CN1051710A

CN1051710A - Process for preparing of high silicon y zeolite

Info

Publication number: CN1051710A
Application number: CN 89108480
Authority: CN
Inventors: 张国宏
Original assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 1989-11-13
Filing date: 1989-11-13
Publication date: 1991-05-29

Abstract

A kind of process for preparing of high silicon Y zeolite uses NaY or other Y zeolite and sodium hexafluorisilicate or other hexafluorosilicates directly to carry out the dealumination complement silicon reaction in acidic medium, does not generate stray crystal in the process, and product high-silicon Y-Zeolite degree of crystallinity is higher than 85%.

Description

Process for preparing of high silicon Y zeolite

The present invention relates to a kind of preparation method of high-silicon Y-Zeolite.

As everyone knows, people had continually developed out some novel molecular sieves in the last few years, but Y zeolite still occupies very consequence, the high-silicon Y-Zeolite that especially utilizes prepared in various methods to go out in research with in using.

At first, what produce breakthrough in this respect is the steam roasting method that United States Patent (USP) 3293192 is reported, and is about to NaY or NH ₄The higher overstable gamma zeolite of framework si-al ratio is prepared in Y zeolite high-temperature roasting under spontaneous or the water vapor that adds; Another kind method is a United States Patent (USP) 3506400,3640681, the 3691099 dealuminzation methods of being reported, promptly utilize certain compound under certain condition in liquid phase with the Y zeolite skeleton in aluminium certain chemical action takes place, thereby leave the silica alumina ratio that skeleton has improved skeleton, commonly used is those inorganic or organic compound that aluminium had effects such as complexing or hydrolysis; The third method of preparation high-silicon Y-Zeolite is roasting-dealuminzation method that United States Patent (USP) 3493519 is reported, promptly earlier by high-temperature roasting or steam roasting, handles with acid or aluminum complexing agent more at last, has so also prepared high-silicon Y-Zeolite; The 4th kind of method of preparation high-silicon Y-Zeolite is United States Patent (USP) 4297335,4388178 and the gas-solid reaction method reported of Deutsches Reichs-Patent 3132380, the fluid cpds that promptly utilizes gaseous compound or high volatility under certain condition with Y zeolite generation dealumination reaction or silicon substitution reaction; The 5th kind of method of preparation high-silicon Y-Zeolite is the dealumination complement silicon method of the ammonium hexafluorosilicate reported of United States Patent (USP) 4503023 European patents 124120, promptly containing NH ₄Y or NH ₄Drip the hexafluorosilicic acid aqueous ammonium in the slurries of NaY zeolite, the replacement(metathesis)reaction by dealumination complement silicon also can generate the high-silicon Y-Zeolite product.

Above-mentioned five kinds of methods have been summarized the state of the art of high-silicon Y-Zeolite preparation.Be used widely although these methods are industrial, they all exist many weak points separately.For roasting method, the aluminium of taking off from zeolite framework can not effectively separate usually makes its specific surface, and pore volume and degree of crystallinity reduce; For dealumination process, usually contain more textural defect in the product Y zeolite, cause chemical stability to reduce.For gas-solid method, its operational condition has been subjected to certain restriction, almost avoided shortcoming in the several method of front for the ammonium silicofluoride method, but also existed the following problem needs further to solve and improve: the NH that 1) can not replace twice ammonium exchange with the most cheap NaY ₄The NaY zeolite is as raw material, if be raw material with NaY, can generate a large amount of sodium fluoroaluminate stray crystals in the product, and the separation of this stray crystal is extremely difficult; 2) can not use Na ₂SiF ₆Replace (NH ₄) ₂SF ₆Be raw material reagent, Na ₂SiF ₆Be the industrial product of paying with phosphorus lime (calcium monofluorophosphate) production phosphate fertilizer, price is extremely low; China does not also have (NH at present on the other hand ₄) ₄SiF ₆The equipment of industrial product and product, but because Na ₂SiF ₆Water insoluble, and because Na ⁺A large amount of introducings have a large amount of sodium fluoroaluminate stray crystal and generate, still do not have a kind of effective means to address these problems at present; 3) in this method, although with (NH ₄) ₂SiF ₆And NH ₄The NaY zeolite is a reaction raw materials, needs further to separate but still contain some stray crystals in the product, makes technical process become complicated; 4) production cycle of this method also long, from the report need tens of hours at least, caused bigger industrial consumption.

The object of the present invention is to provide a kind of method for preparing high-silicon Y-Zeolite, can directly be used as the dealumination complement silicon reaction raw materials, save the ammonium exchanger with the Y zeolite of multiple positively charged ion form; And can avoid generating in the reaction process stray crystal and block the duct or cause the skeleton defective with multiple hexafluorosilicate as the silicon source, shorten preparation cycle, thereby prepare high-quality high-silicon Y-Zeolite.

In the present invention, the step of preparation F-1 zeolite is as follows:

1, hexafluorosilicate choice of Solvent

Hexafluorosilicate is both water miscible also water-insoluble, as (NH ₄) ₂SiF ₆, Li ₂SiF ₆, Na ₂SiF ₆, K ₂SiF ₆, BeSiF ₆, MgSiF ₆, CaSiF ₆, SrSiF ₆, BaSiF ₆Deng.Its dissolved solvent should be chosen the weakly acidic solution of PH4-6, preferably chooses rare inorganic or aqueous solutions of organic acids and strong acid ammonium salt aqueous solution.Can suitably heat and stir during dissolving, make the solution I.The concentration of hexafluorosilicate is 0.05-0.50M, preferably 0.10-0.30M.

2, the preparation of raw material zeolite reaction initial slurry

The raw material zeolite can be an any kind of positively charged ion Y zeolite, as NaY, NH ₄Y, NH ₄NaY, KY, CaY, REY, MgY etc.The solution that is adopted is any kind of acidic solution of PH=3-6, and strong acid ammonium salt solution preferably is as NH ₄NO ₃, NH ₄Cl, (NH ₄) ₂SO ₄, (NH ₄) ₃PO ₄, (NH ₄) ₂HPO ₄, (NH ₄) H ₂PO ₄Deng.The preparation slurries, wherein Y zeolite content is generally 0.05-0.50g/ml, preferably 0.1-0.2g/ml.

3, the selection of reaction conditions

Before hexafluorosilicate solution drips, the slurries II is warmed up to 40-200 ℃, preferably 80-150 ℃, under agitation condition, with 0.01-1.00mol SiF ^2- ₆/ hour kilogram Y zeolite (0.1-0.8mol SiF preferably ^2- ₆/ hour kilogram Y zeolite) speed drips hexafluorosilicic acid salts solution I; Its dripping quantity determines that by the required dealuminzation amount of purpose product the mol ratio of required hexafluorosilicate and dealuminzation is 1: 1; Reaction mixed serum after dropwising continues to stir at least 0.5 hour under 70-200 ℃ of condition, is preferably in to continue under the 80-120 ℃ of condition to stir more than 1 hour; Then, suction filtration and washing obtain the filter cake III, and preferably hot suction filtration is also used hot deionization washing 1-3 time.

4, the selection of secondary reaction condition

The filter cake that step 3 is obtained places the acidic solution of PH=2-6, and the preferably rare inorganic or aqueous solutions of organic acids and the aqueous solution of strong acid weak base salt are as H ₂SO ₄, HCl, H ₃PO ₄, HAc, HNO ₃, NH ₄Cl, NH ₄NO ₃, (NH ₄) ₂SO ₄Or the like; In the slurries that stirring makes, the content of zeolite is generally 0.05-0.50g/ml, preferably 0.1-0.2g/ml; These slurries are warming up to 50-150 ℃, preferably 70-120 ℃; Then, stirred 1 hour preferably 2-6 hour at least; At last, filter and wash 1-3 time.

5, ammonium ion exchange

Ammonium ion exchange method can adopt any method so far, and the exchange number of times depends on purpose product Na ₂The requirement of O content.

Compared with prior art, process for preparing of high silicon Y zeolite of the present invention has following characteristics: (1) is applicable to by multiple Y zeolite raw material, prepares high-silicon Y-Zeolite, exchange and need not that the raw material Y zeolite is carried out ammonium.(2) preparation process is simple, owing to do not generate stray crystal in the reaction process, need not to separate.(3) it is in extensive range to can be used as the hexafluorosilicate in silicon source.(4) shortened preparation cycle.(5) be that raw material directly prepares high-silicon Y-Zeolite and has remarkable economical and be worth particularly with sodium Y zeolite and sodium hexafluorisilicate.

Adopt the high-silicon Y-Zeolite of method preparation of the present invention, have pore volume and specific surface big (common pore volume and specific surface) greater than the raw material zeolite, degree of crystallinity height (being not less than 86%), product silica alumina ratio scope is big, the advantage that lattice constant is little.

Content above-mentioned has proved absolutely implementation step of the present invention and feature.Following Example is used to explain implementation process of the present invention, but does not limit the present invention.

Example

Example 1

(1) takes by weighing 5.32g K ₂SiF ₆Crystal joins 100ml 1M(NH ₄) ₂SO ₄In the aqueous solution, the heated and stirred dissolving makes solution A.

(2) take by weighing the NH of 10g butt ₄Y zeolite (SiO ₂/ Al ₂O ₃=5.03), join 100ml(NH is housed ₄) ₂SO ₄In the aqueous solution,, make slurries B 95 ℃ of following mechanical stirring 0.5 hour.

(3) solution A is added dropwise among the slurries B under 95 ℃ of constant temperature mechanical stirring, control adding speed makes it to add in 2 hours, and add the back and continue to stir 2 hours, heat filtering then, boiling water is washed till no fluorion, makes filter cake C.

(4) filter cake C is joined be equipped with in the rare HCl aqueous solution of 100mlPH=3.8,, filter then and be washed to no chlorion, make product F-1 zeolite 95 ℃ of following constant temperature mechanical stirring 2 hours.

Chemical analysis results is as follows:

* degree of crystallinity: 96%

* lattice constant: 24.46A

＊SiO ₂/Al ₂O ₃：12.7

* stray crystal analysis: do not have

* degree of crystallinity: refer to value by the ratio gained of X-ray diffraction relative intensity.

* lattice constant: refer to by the measured result in X-ray diffraction peak position.

* SiO ₂/ Al ₂O ₃: referring to mol ratio here, is resulting by conventional quantitative analysis.

* stray crystal analysis: by X-ray diffraction gained.

Comparative example 1

Draw embodiment 17 from United States Patent (USP) 4503023:

(1) takes by weighing the NH of 10g butt ₄Y zeolite (SiO ₂/ Al ₂O ₃=4.93), join 100ml3.4M NH ₄In the AC aqueous solution, 75 ℃ of following stirrings make slurries A.

(2) take by weighing 5.32g K ₂SiF ₆Crystal, and it is joined among the slurries A 75 ℃ of reactions 2 days down, filters and is washed till free-floride and aluminum ion with boiling water, makes product LZ-210 zeolite.

Chemical analysis results is as follows:

Degree of crystallinity: 44%

Lattice constant: 24.51A

SiO ₂/Al ₂O ₃：11.4

Stray crystal is analyzed: a large amount of

Example 2

(1) takes by weighing the NH of 82% ammonium ion exchange of 14g butt ₄NaY zeolite (SiO ₂/ Al ₂O ₃=5.14), join 140ml 2M NH ₄NO ₃In the aqueous solution,, make slurries A 80 ℃ of mechanical stirring 0.5 hour.

(2) take by weighing 3.96g(NH ₄) ₂SiF ₆Crystal joins 100ml2M NH ₄NO ₃In the aqueous solution, the heated and stirred dissolving makes solution B.

(3) solution B is joined among the slurries A under 80 ℃ of constant temperature mechanical stirring, control adding speed makes it to add in 2 hours, and add the back and continue to stir 2 hours, heat filtering then, boiling water is washed till no fluorion, makes filter cake C.

(4) with step (4) in the example 1.

Chemical analysis results is as follows:

Degree of crystallinity: 108%

Lattice constant: 24.50A

SiO ₂/Al ₂O ₃：10.1

Stray crystal is analyzed: do not have

Comparative example 2

Draw embodiment 1 in United States Patent (USP) 4503023.

(1) takes by weighing 396g(NH ₄) ₂SiF ₆Crystal is dissolved in 50 ℃ of water of 3l and makes solution A.

(2) take by weighing the NH of 85% ammonium ion exchange of 1420g butt ₄NaY zeolite (SiO ₂/ Al ₂O ₃=4.85), join 75 ℃ NH ₄(6400g NH in the Ac aqueous solution ₄Ac+8l H ₂O), stirring makes slurries B.

(3) solution A is added dropwise among the slurries B under 75 ℃ of agitation conditions, speed is dripped in control to be made it to add in 2.5 hours, stirs down at 95 ℃ then and spends the night, and filters at last and with hot water and NH ₄The Ac aqueous solution is washed till free-floride and aluminum ion, makes product LZ-210 zeolite.

Chemical analysis results is as follows:

Degree of crystallinity: 94%

Lattice constant: 24.51A

SiO ₂/Al ₂O ₃：9.54

Stray crystal is analyzed: undeclared

Comparative example 3

We have made the LZ-210 zeolite according to identical experimental procedure in the comparative example 2, and chemical analysis results is as follows:

Degree of crystallinity: 92%

Lattice constant: 24.50A

SiO ₂/Al ₂O ₃：9.72

Stray crystal is analyzed: a small amount of

Example 3

(1) takes by weighing 5g(NH ₄) ₂SiF ₆Crystal joins rare H of 100ml PH=5.2 ₂SO ₄In the aqueous solution, dissolving makes solution A.

(2) take by weighing the NaY zeolite (SiO of 10g butt ₂/ Al ₂O ₃=5.03), join the NH of 100mlPH=4.6 ₄(NH in the Cl-HCl aqueous solution ₄Cl concentration is 3M), 70 ℃ of following mechanical stirring 1 hour make slurries B.

(3) solution A is splashed among the slurries B under 70 ℃ of stirrings, speed is dripped in control to be made it to add in 3 hours, is warming up to 120 ℃ after adding, and stirs 1 hour under this temperature, and heat filtering and boiling water are washed till no fluorion then, make filter cake C.

(4) filter cake C is joined the NH that 100ml 3M is housed ₄In the Cl aqueous solution,, filter then and be washed to no chlorion, make product F-1 zeolite 100 ℃ of following constant temperature mechanical stirring 2 hours.

Chemical analysis results is as follows:

Degree of crystallinity: 94%

Lattice constant: 24.43A

SiO ₂/Al ₂O ₃：16.4

Stray crystal is analyzed: do not have

Example 4

(1) takes by weighing 2.26g Na ₂SiF ₆Crystal joins the NH of 100ml 3M ₄Dissolve in the Cl aqueous solution, make solution A.

(2) take by weighing 10g butt NaY zeolite (SiO ₂/ Al ₂O ₃=5.03), join 100ml3M NH ₄In the Cl aqueous solution, 70 ℃ of following mechanical stirring 1 hour make slurries B.

(3) with step (3) in the example 3.

(4) with step (4) in the example 3.

Chemical analysis results is as follows:

Degree of crystallinity: 98%

Lattice constant: 24.49A

SiO ₂/Al ₂O ₃：7.04

Stray crystal is analyzed: do not have

Example 5

(1) with step (1) in the example 4.

(2) take by weighing 10g butt HY zeolite (SiO ₂/ Al ₂O ₃=5.42), join in rare HCl aqueous solution of 100ml PH=4.8, made slurries B in 0.5 hour 95 ℃ of following mechanical stirring.

(3) solution A is added dropwise among the slurries B under 95 ℃ of stirrings, speed is dripped in control to be made it to add in 2 hours, continue then under this temperature, to stir 2 hours, and last heat filtering, boiling water is washed till no fluorion, makes filter cake C.

(4) filter cake C is joined in rare HCl aqueous solution that 100ml PH=3.9 is housed,, filter at last and be washed to no chlorion, make product F-1 zeolite 95 ℃ of following constant temperature mechanical stirring 3 hours.

Chemical analysis results is as follows:

Degree of crystallinity: 99%

Lattice constant: 24.48A

SiO ₂/Al ₂O ₃：8.12

Stray crystal is analyzed: do not have

Example 6

(1) with step (1) in the example 4.

(2) take by weighing the NH of 10g butt ₄Y zeolite (SiO ₂/ Al ₂O ₃=5.42), other operation is with step (2) in the example 4.

(3) with step (3) in the example 4.

(4) with step (4) in the example 4.

Chemical analysis results is as follows:

Degree of crystallinity: 98%

Lattice constant: 24.50A

SiO ₂/Al ₂O ₃：7.83

Stray crystal is analyzed: do not have

Example 7

(1) with step (1) in the example 4.

(2) take by weighing the KY zeolite (SiO of 10g butt ₂/ Al ₂O ₃=5.21), other operation is with step (2) in the example 4.

(3) with step (3) in the example 4.

(4) with step (4) in the example 4.

Chemical analysis results is as follows:

Degree of crystallinity: 94%

Lattice constant: 24.49A

SiO ₂/Al ₂O ₃：7.77

Stray crystal is analyzed: do not have

Example 8

(1) with step (1) in the example 4.

(2) take by weighing the CaY zeolite (SiO of 10g butt ₂/ Al ₂O ₃=5.36), other operation is with step (2) in the example 4.

(3) with step (3) in the example 4.

(4) with step (4) in the example 4.

Chemical analysis results is as follows:

Degree of crystallinity: 89%

Lattice constant: 24.47A

SiO ₂/Al ₂O ₃：8.05

Stray crystal is analyzed: do not have

Example 9

(1) with step (1) in the example 4.

(2) take by weighing the REY zeolite (SiO of 10g butt ₂/ Al ₂O ₃=5.41), other operation is with step (2) in the example 4.

(3) with step (3) in the example 4.

(4) with step (4) in the example 4.

Chemical analysis results is as follows:

Degree of crystallinity: 91%

Lattice constant: 24.53A

SiO ₂/Al ₂O ₃：7.65

Stray crystal is analyzed: do not have

Example 10

(1) with step (1) in the example 4.

(2) take by weighing the USY zeolite (SiO of 10g butt ₂/ Al ₂O ₃=5.72), other operation is with step (2) in the example 4.

(3) with step (3) in the example 4.

(4) with step (4) in the example 4.

Chemical analysis results is as follows:

Degree of crystallinity: 87%

Lattice constant: 24.42A

SiO ₂/Al ₂O ₃：9.4

Stray crystal is analyzed: do not have

Example 11

(1) with step (1) in the example 4.

(2) take by weighing the REUSY(SiO of 10g butt ₂/ Al ₂O ₃=5.87), other operation is with step (2) in the example 4.

(3) with step (3) in the example 4.

(4) with step (4) in the example 4.

Chemical analysis results is as follows:

Degree of crystallinity: 89%

Lattice constant: 24.43A

SiO ₂/Al ₂O ₃：9.2

Stray crystal is analyzed: do not have

Example 12

(1) takes by weighing 1.66g MgSiF ₆Crystal joins the NH of 50ml 2M ₄NO ₃In the aqueous solution, dissolving makes solution A.

(2) take by weighing the NH of 10g butt ₄NaY zeolite (secondary ammonium ion exchange SiO ₂/ Al ₂O ₃=5.10), join 100ml 2M NH ₄NO ₃In the aqueous solution, 80 ℃ of mechanical stirring 0.5 hour make slurries B.

(3) solution A is added dropwise among the slurries B under 98 ℃ of agitation conditions, speed is dripped in control to be made it to add in 2 hours, continues then to stir 1.5 hours under this temperature, and last heat filtering and boiling water are washed till no fluorion, make filter cake C.

(4) filter cake C is joined rare HNO of 100ml PH=3.6 ₃In the aqueous solution,, filter and be washed to neutrality then, make product F-1 zeolite 90 ℃ of following constant temperature mechanical stirring 1 hour.

Chemical analysis results is as follows:

Degree of crystallinity: 89%

Lattice constant: 24.48A

SiO ₂/Al ₂O ₃：7.14

Stray crystal is analyzed: do not have

Example 13

(1) takes by weighing 1.82g CaSiF ₆Crystal joins 50ml 2M NH ₄NO ₃In the aqueous solution, dissolving makes solution A.

(2) with step (2) in the example 12.

(3) with step (3) in the example 12.

(4) with step (4) in the example 12.

Chemical analysis results is as follows:

Degree of crystallinity: 86%

Lattice constant: 24.49A

SiO ₂/Al ₂O ₃：7.69

Stray crystal is analyzed: do not have

Example 14

(1) takes by weighing 2.30g SrSiF ₆Crystal joins 50ml 2M NH ₄NO ₃In the aqueous solution, dissolving makes solution A.

(2) with step (2) in the example 12.

(3) with step (3) in the example 12.

(4) with step (4) in the example 12.

Chemical analysis results is as follows:

Degree of crystallinity: 91%

Lattice constant: 24.48A

SiO ₂/Al ₂O ₃：7.46

Stray crystal is analyzed: do not have

Comparative example 4(USY prepare zeolite)

The USY zeolite can prepare by the following step.

(1) takes by weighing the NaY zeolite (SiO of 10g butt ₂/ Al ₂O ₃=5.03), join 100ml 2M NH ₄NO ₃In the aqueous solution, stirred 1 hour, filter then, wash three times at 95 ℃ of following constant temperature.Repeat exchange again and do once, can make filter cake A.

(2), and remain 1kgf/cm with filter cake A 550 ℃ of steam roastings 2 hours in the elevated-temperature seal stove ²Pressure makes product B.

(3) with the B swap operation three times of repeating step (1) again,, just make comparative sample USY zeolite at last with filtration cakes torrefaction.

Chemical analysis results is as follows:

Degree of crystallinity: 92%

Lattice constant: 24.56A

SiO ₂/Al ₂O ₃：5.72

Stray crystal is analyzed: do not have

Example 15

The pyrolysis reactivity of F-1 zeolite can be illustrated by following step.

(1) with the butt product F-1 in the example 4, butt product LZ-210 in the comparative example 3 and the butt product USY in the comparative example 4 are respectively the zeolite component and make normal heptane scission reaction catalyzer.The weight percent of this catalyzer is composed as follows:

Adhesive A l ₂O ₃Molecular sieve WO ₃+ NiO

20 50 30

(2) the normal heptane crack reacting condition is determined by the following table data:

Pre-curing temperature

Prevulcanized pressure

The prevulcanized time

Temperature of reaction

Reaction pressure

Reaction velocity

H ₂/ hydrocarbon volume ratio

250℃

60atm

6 hours

260－300℃

60atm

2.0hr ^-1

1500

(3) resulting normal heptane scission reaction result is provided by following table on little inverse spectrum:

By top result as can be seen, the F-1 zeolite has higher pyrolysis reactivity than LZ-210 and USY zeolite, and under identical reaction conditions, its temperature of reaction is lower about 10 ℃ than LZ-210, and is lower more than 20 ℃ than USY.

Claims

1, a kind of is the method for feedstock production high-silicon Y-Zeolite with hexafluorosilicate and Y zeolite, is that Y zeolite is made slurries, slowly adds the hexafluorosilicic acid salts solution under finite concentration and agitation condition, it is characterized in that adopting following steps:

A, hexafluorosilicate comprise water-soluble and water-fast hexafluorosilicate, and it is made hexafluorosilicic acid salts solution I with the weakly acidic solution heating for dissolving;

B, can adopt the zeolite raw material of any kind of positively charged ion Y zeolite, and this zeolite made acid slurries II for reaction;

C, the slurries II is warmed up to 40-200 ℃, and under agitation condition with 0.01-1.00mol SiF ^2- ₆The speed of/hour kilogram Y zeolite drips a certain amount of solution I, continues then to stir at least 0.5 hour under 70-200 ℃ of condition, and filtration, washing make the filter cake III;

D, the filter cake III is placed acidic solution, be warming up to 50-150 ℃ of stirring after at least 1 hour, filter, washing makes the filter cake IV;

E, basis are to product Na ₂The requirement of O content exchanges the filter cake IV 1-5 time with ammonium salt solution.

2, in accordance with the method for claim 1, the PH that it is characterized in that the used weakly acidic solution of step a is 4-6, and the hexafluorosilicic acid salt concn is 0.05-0.50M, preferably 0.10-0.30M.

3, in accordance with the method for claim 2, it is characterized in that preferably strong acid ammonium salt solution of the used weakly acidic solution of step a.

4, in accordance with the method for claim 1, the PH that it is characterized in that the slurries II is 3-6, the most handy strong acid ammonium salt solution.

5, in accordance with the method for claim 1, it is characterized in that Y zeolite content is 0.05-0.50g/ml, preferably 0.1-0.2g/ml in the slurries II.

6, in accordance with the method for claim 1, it is characterized in that step c preferably is warming up under the 80-150 ℃ of agitation condition with 0.1-0.8mol SiF in the slurries II ^2- ₆The speed of/hour kilogram Y zeolite drips the solution I.

7, in accordance with the method for claim 1, it is characterized in that among the step c that the reaction mixed serum after the solution I dropwises is preferably in and continues under the 80-120 ℃ of condition to stir to be no less than 1 hour, and filters the deionized water of using heat when washing.

8, in accordance with the method for claim 1, it is characterized in that steps d is that the filter cake III is placed PH is the acidic solution of 2-6, making Y zeolite content is 0.05-0.50g/ml, preferably the slurries IV of 0.1-0.2g/ml, these slurries preferably are warming up to 70-120 ℃, stir 2-6 hour.