve obtained by step (4)；Wherein hydrothermal conditions: gauge pressure is 0.10 ~ 0.50MPa, temperature are 500 ~ 700 DEG C, and the processing time is 0.5 ~ 5.0 hour；
Wherein, in step (1) big crystal grain NaY type molecular sieve preparation method, include the following steps:
I, gel is directly prepared: at a temperature of 20 DEG C ~ 40 DEG C, according to Na2O:Al2O3: SiO2: H2O=10 ~ 15:1:10 ~ 20:500 ~ Waterglass is slowly added into high alkali deflection aluminium acid sodium solution is uniformly mixed under stirring conditions by 600 molar ratio, it Afterwards, aluminum sulfate solution and low alkali aluminium acid sodium solution are sequentially added, is stirred evenly at the temperature disclosed above；Then in confined conditions Constant temperature aging, obtains gel；
II, crystallization: the gel that step I is obtained is at 80 DEG C ~ 120 DEG C and hydrothermal crystallizing 12 ~ 24 hours under conditions of stirring, crystallization By being filtered, washed, drying, big crystal grain NaY type molecular sieve is obtained.
4. according to the method described in claim 3, it is characterized by: the property of big crystal grain NaY type molecular sieve described in step (1) As follows: average grain diameter is 2.0 ~ 5.0 μm, and bore dia is that Kong Rong shared by the hole of 1nm ~ 10nm accounts for the 70% ~ 90% of total pore volume, Relative crystallinity is 110% ~ 150%, cell parameter 2.460nm ~ 2.465nm.
5. according to the method described in claim 3, it is characterized by: big crystal grain NaY type molecular sieve described in step (1), compares 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 described in claim 3, it is characterized by: big crystal grain NaY type molecular sieve, SiO described in step (1)2/ Al2O3Molar ratio 3.5 ~ 6.5.
7. according to the method described in claim 3, it is characterized by: the big crystal grain NH of step (2) preparation4The weight of sodium oxide molybdena in NaY Measuring content is 2.5% ~ 5.0%.
8. according to the method described in claim 3, it is characterized by: step (3) be by material obtained in step (2) with (NH4)2SiF6Aqueous solution contact, process is as follows: being first beaten molecular sieve obtained in step (2) in aqueous solution, liquid is solid Weight ratio is 3:1 ~ 8:1, and temperature is 70 ~ 100 DEG C；Then, (NH is added into slurry4)2SiF6Aqueous solution, according to every 100 grams of Y 10 ~ 35 grams of (NH are added in molecular sieve4)2SiF6Amount be added (NH4)2SiF6Aqueous solution, every 100gY type molecular sieve is added per hour 3 ~ 30 grams of (NH4)2SiF6, add (NH4)2SiF6For slurry in the case where temperature is 80 ~ 120 DEG C, stirring 0.5 ~ 5.0 is small after aqueous solution When, then filtration drying.
9. according to the method described in claim 3, it is characterized by: step (4) is existed using the alcoholic solution even application of organosilicon Step (3) obtains on molecular sieve, wherein the mass ratio of molecular sieve and organosilicon on the basis of the quality of organosilicon for 10:1 ~ 30:1, ratio of the organosilicon in alcohol are 20 ~ 45wt%, organosilicon be silicon ether, ethyl orthosilicate, methyl-silicone oil, in ethyl silicon oil One or more, alcohol is one or more of methanol, ethyl alcohol or propyl alcohol.
10. according to the method described in claim 3, it is characterized by: the hydro-thermal process of step (5) is handled with saturated steam Molecular sieve obtained in step (4), treatment conditions: 0.05 ~ 0.25MPa of gauge pressure, handles the time 0.5 ~ 5.0 by 500 ~ 800 DEG C of temperature Hour.
11. according to the method described in claim 3, it is characterized by: water is individually added into step I, or adding together with solution Enter.
12. according to the method described in claim 3, it is characterized by: aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali are inclined in step I The ratio of the additional amount of sodium aluminate, is calculated as 1:(0.5 ~ 0.7 with aluminium oxide): (0.6 ~ 0.8).
13. Modified Zeolite Y described in claim 1 is preparing the application in catalyst as acidic components.
14. a kind of hydrogenation catalyst, the hydrogenation catalyst includes active component and carrier, and the carrier contains modified Y type molecule Sieve, it is characterised in that: the Modified Zeolite Y, property are as follows: average grain diameter is 2.0 ~ 5.0 μm, relative crystallinity 100% ~ 140%, SiO2/Al2O3Molar ratio is 30 ~ 100, and cell parameter is 2.428 ~ 2.445nm, and bore dia is the hole of 2nm ~ 8nm 80% ~ 95%, NH of shared Kong Rongwei total pore volume3- TPD 0.2 ~ 1.0mmol/g of total acid content, wherein strong acid Zhan is total in > 250 DEG C 75% or more of acid amount, the Kong Rongwei 0.55cm of the Y type molecular sieve3/g~0.70cm3/ g, specific surface area 700m2/g~ 1000m2/g。
15. catalyst according to claim 14, it is characterised in that: the hydrogenation active component is group VIB and the The metal of VIII group, vib metals are Mu He ∕ or tungsten, and the metal of group VIII is Gu He ∕ or nickel, with the weight of catalyst Meter, content of the vib metals in terms of oxide are 10.0% ~ 20.0%, and content of the group VIII metal in terms of oxide is 4.0%~8.0%。
16. catalyst according to claim 14, it is characterised in that: further contain aluminium oxide in the carrier, to urge On the basis of the weight of agent, the content of Modified Zeolite Y is 40% ~ 60%, and the content of aluminium oxide is 10% ~ 50%.
17. catalyst according to claim 14, it is characterised in that: further containing aluminium 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%, the content of amorphous silica-alumina is 30% ~ 60%, the content of aluminium oxide is 10% ~ 60%.
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