CN107973314B - A kind of phosphorous and rare earth Y molecular sieve and preparation method thereof - Google Patents

A kind of phosphorous and rare earth Y molecular sieve and preparation method thereof Download PDF

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CN107973314B
CN107973314B CN201610920506.3A CN201610920506A CN107973314B CN 107973314 B CN107973314 B CN 107973314B CN 201610920506 A CN201610920506 A CN 201610920506A CN 107973314 B CN107973314 B CN 107973314B
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acid
molecular sieve
weight
rare earth
ratio
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CN107973314A (en
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庄立
刘建强
欧阳颖
罗一斌
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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China Petrochemical Corp
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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
    • C01B39/026—After-treatment
    • 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
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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

Abstract

Present disclose provides a kind of phosphorous and rare earth Y molecular sieves and preparation method thereof, and the cell parameter of the molecular sieve is 24.35-24.55 angstroms, with P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.3-10.0 weight %；With RE2O3It counts and on the basis of the dry weight of molecular sieve, the content of rare earth of the molecular sieve is 0.5-19 weight %；The Al distribution parameter D of the molecular sieve meets: 0.4≤D≤0.9；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 25%-65%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 65-78%, and the ratio between B acid acid amount and L acid acid amount are 21-98.The molecular sieve that the disclosure provides prepares catalyst as active component, and when reacting for residual oil cracking with excellent heavy oil conversion performance and higher yield of gasoline, low coke yield, olefin(e) centent is low in gasoline.

Description

A kind of phosphorous and rare earth Y molecular sieve and preparation method thereof
Technical field
This disclosure relates to a kind of phosphorous and rare earth Y molecular sieve and preparation method thereof.
Background technique
Molecular sieve is due to being widely used in catalysis, absorption with Shape-selective, higher specific surface and stronger acidity With separation etc. fields.Y molecular sieve (HY, REY, USY) is since the sixties in last century of use for the first time, just always catalytic cracking (FCC) the chief active constituent element of catalyst.However, the polycyclic compound content with the aggravation of crude oil heaviness, in FCC feedstock It dramatically increases, diffusivity of the FCC feedstock in molecular sieve pore passage is but remarkably decreased.And the Y molecule as predominant cracking group member Mesh size only has 0.74nm, is used to the heavy ends such as process residual oils, and the accessibility of catalyst active center will become wherein institute Major obstacle containing polycyclic compound (such as polycyclic aromatic hydrocarbon, polycyclic ring alkane) cracking.Simultaneously as molecular sieve outer surface acidity Presence so that cannot enter duct heavy oil molecules surface occur without selection react, influence product distribution.
Poromerics aperture is smaller, surface has more polyoxybiontic weakness in order to overcome, surface Silicon-rich and rich in mesoporous The synthesis of catalysis material is increasingly subject to the attention of people.
Simultaneously as the limitation that environmental regulation forms vehicle fuel is increasingly stringent, such as national environmental protection portion in 2011 " motor petrol hazard substance control standard (fourth, fifth stage) " formulated, it is desirable that olefin(e) centent in fourth stage gasoline≤ 28v%, olefin(e) centent≤25v% in the 5th stage gasoline.In order to meet environmental requirements, exploitation reduces the catalyst of olefin(e) centent Also seem very urgent.
A kind of preparation side of the Y molecular sieve of containing mesopore is disclosed in United States Patent (USP) US5,069,890 and US5,087,348 Method is mainly comprised the processes of using commercially available USY as raw material, in the atmosphere of 100% vapor, is handled for 24 hours at 760 DEG C.This method Obtained Y molecular sieve mesopore volume increases to 0.14mL/g by 0.02mL/g, but crystallinity drops to 70% by 100%, compares table Area is by 683m2/ g is reduced to 456m2/ g, sour density more drop to 6% by 28.9%.
United States Patent (USP) US5 is original with HY or USY in the method for the Y molecular sieves of 601,798 disclosed preparation containing mesopores Material, is placed in autoclave and NH4NO3Solution or NH4NO3With HNO3Mixed solution mix, 115 DEG C -250 DEG C at a temperature of 2h-20h is handled, the mesopore volume of obtained Y molecular sieve is up to 0.2mL/g-0.6mL/g, but crystallinity and specific surface area have It is remarkably decreased.
Chinese patent CN101722022 discloses a kind of alkali treatment modifying method of Y molecular sieve, including according to molecular sieve (butt): highly basic: distilled water=(0.1-2): (0.05-2): Y molecular sieve and strong alkali aqueous solution are beaten by the mass ratio of (4-15) It is uniformly mixed, the alkali process 0.1-24h at 0-120 DEG C, obtained molecular sieve has higher N compared with parent Y molecular sieve2 Adsorbance.
The method that skeleton rich silicon Y molecular sieve is prepared disclosed in Chinese patent CN 101723399, first with lye to NaY points Son sieve carries out desiliconization pretreatment, then carries out ammonium exchange, dealumination complement silicon processing, obtained Y molecular sieve to the molecular sieve after alkali process It is mesoporous to increased.
Chinese patent CN103172082 discloses a kind of preparation method of the Y molecular sieve of containing mesopore, first to sodium form Y points Son sieve carries out ammonium exchange, handles followed by aqueous solutions of organic acids, is carrying out NaOH processing to the molecular sieve after acid processing, most It is handled afterwards using aqueous ammonium nitrate solution, obtains the Y molecular sieve of containing mesopore.Obtained Y molecular sieve, micropore rich in are mesoporous Pore volume can arrive 0.5mL/g-1.5mL/g.
Chinese patent CN104760973 discloses a kind of Y molecular sieve and preparation method thereof of mesoporous content of superelevation, first will Y-type zeolite pre-processes 1-5h at 300-600 DEG C；It is cooled to 200-600 DEG C；In dried over anhydrous environment, to by pre-processing Y-type zeolite in be passed through by dealumination complement silicon be saturated dry gas, react 0.5-7h, obtain crude product；Or in dried over anhydrous ring Under border, while temperature to be at the uniform velocity warming up to 250-700 DEG C, satisfied to by being passed through in pretreated y-type zeolite by dealumination complement silicon The dry gas of sum reacts 0.5-7h, obtains crude product；Crude product carries out sour processing；Alkali is carried out to acid treated crude product Processing, obtains Y molecular sieve.Y molecular sieve made from this method has the mesoporous content of superelevation, but micro pore volume is lower.
United States Patent (USP) USP5037531 discloses a kind of catalytic cracking catalyst, the catalyst contain using aluminium exchange and it is dilute The framework dealumination y-type zeolite ingredient of soil exchange, the gasoline selective having had.
Chinese patent CN1284403A discloses a kind of rare-earth Y molecular sieve and preparation method thereof.The opposite knot of the molecular sieve For brilliant degree in 65%-85%, the percentage that second level pore volume accounts for total pore volume is 20%-80%.It utilizes Na2O content 2.5-8 weight The rare-earth Y molecular sieve for measuring % is then dry with a kind of siliceous solution dipping, so that the rare-earth Y molecular sieve contains 1-15 weight % Dipping silicon (with SiO2Meter), then by gained dipping silicon rare-earth Y molecular sieve in water vapour 500-850 DEG C of hydrothermal calcine 0.5-30 hours.Rare earth exchanged Y zeolite heavy oil conversion performance with higher is suitble to process residual oils.
Chinese patent CN1436728A discloses a kind of preparation method of hyperastable Y-type RE molecular sieve, is to be with NaY molecular sieve Raw material containing oxalic acid or oxalates and its mixture in chemical dealuminization complexing agent, while introducing in the chemical dealuminization reaction later period dilute Native ion forms rare-earth precipitation, using hydro-thermal process, realizes super stabilizing and introduces the purpose of rare earth ion and rare earth oxide.
Chinese patent CN100577566C discloses a kind of phosphorous and rare earth Y molecular sieve and preparation method thereof, with silicon NaY molecular sieve of the aluminium than >=4.5 is reacted at 60-95 DEG C with the aqueous solution of aqueous solution and phosphorus aluminium modifying agent containing rare earth ion After 10-120min, filtering, elution obtain filter cake, by filter cake at 450-800 DEG C, ambiance be 10-100 volume % water steam 0.4-4h is handled under gas atmosphere.
Summary of the invention
Purpose of this disclosure is to provide a kind of phosphorous and rare earth Y molecular sieve and preparation method thereof, point that the disclosure provides Son sieve prepares catalyst as active component, when reacting for residual oil cracking with excellent heavy oil conversion performance and higher Yield of gasoline, low coke yield, olefin(e) centent is low in gasoline.
To achieve the goals above, the disclosure provides a kind of phosphorous and rare earth Y molecular sieve, the cell parameter of the molecular sieve It is 24.35-24.55 angstroms, with P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.3- 10.0 weight %；With RE2O3It counts and on the basis of the dry weight of molecular sieve, the content of rare earth of the molecular sieve is that 0.5-19 is weighed Measure %；The Al distribution parameter D of the molecular sieve meets: 0.4≤D≤0.9, wherein D=Al (S)/Al (C), Al (S) expression are adopted The inside H in crystal face edge of the zeolite crystal measured with TEM-EDS method is apart from interior any aluminium for being greater than 100 square nanometers regions Content, Al (C) indicate that the outside H distance of the geometric center of crystal face described in the zeolite crystal using the measurement of TEM-EDS method is interior and appoint Meaning is greater than the aluminium content in 100 square nanometers regions, wherein the H is that the crystal face edge point arrives the crystal face geometric center distance 10%；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 25%-65%；The strong acid acid amount of the molecular sieve accounts for The ratio of total acid content is 65-78%, and the ratio between B acid acid amount and L acid acid amount are 21-98.
Preferably, the cell parameter of the molecular sieve is 24.40-24.52 angstroms；With P2O5It counts and with the dry basis of molecular sieve On the basis of amount, the phosphorus content of the molecular sieve is 1-8 weight %；With RE2O3Count and on the basis of the dry weight of molecular sieve, institute The content of rare earth for stating molecular sieve is 3-16 weight %；The Al distribution parameter D of the molecular sieve meets: 0.55≤D≤0.8；It is described The ratio that the mesopore volume of molecular sieve accounts for total pore volume is 30%-61%；The strong acid acid amount of the molecular sieve accounts for the ratio of total acid content Example is 65-75%, and the ratio between B acid acid amount and L acid acid amount are 35-75.
Preferably, the rare earth is selected from least one of lanthanum, cerium, praseodymium and neodymium.
Preferably, it is described it is mesoporous for aperture be greater than 2 nanometers of molecular sieve pore passages less than 100 nanometers；The molecular sieve it is strong Sour amount accounts for the ratio of total acid content using NH3- TPD method measures, and the acid site of the strong acid is NH3Desorption temperature is greater than Acid site corresponding to 300 DEG C；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
The disclosure also provides a kind of preparation method of phosphorous provided by the disclosure and rare earth Y molecular sieve, the preparation side Method includes: a, NaY molecular sieve is carried out ammonium exchange processing, and after being filtered and washed, obtains ammonium exchange molecular sieve；Wherein, It is counted by sodium oxide molybdena and on the basis of the dry weight of ammonium exchange molecular sieve, the sodium oxide content of ammonium exchange molecular sieve is small In 5 weight %；B, gained ammonium exchange molecular sieve in step a is subjected in steam atmosphere the first hydrothermal calcine processing, obtained Water roasts molecular sieve；C, gained water roasting molecular sieve in step b is carried out first in the acid solution being made of organic acid and inorganic acid Dealumination treatment, and after being filtered and washed, obtain the first dealuminzation molecular sieve；D, by the first dealuminzation molecule obtained in step c Sieve carries out alkali process in inorganic alkali solution, and after being filtered and washed, obtains alkali process molecular sieve；E, by institute in step d Alkali process molecular sieve is obtained to carry out at the second dealuminzation in the Compound-acid dealuminzation agent solution being made of fluosilicic acid, organic acid and inorganic acid Reason, and after being filtered and washed, obtain the second dealuminzation molecular sieve；F, the second dealuminzation molecular sieve of gained in step e is being contained Impregnation is carried out in the dipping solution of phosphorus-containing compound and compounds containing rare earth, and is filtered, washed and in vapor gas After carrying out the second hydrothermal calcine processing in atmosphere, described phosphorous and rare earth Y molecular sieve is obtained.
Preferably, the organic acid in acid solution described in step c is selected from ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulphur At least one of base salicylic acid, inorganic acid are selected from least one of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the condition of the first dealumination treatment described in step c includes: with the molecular sieve of dry basis, organic acid Weight ratio with inorganic acid is 1:(0.03-0.3): (0.02-0.4)；First dealumination treatment temperature is 25-100 DEG C, and first is de- The aluminium processing time is 0.5-6 hours.
Preferably, the condition of the first dealumination treatment described in step c includes: with the molecular sieve of dry basis, organic acid Weight ratio with inorganic acid is 1:(0.05-0.25): (0.05-0.25).
Preferably, inorganic alkali solution described in step d is selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide At least one of solution and ammonium hydroxide.
Preferably, the condition of alkali process described in step d includes: the weight with the molecular sieve of dry basis and inorganic base The ratio between be 1:(0.02-0.6)；Alkali purification temp is 25-100 DEG C, and the alkali process time is 0.5-6 hours.
Preferably, organic acid described in Compound-acid dealuminzation agent solution described in step e is selected from ethylenediamine tetra-acetic acid, grass At least one of acid, citric acid and sulfosalicylic acid, inorganic acid are selected from least one of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the condition of the second dealumination treatment described in step e include: with the molecular sieve of dry basis, fluosilicic acid, The weight ratio of organic acid and inorganic acid is 1:(0.03-0.3): (0.05-0.3): (0.05-0.25)；Second dealumination treatment temperature Degree is 25-100 DEG C, and the second dealumination treatment time was 0.5-6 hours.
Preferably, the condition of the second dealumination treatment described in step e include: with the molecular sieve of dry basis, fluosilicic acid, The weight ratio of organic acid and inorganic acid is 1:(0.035-0.2): (0.06-0.2): (0.1-0.2).
Preferably, phosphorus-containing compound described in step f is in phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate At least one, the compounds containing rare earth be selected from chlorate and/or nitric acid containing at least one of lanthanum, cerium, praseodymium and neodymium Salt.
Preferably, the condition of impregnation described in step f includes: with P2O5The phosphorus-containing compound of meter, with RE2O3Meter Compounds containing rare earth and with the weight ratio of the molecular sieve of dry basis be (0.001-0.1): (0.11-0.32): 1, the leaching Stain solution with the weight ratio of the molecular sieve of dry basis be (6-25): 1；The temperature of the dipping is 30-90 DEG C, dipping Time is 0.5-3 hours.
Preferably, the condition of the processing of the first hydrothermal calcine described in step b and the processing of the second hydrothermal calcine described in step f It is independent are as follows: temperature is 450-750 DEG C, and the time is 0.5-6 hours, and steam atmosphere is 100 body % steam atmospheres.
The containing by ammonium exchange, hydrothermal calcine, the first dealumination treatment, alkali process and the second dealumination treatment that the disclosure provides The Y molecular sieve of phosphorus and rare earth, molecular sieve surface Silicon-rich can inhibit the generation of the non-selective side reaction in surface, mesoporous abundant, phosphorus and Content of rare earth is suitable for the progress for being conducive to residual oil cracking reaction, can be improved heavy oil conversion rate, reduces coke yield, while can Reduce olefin(e) centent in gasoline.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Specific embodiment
The specific embodiment of the disclosure is described in detail below.It should be understood that described herein specific Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
The disclosure provides a kind of phosphorous and rare earth Y molecular sieve, and the cell parameter of the molecular sieve is 24.35-24.55 angstroms, With P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.3-10.0 weight %；With RE2O3 It counts and on the basis of the dry weight of molecular sieve, the content of rare earth of the molecular sieve is 0.5-19 weight %；The molecular sieve Al distribution parameter D meets: 0.4≤D≤0.9, wherein D=Al (S)/Al (C), Al (S) indicate to measure using TEM-EDS method Zeolite crystal the inside H in crystal face edge apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C) expression is adopted The outside H of geometric center of crystal face described in the zeolite crystal measured with TEM-EDS method is arbitrarily greater than 100 square nanometers apart from interior The aluminium content in region, wherein the H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The molecular sieve Mesopore volume account for total pore volume ratio be 25%-65%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 65- The ratio between 78%, B acid acid amount and L acid acid amount are 21-98；Preferably, the cell parameter of the molecular sieve is 24.40-24.52 angstroms； With P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 1-8 weight %；With RE2O3Count and with On the basis of the dry weight of molecular sieve, the content of rare earth of the molecular sieve is 3-16 weight %, preferably 7-15 weight %；It is described The Al distribution parameter D of molecular sieve meets: 0.55≤D≤0.8；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 30%-61%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 65-75%, and the ratio between B acid acid amount and L acid acid amount are 35-75。
According to the disclosure, rare earth is well-known to those skilled in the art, the hydrothermal stability etc. with increase molecular sieve Effect, the rare earth can be for selected from least one of lanthanum, cerium, praseodymium and neodymiums, preferably lanthanum.
According to the disclosure, the aluminium content using TEM-EDS method measurement molecular sieve be it is well-known to those skilled in the art, Wherein the geometric center is also well-known to those skilled in the art, can be calculated according to formula, and the disclosure is no longer superfluous It states, the geometric center of generally symmetrical figure is the intersection point of each opposed apexes line, and the crystal face is a face of regular crystal grain, The direction inwardly or outwardly refers both to the direction inwardly or outwardly on the crystal face.
According to the disclosure, the mesopore volume of the molecular sieve account for the ratio of total pore volume using nitrogen adsorption desorption method into Row measurement, it is described it is mesoporous for aperture be greater than 2 nanometers of molecular sieve pore passages less than 100 nanometers；The strong acid acid amount of the molecular sieve accounts for The ratio of total acid content uses NH3- TPD method measures, and the acid site of the strong acid is NH3It is right that desorption temperature is greater than 300 DEG C of institutes The acid site answered；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
The disclosure also provides a kind of preparation method of the Y molecular sieve of phosphorous and rare earth described provided by the disclosure, should Preparation method includes: a, NaY molecular sieve is carried out ammonium exchange processing, and after being filtered and washed, obtains ammonium exchange molecular sieve； Wherein, it is counted by sodium oxide molybdena and on the basis of the dry weight of ammonium exchange molecular sieve, the sodium oxide molybdena of ammonium exchange molecular sieve Content is less than 5 weight %；B, gained ammonium exchange molecular sieve in step a is carried out at the first hydrothermal calcine in steam atmosphere Reason obtains water roasting molecular sieve；C, by step b gained water roasting molecular sieve in the acid solution being made of organic acid and inorganic acid into The first dealumination treatment of row, and after being filtered and washed, obtain the first dealuminzation molecular sieve；D, obtained in step c first is taken off Aluminum molecular screen carries out alkali process in inorganic alkali solution, and after being filtered and washed, obtains alkali process molecular sieve；E, by step Gained alkali process molecular sieve carries out second in the Compound-acid dealuminzation agent solution being made of fluosilicic acid, organic acid and inorganic acid in d Dealumination treatment, and after being filtered and washed, obtain the second dealuminzation molecular sieve；F, by the second dealuminzation molecular sieve of gained in step e Impregnation is carried out in the dipping solution containing phosphorus-containing compound and compounds containing rare earth, and is filtered, washed and in water After carrying out the second hydrothermal calcine processing in vapor atmosphere, described phosphorous and rare earth Y molecular sieve is obtained.
According to the disclosure, the processing of ammonium exchange described in step a is well-known to those skilled in the art, for example, can incite somebody to action NaY molecular sieve is according to molecular sieve: ammonium salt: H2O=1:(0.1-1): the weight ratio of (5-10) is in room temperature to exchanging 0.5- at 100 DEG C It is filtered after 2 hours, this exchange process can repeat 1-4 times, make the Na on molecular sieve2O content % heavy less than 5.The ammonium salt It can be common inorganic ammonium salt, for example, selected from least one of ammonium chloride, ammonium sulfate and ammonium nitrate.
According to the disclosure, organic acid and inorganic acid in acid solution described in step c are that those skilled in the art institute is ripe Know, for example, the organic acid in the acid solution can be in ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid At least one, preferably citric acid；Inorganic acid is selected from least one of hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid.
According to the disclosure, dealumination treatment be it is well-known to those skilled in the art, first dealumination treatment can be primary Or be performed in multiple times, first organic acid can be mixed with water roasting molecular sieve, inorganic acid and the water are then roasted into molecular sieve Mixing；First inorganic acid can also be mixed with water roasting molecular sieve, then mix organic acid with water roasting molecular sieve； Inorganic acid, organic acid can be mixed with water roasting molecular sieve simultaneously.The condition of first dealumination treatment can be with are as follows: with dry basis The weight ratio of the molecular sieve of meter, organic acid and inorganic acid is 1:(0.03-0.3): (0.02-0.4), preferably 1:(0.05- 0.25):(0.05-0.25)；First dealumination treatment temperature is 25-100 DEG C, and the first dealumination treatment time was 0.5-6 hours.
According to the disclosure, what inorganic alkali solution described in step d was well known to those skilled in the art, such as can be choosing From at least one of sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution and ammonium hydroxide, preferably sodium hydroxide is molten Liquid.The condition of alkali process described in step d may include: with the weight ratio of the molecular sieve of dry basis and inorganic base for 1: (0.02-0.6), preferably 1:(0.05-0.4)；Alkali purification temp is 25-100 DEG C, and the alkali process time is 0.5-6 hours.
According to the disclosure, although dealumination treatment be it is well-known to those skilled in the art, do not reported inorganic acid, had Machine acid and fluosilicic acid are used for dealumination treatment together.Second dealumination treatment can be primary or be performed in multiple times, and will can first have Machine acid is mixed with the alkali process molecular sieve, then mixes fluosilicic acid and inorganic acid with the alkali process molecular sieve, it can For first organic acid is added in alkali process molecular sieve, then by fluosilicic acid and inorganic acid, cocurrent is added at a slow speed, or fluorine silicon is first added Acid adds inorganic acid, and preferably cocurrent is added at a slow speed for fluosilicic acid and inorganic acid.In Compound-acid dealuminzation agent solution described in step e The organic acid can be for selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid, preferably grass Acid or citric acid, further preferably oxalic acid, inorganic acid can be selected from least one of hydrochloric acid, sulfuric acid and nitric acid, preferably For hydrochloric acid or sulfuric acid, further preferably hydrochloric acid.The condition of second dealumination treatment can be with are as follows: with the molecule of dry basis Sieve, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.03-0.3): (0.05-0.3): (0.05-0.25), preferably For 1:(0.035-0.2): (0.06-0.2): (0.1-0.2)；Treatment temperature is 25-100 DEG C, and the processing time is 0.5-6 hours.
According to the disclosure, phosphorus-containing compound and compounds containing rare earth be it is well-known to those skilled in the art, for example, step Phosphorus-containing compound described in f can be described for selected from least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate Compounds containing rare earth can be for selected from chlorate and/or nitrate containing at least one of lanthanum, cerium, praseodymium and neodymium, preferably chlorine Change lanthanum and/or lanthanum nitrate.
According to the disclosure, impregnation is well-known to those skilled in the art, the condition of impregnation described in step f It may include: with P2O5The phosphorus-containing compound of meter, with RE2O3Compounds containing rare earth of meter and with the molecular sieve of dry basis Weight ratio is (0.001-0.1): (0.11-0.32): 1, preferably (0.005-0.08): (0.15-0.23): 1, the dipping is molten Liquid with the weight ratio of the molecular sieve of dry basis be (6-25): 1, preferably (8-15): 1；The temperature of the dipping is 30- 90 DEG C, preferably 60-85 DEG C, the time of dipping are 0.5-3 hours, preferably 1-2 hours.
According to the disclosure, hydrothermal calcine be it is well-known to those skilled in the art, for keeping molecular sieve more stable, step The condition of the processing of first hydrothermal calcine described in b and the processing of the second hydrothermal calcine described in step f can be independent are as follows: temperature Degree be 450-750 DEG C, preferably 550-700 DEG C, the time be 0.5-6 hours, preferably 1-2 hours, steam atmosphere 100 Body % steam atmosphere.The processing of first hydrothermal calcine described in step b also has the function of de- ammonium, makes to exchange processing by ammonium Ammonium exchanges molecular sieve (NH4NaY) processing is that water roasts molecular sieve (HNaY), optimum condition are as follows: temperature is 500 DEG C -600 DEG C, the time It is 1-3 hours, is more preferably handled using flowing water steam, the weight for consuming vapor per hour can be ammonium exchange point 1-2 times of weight of son sieve.
Washing described in the disclosure is well-known to those skilled in the art, refers generally to wash, for example, 5-10 times can be used 30-60 DEG C of water of molecular sieve elutes molecular sieve.
The disclosure will be further illustrated by embodiment below, but therefore the disclosure is not any way limited, Instrument and reagent used by the embodiment of the present disclosure, unless otherwise instructed, be instrument commonly used by those skilled in the art and Reagent.
Influence of the molecular sieve in catalytic cracking of petroleum hydrocarbon to gasoline yield and olefin(e) centent counter is commented using heavy oil is micro- Valence.Under 100 volume % water vapour atmospheres, 800 DEG C after aging 17 hours, carry out anti-molecular sieve with Zhenghai VGO (property is shown in Table 1) It answers, catalyst loading 2g, 500 DEG C of reaction temperature, 600 DEG C of regeneration temperature, oil ratio 1.47, air speed 40h-1。
After the reaction was completed, it calculates cracked gas volume and analyzes its composition with gas chromatography, product oil is through gas-chromatography mould Quasi- way of distillation measurement is not more than 220 DEG C of gasoline fractions, 220-330 DEG C of diesel oil distillate and the content greater than 330 DEG C of heavy oil fractions, burnt Charcoal is measured by infrared carbometer.Products obtained therefrom oil is through gas chromatographicanalyzer measurement gasoline fraction hydro carbons composition (PIONA).
Disclosure cell parameter is measured using RIPP145-90 standard method, and the measuring method is shown in " Petrochemical Engineering Analysis Method (RIPP test method) ", Yang Cui delimits the organizational structure, Science Press, and nineteen ninety publishes.
The P of the disclosure2O5、Re2O3, sodium oxide content is measured using GB/T 30905-2014 standard method.
Research method of the TEM-EDS measuring method of the disclosure referring to solid catalyst, petrochemical industry, 29 (3), 2000: 227。
The mesoporous pore volume of the disclosure, the measuring method of total pore volume are as follows:
The AS-3 produced using Quantachrome instrument company, the measurement of AS-6 static state n2 absorption apparatus.
Instrument parameter: being placed in sample processing system for sample, is evacuated to 1.33 × 10 at 300 DEG C-2Pa, heat-insulation pressure keeping 4h purifies sample.At -196 DEG C of liquid nitrogen temperature, test purification sample is not pressing P/P on year-on-year basis0Under the conditions of to the adsorbance of nitrogen And desorption rate, obtain N2Adsorption-desorption isothermal curve.Then total specific surface area is calculated using two parameter BET formula, micropore compares table Area and mesopore surface area take than pressing P/P0=0.98 adsorbance below is the total pore volume of sample, utilizes BJH formula meter The pore-size distribution of mesoporous part is calculated, and mesoporous pore volume (2-100 nanometers) and 2-20 nanometers of mesoporous hole are calculated using integration method Volume.
The B acid acid amount of the disclosure and the measuring method of L acid acid amount are as follows:
The FTS3000 type Fourier infrared spectrograph produced using BIO-RAD company, the U.S..
Test condition: tabletted be placed in the pond in situ of infrared spectrometer of sample is sealed, is vacuumized at 350 DEG C To 10-3Pa keeps 1h, the gas molecule of sample surfaces is desorbed clean, is cooled to room temperature.Pressure is imported into pond in situ is The pyridine steam of 2.67Pa is warming up to 200 DEG C, is evacuated to 10 again after balancing 30min-3Pa keeps 30min, is cooled to room Temperature, in 1400-1700cm-1Scanning, records the infrared spectrum spectrogram of 200 DEG C of pyridine adsorptions in wave-number range.Again by infrared suction Sample in receives pond moves to heat-treatment zone, is warming up to 350 DEG C, is evacuated to 10-3Pa keeps 30min, is cooled to room temperature, records The infrared spectrum of 350 DEG C of pyridine adsorptions.Instrument automatic integration obtains B acid acid amount and L acid acid amount.
The total acid content of the disclosure and the measuring method of strong acid acid amount are as follows:
Using II 2920 temperature programmed desorption instrument of Merck & Co., Inc, U.S. Autochem.
Test condition: weighing 0.2g sample to be tested and be packed into sample cell, is placed in conductance cell heating furnace, and He gas is carrier gas (50mL/ Min), 600 DEG C are warming up to the rate of 20 DEG C/min, purging 60min drives away the impurity of catalyst surface absorption.Then it is cooled to 100 DEG C, constant temperature 30min switches to NH3- He gaseous mixture (10.02%NH3+ 89.98%He) absorption 30min, it is further continued for He gas It is steady to baseline to purge 90min, the ammonia of physical absorption is desorbed.600 DEG C are warming up to 10 DEG C/min heating rate to be taken off It is attached, 30min is kept, desorption terminates.Using TCD detector detection gas change of component, instrument automatic integration obtain total acid content and Strong acid acid amount, the acid site of strong acid are NH3Desorption temperature be greater than 300 DEG C corresponding to acid site.
The calculation method of D value is as follows: choosing a crystal grain in transmission electron microscope and some crystal face of the crystal grain is formed One polygon, there are 10% distance H of geometric center, edge and geometric center to edge point is (different for the polygon Edge point, H value are different), choose respectively any one piece in the inside H distance in the crystal face edge be greater than 100 square nanometers regions with And any one piece in the outside H distance of crystal face geometric center is greater than 100 square nanometers regions, measures aluminium content, as Al (S1) With Al (C1), and D1=Al (S1)/Al (C1) is calculated, chooses different crystal grain respectively and measure 5 times, calculating average value is D.
Embodiment 1
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 3g is added in stirring, 400g hydrochloric acid (matter is then added Measure score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water Be beaten solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 5g is added in stirring Then oxalic acid is slowly added dropwise 50g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%) simultaneously, is warming up to 50 DEG C of perseverances Temperature stirring 1h, filtration washing to neutrality；By filter cake plus water be beaten 10 weight % of solid content molecular sieve pulp, be added 6.72gH3PO4(concentration 85%) and concentration are re chloride (the mixed chlorinated rare earth solution, wherein with oxide of 160g/L Count La2O3Account for 36 weight %, CeO2Account for 64 weight %) 120mL, 60 DEG C of constant temperature stirring 1h are warming up to, filtration washing exists filter cake 550 DEG C, roast 6h in 100% water vapour atmosphere, obtain sieve sample A.Physico-chemical property, the heavy oil of sieve sample A is micro- anti- Evaluation heavy oil conversion rate, gasoline composition result are listed in table 2 and table 3.
Comparative example 1
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 45g is added in stirring, 200g hydrochloric acid (quality is then added Score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten Molecular sieve pulp of the solid content for 10 weight % is starched to obtain, addition 40gNaOH (purity 96%) is warming up to 50 DEG C of constant temperature stirring 0.5h, Filtration washing is to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 30g grass is added in stirring Then 200g hydrochloric acid (mass fraction 10%) and 100g fluosilicic acid (concentration 20%) is slowly added dropwise in acid, be warming up to 85 DEG C of constant temperature and stir 4h is mixed, filtration washing is dried to obtain sieve sample DB1, and physico-chemical property, the heavy oil micro anti-evaluation heavy oil of sieve sample DB1 turns Rate, gasoline composition result are listed in table 2.
Comparative example 2
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g is added in stirring, 200g sulfuric acid (quality is then added Score 10%), time 30min is added；30 DEG C of constant temperature stirring 2h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten Starch solid content be 10 weight % molecular sieve pulps, be added 31.25gKOH (purity 96%), be warming up to the stirring of 70 DEG C of constant temperature 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, be added in stirring Then 100g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%) is slowly added dropwise in 15g oxalic acid, be warming up to 50 DEG C of perseverances Temperature stirring 1h, filtration washing to neutrality；By filter cake plus water be beaten 10 weight % of solid content molecular sieve pulp, be added 10.7gH3PO4(concentration 85%) and concentration are re chloride (the mixed chlorinated rare earth solution, wherein with oxide of 160g/L Count La2O3Account for 36 weight %, CeO2Account for 64 weight %) 30mL, 60 DEG C of constant temperature stirring 1h are warming up to, filtration washing exists filter cake 550 DEG C, roast 2h in 100% water vapour atmosphere, obtain sieve sample DB2.Physico-chemical property, the heavy oil of sieve sample DB2 Micro anti-evaluation heavy oil conversion rate, gasoline composition result are listed in table 2.
Comparative example 3
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g is added in stirring, 200g sulfuric acid (quality is then added Score 10%), time 30min is added；30 DEG C of constant temperature stirring 2h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten Starch solid content be 10 weight % molecular sieve pulps, be added 31.25gKOH (purity 96%), be warming up to the stirring of 70 DEG C of constant temperature 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, be added in stirring Then 100g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%) is slowly added dropwise in 15g oxalic acid, be warming up to 50 DEG C of perseverances Temperature stirring 1h, filtration washing to neutrality；By filter cake plus water be beaten 10 weight % of solid content molecular sieve pulp, be added concentration be Re chloride (the mixed chlorinated rare earth solution, wherein the La in terms of oxide of 160g/L2O3Account for 36 weight %, CeO2Account for 64 weights Measure %) 30mL, 60 DEG C of constant temperature stirring 1h are warming up to, filtration washing roasts filter cake in 550 DEG C, 100% water vapour atmosphere 2h obtains sieve sample DB3.Physico-chemical property, heavy oil micro anti-evaluation heavy oil conversion rate, the gasoline composition of sieve sample DB3 As a result it is listed in table 2.
Embodiment 2
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g is added in stirring, 200g sulfuric acid (quality is then added Score 10%), time 30min is added；30 DEG C of constant temperature stirring 2h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten Starch solid content be 10 weight % molecular sieve pulps, be added 31.25gKOH (purity 96%), be warming up to the stirring of 70 DEG C of constant temperature 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, be added in stirring Then 15g oxalic acid is slowly added dropwise 100g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%) simultaneously, is warming up to 50 DEG C constant temperature stirs 1h, filtration washing to neutrality；By filter cake plus water be beaten 10 weight % of solid content molecular sieve pulp, be added 5.1gNH4H2PO4Re chloride (the mixed chlorinated rare earth solution, wherein the La in terms of oxide for being 160g/L with concentration2O3It accounts for 36 weight %, CeO2Account for 64 weight %) 130mL, be warming up to 70 DEG C of constant temperature stirring 1.5h, filtration washing, by filter cake 700 DEG C, 1h is roasted in 100% water vapour atmosphere, obtains sieve sample B.Physico-chemical property, the heavy oil micro anti-evaluation weight of sieve sample B Oily conversion ratio, gasoline composition result are listed in table 2.
Embodiment 3
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) add water to be configured to the molecular sieve pulp that solid content 10 weighs %, ethylenediamine tetra-acetic acid 25g is added in stirring, 250g is then added Time 30min is added in nitric acid (mass fraction 10%)；90 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；It will filter Cake add water be beaten solid content be 10 weight % molecular sieve pulps, be added 41gNaOH (purity 96%), be warming up to 80 DEG C of constant temperature and stir Mix 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, be added in stirring Then 102g nitric acid (mass fraction 10%) and 49g fluosilicic acid (concentration 20%) is slowly added dropwise simultaneously in 20g sulfosalicylic acid, rise Temperature to 70 DEG C of constant temperature stir 1h, filtration washing to neutrality；By filter cake plus water be beaten 15 weight % of solid content molecular sieve pulp, 7.0gH is added3PO4(concentration 85%) and concentration are re chloride (the mixed chlorinated rare earth solution, wherein with oxygen of 160g/L Compound meter La2O3Account for 36 weight %, CeO2Account for 64 weight %) 201mL, 90 DEG C of constant temperature stirring 0.5h are warming up to, filtration washing will Filter cake roasts 1h in 700 DEG C, 100% water vapour atmosphere, obtains sieve sample C.The physico-chemical property of sieve sample C, again Oily micro anti-evaluation heavy oil conversion rate, gasoline composition result are listed in table 2.
Embodiment 4
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 30g is added in stirring, 100g hydrochloric acid (matter is then added Measure score 10%), time 1min is added；55 DEG C of constant temperature stirring 2h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten Molecular sieve pulp of the solid content for 10 weight % is starched to obtain, addition 50gNaOH (purity 96%) is warming up to 50 DEG C of constant temperature stirring 0.5h, Filtration washing is to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 30g grass is added in stirring Then acid is slowly added dropwise 100g hydrochloric acid (mass fraction 10%) and 63g fluosilicic acid (concentration 20%) simultaneously, is warming up to 50 DEG C of constant temperature Stir 1h, filtration washing to neutrality；By filter cake plus water be beaten 15 weight % of solid content molecular sieve pulp, be added 9.5gH3PO4 (concentration 85%) and concentration are re chloride (the mixed chlorinated rare earth solution, wherein the La in terms of oxide of 160g/L2O3It accounts for 36 weight %, CeO2Account for 64 weight %) 180mL, be warming up to 80 DEG C of constant temperature stirring 1h, filtration washing, by filter cake 680 DEG C, 1h is roasted in 100% water vapour atmosphere, obtains sieve sample D.Physico-chemical property, the heavy oil micro anti-evaluation weight of sieve sample D Oily conversion ratio, gasoline composition result are listed in table 2.
Embodiment 5
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 20g is added in stirring, 220g nitric acid (matter is then added Measure score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water It is beaten to obtain molecular sieve pulp of the solid content for 10 weight %, addition 24KOH is warming up to 400 DEG C of constant temperature stirring 2h, and filtration washing is into Property；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 5g citric acid is added in stirring, it is then slow simultaneously It is slow that 148g hydrochloric acid (mass fraction 10%) and 125g fluosilicic acid (concentration 20%) is added dropwise, it is warming up to 80 DEG C of constant temperature stirring 1h, filtering It washs to neutrality；By filter cake plus water be beaten 15 weight % of solid content molecular sieve pulp, be added 2.6gH3PO4(concentration 85%) Re chloride (the mixed chlorinated rare earth solution, wherein the La in terms of oxide for being 160g/L with concentration2O336 weight % are accounted for, CeO2Account for 64 weight %) 150mL, it is warming up to 80 DEG C of constant temperature stirring 1h, filtration washing, by filter cake in 650 DEG C, 100% water vapour 2.5h is roasted in atmosphere, obtains sieve sample E.The physico-chemical property of sieve sample E, heavy oil micro anti-evaluation heavy oil conversion rate, Gasoline composition result is listed in table 2.
Embodiment 6
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 45g is added in stirring, 200g hydrochloric acid (quality is then added Score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten Molecular sieve pulp of the solid content for 10 weight % is starched to obtain, addition 45gKOH (purity 96%) is warming up to 50 DEG C of constant temperature stirring 0.5h, mistake Filter washing is to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 8g ethylenediamine is added in stirring Then tetraacethyl is slowly added dropwise 90g nitric acid (mass fraction 10%) and 100g fluosilicic acid (concentration 20%) simultaneously, is warming up to 85 DEG C Constant temperature stirs 4h, filtration washing to neutrality；By filter cake plus water be beaten 15 weight % of solid content molecular sieve pulp, be added 6.8gH3PO4(concentration 85%) and concentration are re chloride (the mixed chlorinated rare earth solution, wherein with oxide of 160g/L Count La2O3Account for 36 weight %, CeO2Account for 64 weight %) 220mL, 80 DEG C of constant temperature stirring 1h are warming up to, filtration washing exists filter cake 650 DEG C, roast 5h in 100% water vapour atmosphere, obtain sieve sample F.Physico-chemical property, the heavy oil of sieve sample F is micro- anti- Evaluation heavy oil conversion rate, gasoline composition result are listed in table 2.
Comparative example 4
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 3g is added in stirring, 400g hydrochloric acid (matter is then added Measure score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water Be beaten solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 5g is added in stirring Oxalic acid is warming up to 50 DEG C of constant temperature stirring 1h, filtration washing to neutrality；By filter cake plus water be beaten 10 weight % of solid content molecule 6.72gH is added in screening the pulp liquid3PO4(concentration 85%) and concentration be 160g/L re chloride (mixed chlorinated rare earth solution, The wherein La in terms of oxide2O3Account for 36 weight %, CeO2Account for 64 weight %) 120mL, 60 DEG C of constant temperature stirring 1h are warming up to, diafiltration is crossed It washs, filter cake is roasted into 6h in 550 DEG C, 100% water vapour atmosphere, obtains sieve sample DA1.The object of sieve sample DA1 Change property, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline composition result and is listed in table 3.
Comparative example 5
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 3g is added in stirring, 400g hydrochloric acid (matter is then added Measure score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water Be beaten solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, slowly drip in stirring Add 50g hydrochloric acid (mass fraction 10%), is warming up to 50 DEG C of constant temperature stirring 1h, filtration washing to neutrality；Filter cake plus water are beaten 6.72gH is added in the molecular sieve pulp of 10 weight % of solid content3PO4(concentration 85%) and concentration are that the rare earth chloride of 160g/L is molten Liquid (mixed chlorinated rare earth solution, wherein the La in terms of oxide2O3Account for 36 weight %, CeO2Account for 64 weight %) 120mL, it is warming up to 60 DEG C of constant temperature stir 1h, and filter cake is roasted 6h in 550 DEG C, 100% water vapour atmosphere, obtains sieve sample by filtration washing DA2.The physico-chemical property of sieve sample DA2, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline composition result are listed in table 3.
Comparative example 6
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 3g is added in stirring, 400g hydrochloric acid (matter is then added Measure score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water Be beaten solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, slowly drip in stirring Add 15g fluosilicic acid (concentration 20%), is warming up to 50 DEG C of constant temperature stirring 1h, filtration washing to neutrality；Filter cake plus water are beaten solid 6.72gH is added in the molecular sieve pulp of 10 weight % of content3PO4(concentration 85%) and concentration are the re chloride of 160g/L (mixed chlorinated rare earth solution, wherein the La in terms of oxide2O3Account for 36 weight %, CeO2Account for 64 weight %) 120mL, it is warming up to 60 DEG C constant temperature stirs 1h, and filter cake is roasted 6h in 550 DEG C, 100% water vapour atmosphere, obtains sieve sample by filtration washing DA3.The physico-chemical property of sieve sample DA3, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline composition result are listed in table 3.
Comparative example 7
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 3g is added in stirring, 400g hydrochloric acid (matter is then added Measure score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water Be beaten solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 5g is added in stirring Then 50g hydrochloric acid (mass fraction 10%) is slowly added dropwise in oxalic acid, be warming up to 50 DEG C of constant temperature stirring 1h, filtration washing to neutrality；It will Filter cake add water be beaten 10 weight % of solid content molecular sieve pulp, be added 6.72gH3PO4(concentration 85%) and concentration are 160g/ Re chloride (the mixed chlorinated rare earth solution, wherein the La in terms of oxide of L2O3Account for 36 weight %, CeO2Account for 64 weight %) 120mL, is warming up to 60 DEG C of constant temperature stirring 1h, and filter cake is roasted 6h in 550 DEG C, 100% water vapour atmosphere, obtained by filtration washing To sieve sample DA4.Physico-chemical property, heavy oil micro anti-evaluation heavy oil conversion rate, the gasoline composition result column of sieve sample DA4 In table 3.
Comparative example 8
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 3g is added in stirring, 400g hydrochloric acid (matter is then added Measure score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water Be beaten solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, 5g is added in stirring Then 15g fluosilicic acid (concentration 20%) is slowly added dropwise in oxalic acid, be warming up to 50 DEG C of constant temperature stirring 1h, filtration washing to neutrality；It will filter Cake add water be beaten 10 weight % of solid content molecular sieve pulp, be added 6.72gH3PO4(concentration 85%) and concentration are 160g/L Re chloride (mixed chlorinated rare earth solution, wherein the La in terms of oxide2O3Account for 36 weight %, CeO2Account for 64 weight %) 120mL, is warming up to 60 DEG C of constant temperature stirring 1h, and filter cake is roasted 6h in 550 DEG C, 100% water vapour atmosphere, obtained by filtration washing To sieve sample DA5.Physico-chemical property, heavy oil micro anti-evaluation heavy oil conversion rate, the gasoline composition result column of sieve sample DA5 In table 3.
Comparative example 9
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 weight %.Above-mentioned molecular sieve is taken to roast 2h under 600 DEG C, 100% vapor.Molecular sieve 100g (butt matter after taking roasting Amount) plus water be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 3g is added in stirring, 400g hydrochloric acid (matter is then added Measure score 10%), time 30min is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water Be beaten solid content be 10 weight % molecular sieve pulps, be added 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulp, slowly drip in stirring Add 50g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%), is warming up to 50 DEG C of constant temperature stirring 1h, filtration washing is extremely It is neutral；By filter cake plus water be beaten 10 weight % of solid content molecular sieve pulp, be added 6.72gH3PO4(concentration 85%) and concentration For re chloride (the mixed chlorinated rare earth solution, wherein the La in terms of oxide of 160g/L2O3Account for 36 weight %, CeO2Account for 64 Weight %) 120mL, 60 DEG C of constant temperature stirring 1h are warming up to, filtration washing roasts filter cake in 550 DEG C, 100% water vapour atmosphere 6h is burnt, sieve sample DA6 is obtained.The physico-chemical property of sieve sample DA6, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline group Table 3 is listed at result.
It can be seen from the data in Table 2 that with excellent weight when the molecular sieve that the disclosure provides is reacted for residual oil cracking Oily conversion capability and higher yield of gasoline, low coke yield, olefin(e) centent is low in gasoline.
For the Y molecular sieve after alkali process desiliconization it can be seen from data in table 3, using single organic acid oxalic acid dealuminzation (DA1), compound using single inorganic acid HCl dealumination (DA2) and using organic acid oxalic acid and two kinds of acid of inorganic acid hydrochloric acid (DA4) all effectively the Al in molecular sieve can not be removed, and preferable dealuminzation effect could be obtained after only having used fluosilicic acid Fruit.When fluosilicic acid dealuminzation is used alone (DA3), strong acid proportion in total acid is lower, and B acid/L acid ratio is lower.Fluosilicic acid Composite organic acid oxalic acid dealuminzation (DA5), is equally unable to get preferable acid distribution.Fluosilicic acid composite inorganic acid HCl dealumination (DA6), strong acid proportion and B acid/L acid ratio in total acid is all not so good as the molecular sieve height of disclosure offer.The disclosure is adopted It can guarantee crystal structure of molecular sieve and mesopore orbit structural integrity under three kinds of sour synergistic effects with compound acid system Property under the premise of effectively adjust aluminium distribution, improve acid distribution, molecular sieve surface Silicon-rich can inhibit the non-selective side reaction in surface Generation, mesoporous abundant, content of rare earth is suitable for the progress for being conducive to residual oil cracking reaction, can be improved heavy oil conversion rate, is reduced Coke yield, while can reduce olefin(e) centent in gasoline.
Table 1
Title Numerical value
Density (20 DEG C), g/cm3 0.9154
Refractive power (70 DEG C) 0.4926
Viscosity (50 DEG C), mm2/s 34.14
Viscosity (70 DEG C), mm2/s 6.962
Acid value, mgKOH/g 0.27
Freezing point, DEG C 35
Aniline point, DEG C 82
Carbon residue, m% 0.18
Four components
Saturated hydrocarbons, m% 64.0
Aromatic hydrocarbons 32.0
Colloid 4.0
Asphalitine 0.0
Tenor, ppm
Ni <0.1
V <0.1
Cu 0.1
Fe 0.5
Na 0.8
H, % 12.03
C, % 85.38
S, % 2.0
N, % 0.16
IBP, DEG C/5% 329/363
10%/30% 378/410
50%/70% 436/462
90%/95% 501/518
Table 2
Table 3

Claims (16)

1. a kind of phosphorous and rare earth Y molecular sieve, the cell parameter of the molecular sieve is 24.35-24.55 angstroms, with P2O5It counts and to divide On the basis of the dry weight of son sieve, the phosphorus content of the molecular sieve is 0.3-10.0 weight %；With RE2O3It counts and with molecular sieve On the basis of dry weight, the content of rare earth of the molecular sieve is 0.5-19 weight %；The Al distribution parameter D of the molecular sieve is full Foot: 0.4≤D≤0.9, wherein D=Al (S)/Al (C), Al (S) indicate the zeolite crystal measured using TEM-EDS method The inside H in crystal face edge indicates to survey using TEM-EDS method apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C) The outside H of the geometric center of crystal face described in fixed zeolite crystal apart from interior any aluminium content for being greater than 100 square nanometers regions, Described in H be the crystal face edge point to the crystal face geometric center distance 10%；The mesopore volume Zhan of the molecular sieve is total The ratio of pore volume be 25%-65%, it is described it is mesoporous for aperture be greater than 2 nanometers of molecular sieve pore passages less than 100 nanometers；Described point The ratio that the strong acid acid amount of son sieve accounts for total acid content is 65-78%, and the ratio between B acid acid amount and L acid acid amount are 21-98.
2. the Y molecular sieve of phosphorous and rare earth according to claim 1, wherein the cell parameter of the molecular sieve is 24.40-24.52 angstroms；With P2O5It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is that 1-8 is weighed Measure %；With RE2O3It counts and on the basis of the dry weight of molecular sieve, the content of rare earth of the molecular sieve is 3-16 weight %；It is described The Al distribution parameter D of molecular sieve meets: 0.55≤D≤0.8；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 30%-61%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 65-75%, and the ratio between B acid acid amount and L acid acid amount are 35-75。
3. according to claim 1 phosphorous and rare earth Y molecular sieve, wherein the rare earth is selected from lanthanum, cerium, praseodymium and neodymium At least one of.
4. according to claim 1 phosphorous and rare earth Y molecular sieve, wherein the strong acid acid amount of the molecular sieve accounts for total acid The ratio of amount uses NH3- TPD method measures, and the acid site of the strong acid is NH3Desorption temperature is greater than corresponding to 300 DEG C Acid site；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
5. the preparation method of phosphorous described in a kind of any one of claim 1-4 and rare earth Y molecular sieve, the preparation method Include:
A, NaY molecular sieve is subjected to ammonium exchange processing, and after being filtered and washed, obtains ammonium exchange molecular sieve；Wherein, with oxygen Change sodium meter and on the basis of the dry weight of ammonium exchange molecular sieve, the sodium oxide content of ammonium exchange molecular sieve is less than 5 Weight %；
B, gained ammonium exchange molecular sieve in step a is subjected in steam atmosphere the first hydrothermal calcine processing, obtains water roasting point Son sieve；
C, gained water roasting molecular sieve in step b is carried out at the first dealuminzation in the acid solution being made of organic acid and inorganic acid Reason, and after being filtered and washed, obtain the first dealuminzation molecular sieve；
D, the first dealuminzation molecular sieve obtained in step c is subjected in inorganic alkali solution alkali process, and be filtered and washed Afterwards, alkali process molecular sieve is obtained；
E, gained alkali process molecular sieve in step d is molten in the Compound-acid dealumination agent being made of fluosilicic acid, organic acid and inorganic acid Carry out the second dealumination treatment in liquid, and after being filtered and washed, obtain the second dealuminzation molecular sieve, inorganic acid be selected from hydrochloric acid, At least one of sulfuric acid and nitric acid；
F, by step e gained the second dealuminzation molecular sieve in the dipping solution containing phosphorus-containing compound and compounds containing rare earth into Row impregnation, and after being filtered, washed and carrying out the second hydrothermal calcine processing in steam atmosphere, it obtains described phosphorous With the Y molecular sieve of rare earth.
6. preparation method according to claim 5, wherein the organic acid in acid solution described in step c is selected from second two At least one of amine tetraacethyl, oxalic acid, citric acid and sulfosalicylic acid, inorganic acid are in hydrochloric acid, sulfuric acid and nitric acid It is at least one.
7. preparation method according to claim 5, wherein the condition of the first dealumination treatment described in step c includes: with dry The weight ratio of the molecular sieve of base weight meter, organic acid and inorganic acid is 1:(0.03-0.3): (0.02-0.4)；At first dealuminzation Managing temperature is 25-100 DEG C, and the first dealumination treatment time was 0.5-6 hours.
8. preparation method according to claim 5, wherein the condition of the first dealumination treatment described in step c includes: with dry The weight ratio of the molecular sieve of base weight meter, organic acid and inorganic acid is 1:(0.05-0.25): (0.05-0.25).
9. preparation method according to claim 5, wherein inorganic alkali solution described in step d is molten selected from sodium hydroxide At least one of liquid, potassium hydroxide solution, lithium hydroxide solution and ammonium hydroxide.
10. preparation method according to claim 5, wherein the condition of alkali process described in step d includes: with dry basis The molecular sieve of meter and the weight ratio of inorganic base are 1:(0.02-0.6)；Alkali purification temp is 25-100 DEG C, the alkali process time It is 0.5-6 hours.
11. preparation method according to claim 5, wherein organic described in Compound-acid dealuminzation agent solution described in step e Acid is selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid.
12. preparation method according to claim 5, wherein the condition of the second dealumination treatment described in step e include: with The molecular sieve of dry basis, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.03-0.3): (0.05-0.3): (0.05-0.25)；Second dealumination treatment temperature is 25-100 DEG C, and the second dealumination treatment time was 0.5-6 hours.
13. preparation method according to claim 5, wherein the condition of the second dealumination treatment described in step e include: with The molecular sieve of dry basis, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.035-0.2): (0.06-0.2): (0.1-0.2)。
14. preparation method according to claim 5, wherein phosphorus-containing compound described in step f is selected from phosphoric acid, phosphoric acid At least one of hydrogen ammonium, ammonium dihydrogen phosphate and ammonium phosphate, the compounds containing rare earth are selected from containing in lanthanum, cerium, praseodymium and neodymium At least one chlorate and/or nitrate.
15. preparation method according to claim 5, wherein the condition of impregnation described in step f includes: with P2O5Meter Phosphorus-containing compound, with RE2O3The compounds containing rare earth of meter and with the weight ratio of the molecular sieve of dry basis be (0.001- 0.1): (0.11-0.32): 1, the dipping solution with the weight ratio of the molecular sieve of dry basis be (6-25): 1；It is described The temperature of dipping is 30-90 DEG C, and the time of dipping is 0.5-3 hours.
16. preparation method according to claim 5, wherein in the processing of the first hydrothermal calcine described in step b and step f The condition of the second hydrothermal calcine processing is independent are as follows: temperature is 450-750 DEG C, and the time is 0.5-6 hours, vapor Atmosphere is 100 body % steam atmospheres.
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