CN102464325B - Preparation method of mesoporous-microporous zeolite molecular sieve - Google Patents
Preparation method of mesoporous-microporous zeolite molecular sieve Download PDFInfo
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Abstract
The invention discloses a preparation method of a mesoporous-microporous zeolite molecular sieve. The method comprises the steps of: firstly, treating microporous zeolite in a closed system containing an organic solvent with low molecular weight by utilizing alkali solution; secondly, treating the microporous zeolite by acid solution; and lastly, separating, washing and drying to obtain the mesoporous-microporous zeolite. According to a modification method of the zeolite provided by the invention, when the alkali is treated, the generation of a mesoporous structure is promoted by the added organic solvent, so that a microporous structure is more effectively converted to a mesopore while the microporous structure is stabilized and protected; and amorphous alumina in a zeolite crystal can be eluted by a sequential acid treatment process, so that a hole channel is dredged and a total specific surface area is increased, thus the method provided by the invention can be used for keeping more integrated micropores in the mesoporous-microporous zeolite, providing more mesopores and increasing the BET (Brunauer Emmett Teller) specific surface area.
Description
Technical field
The present invention relates to a kind of preparation method of mesoporous-microporous zeolite molecular sieve, belong to Zeolite synthesis modification field, specifically a class micro-pore zeolite is prepared to a kind of zeolite molecular sieve with mesoporous-compound pore canal system of micropore through modification.
Background technology
Micro-pore zeolite is because of its regular microvoid structure, suitable acidity, and good thermostability and hydrothermal stability are widely used in petroleum industry.But micro-pore zeolite inevitably has some natural defects, its narrow duct (being less than 2nm) is in relating to macromolecular reaction, the mass transfer diffusional resistance of material of very easily inducing reaction is excessive, react inside, macromolecular reaction thing crystal extremely difficult to get access duct, so just can not give full play to the catalysis efficiency of zeolite; And macromole product is out also comparatively difficult from duct internal divergence, and very easily coking causes catalyst deactivation.The invention of M41S series mesopore molecular sieve, for micro-pore zeolite synthesis modification provides good reference.M41S series mesopore molecular sieve has the adjustable mesoporous aperture structure of 2～10nm, can solve the mass transfer problem in micro-pore zeolite such as reaction mass, but because it is thermally-stabilised and hydrothermal stability is poor, the too low and very difficult industrial application of acid amount.Exploitation has the micro-pore zeolite molecular sieve of meso-hole structure, makes micropore and mesoporous organic combination, is a focus in the synthetic field of current catalytic material.
< < Appl Catal > > (2001,219:33-43) adopt the NaOH solution-treated ZSM-5 zeolite 300min of 0.2mol/L, obtain a kind of Microporous zeolite ZSM-5 with meso-hole structure, after alkali modification, mesoporous specific surface area is from 6.6 m
2/ g is increased to 115.4m
2/ g, micropore specific area is from 296.4 m
2/ g is reduced to 205m
2/ g.Although it is more that micropore specific area retains, mesoporous content is also lower.
Patent CN101428817A processes ZSM-5 zeolite 10～48 hours in 20～90 ℃ with the alkaline solution of 0.1～5mol/L, obtains the ZSM-5 zeolite that a kind of diameter is the large cavity structure of 160～190nm, and mesoporous specific surface area is the highest can reach 217 m for it
2/ g left and right, but its micropore specific area is seriously damaged, and only has 141.3m
2/ g, can reduce the reactive behavior of zeolite so greatly.
Patent CN1530322A processes ZSM-5 zeolite 1～7 hour in 50～100 ℃ with the alkaline solution of 0.1～0.5mol/L, the highlyest can obtain 250 m
2the mesoporous specific surface area of/g, but its microvoid structure is also to destroy seriously.
< < Journal of Catalysis > > (2007,251:21-27) adopt the NaOH solution of 0.2mol/L to process mordenite 30min at 65 ℃, also obtain a kind of microporous filament geolyte with meso-hole structure, after alkali modification, mesoporous specific surface area is from 8 m
2/ g is increased to 115m
2/ g.
< < Microporous and Mesoporous Materials > > (2004,69:29 – 34) with micro-pore zeolites such as NaOH solution-treated β, mordenite, ZSM-5, all obtain the zeolitic material that contains meso-hole structure.Wherein after alkali modification the mesoporous specific surface area of β zeolite from 45m
2/ g is increased to 325m
2/ g; The mesoporous specific surface area of mordenite is from 50m
2/ g is increased to 140m
2/ g; The mesoporous specific surface area of ZSM-5 zeolite is from 40 m
2/ g is increased to 225m
2/ g.But the preparation efficiency of this mesoporous-microporous zeolite material is lower, the mesoporous area producing needs to improve.
At present, that has reported prepares document and the patent of mesoporous-microporous zeolite about alkali treatment modifying, main purpose is to manufacture mesoporous with the part microvoid structure of alkali destruction micro-pore zeolite, improve mesoporous specific surface area, the internal diffusion of material in zeolite crystal improved in the aperture that expands zeolite crystal, thereby reaches the object that improves catalytic performance.Yet prior art also has two obvious shortcomings: the one, and the mesoporous specific surface area producing is also lower; The 2nd, when obtaining higher mesoporous specific surface area, the microporous crystal structure deteriorate of micro-pore zeolite is more serious, and micropore surface is long-pending too low, and this can the serious catalytic activity that reduces zeolite.So higher mesoporous specific surface area is provided, and keeps the zeolitic material of complete microvoid structure to need to develop.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, proposed a kind ofly to aim to provide higher mesoporous specific surface area, and kept complete microvoid structure, there is the preparation method of the zeolite molecular sieve of mesoporous-compound pore canal system of micropore.
The preparation method of mesoporous-microporous zeolite molecular sieve provided by the invention mainly comprises alkaline purification and acid treatment.Alkaline purification process Main Function be alkali in the closed environment that contains lower molecular weight organic solvent, the element silicon in selectively removing zeolite framework and formed mesopore orbit in zeolite crystal, and retain the microporous crystal structure of original micro-pore zeolite; Acid treatment process is the amorphous aluminium in wash-out zeolite crystal, thereby reaches the object in dredging duct.
The preparation method of mesoporous-microporous zeolite molecular sieve provided by the invention comprises the following steps:
(1) get micro-pore zeolite, according to the liquid-solid ratio of 8～100 mL/g, add alkaline solution, under room temperature, stir 0～60 min;
(2) mixture step (1) being obtained is placed in encloses container, according to the liquid-solid ratio of 0.5～10 mL/g, adds lower molecular weight organic solvent, in 30～180 ℃, processes 0.5～7h;
(3) step (2) gained mixture is carried out to separation and washing;
(4) zeolite after the resulting alkaline purification of step (3) is mixed according to a certain ratio with acid solution, under room temperature, stir 5～60 min, then stir process 0.5～7 h at 40～150 ℃;
(5) products therefrom that step (4) obtains passes through separation, washs, is drying to obtain the compound pore canal system zeolite molecular sieve of mesoporous-micropore.
According to the preparation method of mesoporous-microporous zeolite of the present invention, wherein the micro-pore zeolite described in step (1) is selected from one or more in β zeolite, mordenite, ZSM-22 zeolite, ZSM-5 zeolite and MCM-22 zeolite.The silica alumina ratio scope of described micro-pore zeolite is 10～200, preferably 10～50.
Alkaline solution described in step (1) can be a kind of or several mixing solutions in NaOH, KOH, the LiOH aqueous solution.The concentration of alkaline solution is 0.1～7 mol/L, preferably 0.2～2 mol/L; The liquid-solid ratio that adds alkaline solution and micro-pore zeolite is 8～100 mL/g, preferably 10～80 mL/g.Preferably after adding alkaline solution, stir for some time, churning time is generally 10～60min, preferably stirs 20～40min.
Alkaline purification process in step (2) is carried out in encloses container.Described its alkali purification temp is 30～180 ℃, preferably 40～120 ℃; Treatment time is generally 0.5～7h, preferably 2～4h.
The liquid-solid ratio that adds lower molecular weight organic solvent and micro-pore zeolite described in step (2) is 0.5～10 mL/g, preferably 1～5 mL/g.Described lower molecular weight organic solvent generally refers to that carbonatoms is 1～4 alcohol and ketone, is selected from one or more in methyl alcohol, ethanol, propyl alcohol, Virahol and acetone conventionally.
Separation described in step (3) and washing are routine operation well known to those skilled in the art.As separation, can take the method for filtering, washing generally refers to uses deionized water wash.Step generally includes separating for several times and washing operation in (3), is generally 1～6 time.
Acid solution described in step (4) can be a kind of or several mixing solutions in sulfuric acid, hydrochloric acid and salpeter solution.The concentration of acid solution is generally 0.1～3mol/L, preferably 0.2～2mol/L.The liquid-solid ratio of described acid solution and micro-pore zeolite is 20～100 mL/g, is preferably 30～80 mL/g.
Described in step (4), churning time is 5～60min, preferably 20～40min.Described acid-treated temperature is 40～150 ℃, preferably 50～120 ℃; Treatment time is 0.5～7 h, preferably 2～5h.
The mesoporous-microporous zeolite molecular sieve of preparing according to method of the present invention has following feature: this material has the XRD feature spectrogram of original micro-pore zeolite; At N
2the measured aperture of adsorption-desorption exists mesoporous aperture to concentrate.
Compared with prior art, the preparation method of mesoporous-microporous zeolite molecular sieve of the present invention has following characteristics:
Mesoporous-microporous zeolite molecular sieve preparation method provided by the invention can form meso-hole structure, far above prior art in micro-pore zeolite crystal.And mesoporous-microporous zeolite molecular sieve provided by the invention not only has higher mesoporous specific surface area, can also keep complete microvoid structure, be greatly better than prior art; And the BET surface-area of zeolite also has significantly lifting.
In the prior art, in micro-pore zeolite, manufacturing meso-hole structure is mainly rely on alkaline solution to destroy the microvoid structure of zeolite and produce a large amount of losses that mesoporous, such consequence must be brought micropore, reduces the chain carrier of zeolite.And preparation method provided by the invention is airtight, exists and carry out in the environment of lower molecular weight organic solvent.In the alkaline purification process of zeolite, the lower molecular weight organic solvent adding can promote the generation of meso-hole structure, microvoid structure is changed into more efficiently mesoporous, also microvoid structure is played to stable provide protection simultaneously.Alkaline solution can optionally remove the part element silicon in micro-pore zeolite crystal, makes part microvoid structure recurring structure reset and form mesoporous; Acid treatment process after alkaline purification, the amorphous aluminium in can wash-out zeolite crystal, thus reach dredging duct and increase the object of total specific surface area.Therefore of the present invention mesoporous-zeolite molecular sieve of the compound pore canal system of micropore can retain more complete micropore, provide more mesoporous, but also can increase total BET specific surface area.
Accompanying drawing explanation
Fig. 1 is the XRD spectrogram of the mordenite that obtains of embodiment 1.
Fig. 2 is the hole XRD spectrogram of the β zeolite that obtains of embodiment 3.
Fig. 3 is the graph of pore diameter distribution of the mordenite that obtains of embodiment 1.
Fig. 4 is the graph of pore diameter distribution of the β zeolite that obtains of embodiment 3.
Embodiment
In the inventive method, obtained mesoporous-D/max-2500 type full-automatic rotating target x-ray diffractometer that the crystalline structure of the zeolite sample in the compound duct of micropore adopts Rigaku Co., Ltd. to produce characterizes.Experiment condition: Cu target, K α source of radiation, graphite monochromator, operating voltage 40kV, tube current 80mA, sweep limit is 5～40 °, and sweep velocity is 8 °/min, and step-length is 0.1 °.
On the ASAP2420 physical adsorption appearance that the porous of sample is produced in U.S. Mai Ke company, carry out.Experiment condition is: sample is at 300 ℃, under 0.1MPa condition degassed 4 hours, after the nitrogen that is filled with 101.325kPa until sample bottle, take off sample, and after accurately weighing, analyze.Total specific surface area obtains according to BET thermoisopleth Equation for Calculating, and micro pore volume and outer surface area are tried to achieve according to t-Plot graphing method, and pore size distribution adopts BJH method to calculate.
Below by specific embodiment, mesoporous-microporous zeolite molecular sieve preparation method of the present invention is given to detailed description, but be not limited to embodiment.
The raw material sources that use in the embodiment of the present invention and comparative example: ZSM-5 zeolite, β zeolite, mordenite are all purchased from Fushun Petrochemical Company catalyst plant, and silica alumina ratio is respectively 18.7,20.1 and 30.8; ZSM-12 zeolite, MCM-22 zeolite are self-control, and its silica alumina ratio is 28.6 and 26.5.The main porous of micro-pore zeolite is listed in table 1.The acid of using, alkali and solvent are analytical pure chemical reagent.
Embodiment 1
The NaOH solution 2400mL that gets 30g microporous filament geolyte, 0.30 mol/L is placed in beaker, under room temperature condition, stirs 30min, proceeds in a closed reactor, then adds the methyl alcohol of 75mL, in 60 ℃, processes 4h, filtration, washing.Mordenite after washing is placed in to beaker, adds 0.2mol/L hydrochloric acid soln 1500mL, under room temperature condition, stir 20min, proceed to 70 ℃ of processing 3h in water-bath, filter, wash, then be placed in 110 ℃ of dry 12h of baking oven, gained sample number into spectrum is CL1.
As seen from Figure 1, CL1 sample has the feature spectrogram of mordenite, still keeps good zeolite structured.As seen from Figure 3, after modification, exist significantly mesoporous aperture to concentrate in microporous filament geolyte, most probable aperture is 3.5nm, illustrates after treatment, has formed a large amount of meso-hole structures in mordenite.
The KOH solution 40mL that gets 1 g Microporous zeolite ZSM-5,0.60 mol/L is placed in beaker, under room temperature condition, stirs 30min, proceeds in a closed reactor, then adds the ethanol of 3mL, in 80 ℃, processes 3h, filtration, washing.ZSM-5 zeolite after washing is placed in to beaker, adds 0.2mol/L salpeter solution 30mL, under room temperature condition, stir 20min, proceed to 90 ℃ of processing 2h in water-bath, filter, wash, then be placed in 110 ℃ of dry 12h of baking oven, gained sample number into spectrum is CL2.
Embodiment 3
The NaOH solution 2100mL that gets 30 g micropore β, 0.50 mol/L is placed in beaker, under room temperature condition, stirs 30min; Then proceed in a closed reactor, then add the propyl alcohol of 150mL, in 100 ℃, process 4h; Filter, wash; β zeolite after washing is placed in to beaker, adds the sulphuric acid soln 1500mL of 0.8mol/L, under room temperature condition, stir 30min, proceed to 90 ℃ of processing 3h in water-bath, filter, wash, then be placed in 110 ℃ of dry 12h of baking oven, gained sample number into spectrum is CL3.
As seen from Figure 2, CL3 sample has the feature spectrogram of β zeolite, still keeps good Beta zeolite structures.As seen from Figure 4, after modification, exist significantly mesoporous aperture to concentrate in micropore β zeolite, most probable aperture is 3.5nm.
Embodiment 4
The LiOH solution 80mL that gets 1 g micropore ZSM-12,0.20 mol/L is placed in beaker, under room temperature condition, stirs 40min, proceeds in a closed reactor, then adds the propyl alcohol of 2mL, in 120 ℃, processes 2h, filtration, washing.ZSM-12 zeolite after washing is placed in to beaker, adds 0.5mol/L sulphuric acid soln 30mL, under room temperature condition, stir 20min, proceed to 100 ℃ of processing 3h in water-bath, filter, wash, then be placed in 110 ℃ of dry 12h of baking oven, gained sample number into spectrum is CL4.
The NaOH solution 70mL that gets 1 g micropore MCM-22 zeolite, 0.35 mol/L is placed in beaker, under room temperature condition, stirs 30min, proceeds in a closed reactor, then adds the propyl alcohol of 2mL, in 50 ℃, processes 3.5h, filtration, washing.MCM-22 zeolite after washing is placed in to beaker, adds 0.5mol/L sulphuric acid soln 40mL, under room temperature condition, stir 40min, proceed to 80 ℃ of processing 3h in water-bath, filter, wash, then be placed in 110 ℃ of dry 12h of baking oven, gained sample number into spectrum is CL5.
Comparative example 1
According to method described in < < Microporous and Mesoporous Materials > > (2004,69:29 – 34), microporous filament geolyte is carried out to modification.The NaOH solution 3000mL that gets 30g mordenite, 0.10 mol/L is placed in beaker, under room temperature condition, stirs 30min.Proceed in flask again, under refluxing, in 60 ℃ of stirring 30min, filter, wash, then be placed in 110 ℃ of dry 12h, gained sample number into spectrum is CL6.
Comparative example 2
According to method described in < < Microporous and Mesoporous Materials > > (2004,69:29 – 34), micropore β zeolite is carried out to modification.The NaOH solution 3000mL that gets 30g β zeolite, 0.20 mol/L is placed in beaker, under room temperature condition, stirs 30min.Proceed in flask again, under refluxing, in 85 ℃ of stirring 30min, filter, wash, then be placed in 110 ℃ of dry 1h, gained sample number into spectrum is CL7.
Comparative example 3
The NaOH solution 70mL that gets 1 g micropore β zeolite, 0.35 mol/L is placed in beaker, under room temperature condition, stirs 30min, proceeds in a closed reactor, in 50 ℃, processes 3.5h, filtration, washing.β zeolite after washing is placed in to beaker, adds 0.5mol/L sulphuric acid soln 40mL, under room temperature condition, stir 40min, proceed to 80 ℃ of processing 3h in water-bath, filter, wash, then be placed in 110 ℃ of dry 12h of baking oven, gained sample number into spectrum is CL8.
Comparative example 4
The NaOH solution 70mL that gets 1 g microporous filament geolyte, 0.35 mol/L is placed in beaker, under room temperature condition, stirs 30min, proceeds in a closed reactor, in 50 ℃, processes 3.5h, filtration, washing.Mordenite after washing is placed in to beaker, adds 0.5mol/L sulphuric acid soln 40mL, under room temperature condition, stir 40min, proceed to 80 ℃ of processing 3h in water-bath, filter, wash, then be placed in 110 ℃ of dry 12h of baking oven, gained sample number into spectrum is CL9.
The pore structure character of the zeolite sample that embodiment 1～5 and comparative example 1～4 are prepared is listed in table 1.
Embodiment 6
According to comparative example 1 method, prepare mordenite.Get the mordenite 20g of preparation, 0.8mol/L NH
4nO
3200mL mixes in 80 ℃ of water bath processing 2h, refilters washing.Repeat above step 2 time.Again gained solid matter is placed in to 110 ℃ of dry 12h of baking oven.Then in 550 ℃, process 4h.Then carry out high pressure compressing tablet, sieve is got 30～40 order samples and in micro-reaction equipment, is carried out xylene isomerization.Raw materials used composition (massfraction) is: be less than C
7straight-chain paraffin and naphthenic hydrocarbon 0.12%, C
8straight-chain paraffin and naphthenic hydrocarbon 5.83%, benzene 0.35%, toluene 0.87%, ethylbenzene 10.85%, p-Xylol 0.87%, m-xylene 54. 77%, o-Xylol 26.34%.Reaction conditions is: air speed 3.0h
-1, hydrogen-oil ratio 1000,390 ℃ of temperature of reaction, reaction pressure 0.9 MPa.C
8hydrocarbon yield 94.23%, p-Xylol accounts for 13.87% in product, and p-Xylol proportion in dimethylbenzene is 21.22%.
Embodiment 7
According to embodiment 1 method, prepare mordenite.Get the mordenite 20g of preparation, 0.8mol/L NH
4nO
3200mL mixes in 80 ℃ of water bath processing 2h, refilters washing.Repeat above step 2 time.Again gained solid matter is placed in to 110 ℃ of dry 12h of baking oven.Then in 550 ℃, process 4h.Then carry out high pressure compressing tablet, sieve is got 30～40 order samples and in micro-reaction equipment, is carried out xylene isomerization.Raw materials used composition (massfraction) is: be less than C
7straight-chain paraffin and naphthenic hydrocarbon 0.12%, C
8straight-chain paraffin and naphthenic hydrocarbon 5.83%, benzene 0.35%, toluene 0.87%, ethylbenzene 10.85%, p-Xylol 0.87%, m-xylene 54. 77%, o-Xylol 26.34%.Reaction conditions is: air speed 3.0h
-1, hydrogen-oil ratio 1000,390 ℃ of temperature of reaction, reaction pressure 0.9 MPa.C
8hydrocarbon yield 97.53%, p-Xylol accounts for 19.05% in product, and p-Xylol proportion in dimethylbenzene is 25.34%.
Embodiment 8
According to comparative example 2 methods, prepare β zeolite.Get the β zeolite 20g of preparation, 0.8mol/L NH
4nO
3200mL mixes in 80 ℃ of water bath processing 2h, refilters washing.Repeat above step 2 time.Again gained solid matter is placed in to 110 ℃ of dry 12h of baking oven.Then in 550 ℃, process 4h.Then carry out high pressure compressing tablet, sieve is got 30～40 order samples and in micro-reaction equipment, be take standard diesel oil (235 ~ 337 ℃ of diesel oil distillates) as stock oil carries out catalytic cracking, reaction conditions is: air speed 0.3
-1, 70 seconds oil-feed time, 460 ℃ of temperature of reaction.Cracking activity index MA 61.5%, yield of gasoline 28.2%.
Embodiment 9
According to embodiment 3 methods, prepare β zeolite.Get the β zeolite 20g of preparation, 0.8 mol/L NH
4nO
3200mL mixes in 80 ℃ of water bath processing 2h, refilters washing.Repeat above step 2 time.Again gained solid matter is placed in to 110 ℃ of dry 12h of baking oven.Then in 550 ℃, process 4h.Then carry out high pressure compressing tablet, sieve is got 30～40 order samples and in micro-reaction equipment, be take standard diesel oil (235 ~ 337 ℃ of diesel oil distillates) as stock oil carries out catalytic cracking, reaction conditions is: air speed 0.3
-1, 70 seconds oil-feed time, 460 ℃ of temperature of reaction.Cracking activity index MA 65.6%, yield of gasoline 30.8%.
The pore structure character of the related sample of table 1 embodiment
| Sample number into spectrum | BET specific surface area, m 2/g | Mesoporous specific surface area, m 2/g | Micropore specific area, m 2/g | Most probable aperture, nm |
| CL1 | 567 | 196 | 371 | 3.5 |
| CL2 | 570 | 276 | 294 | 3.5 |
| CL3 | 837 | 420 | 417 | 3.5 |
| CL4 | 416 | 227 | 189 | 4 |
| CL5 | 398 | 229 | 169 | 4.5 |
| CL6 | 495 | 140 | 355 | 4 |
| CL7 | 700 | 325 | 375 | 8 |
| CL8 | 786 | 375 | 411 | 4 |
| CL9 | 512 | 153 | 359 | 4 |
| Micropore β | 618 | 99 | 518 | Nothing |
| Micropore ZSM-5 | 364 | 66 | 298 | Nothing |
| Microporous filament geolyte | 506 | 70 | 435 | Nothing |
| Micropore ZSM-12 | 330 | 87 | 253 | Nothing |
| Micropore MCM-22 | 403 | 23 | 380 | Nothing |
Claims (11)
1. a preparation method for mesoporous-microporous zeolite molecular sieve, comprises the following steps:
(1) get micro-pore zeolite, according to the liquid-solid ratio of 8～100 mL/g, add alkaline solution, under room temperature, stir 0～60 min;
(2) mixture step (1) being obtained is placed in encloses container, according to the liquid-solid ratio of 0.5～10 mL/g, adds lower molecular weight organic solvent, in 30～180 ℃, processes 0.5～7h; Described lower molecular weight organic solvent refers to that carbonatoms is 1～4 alcohol and ketone;
(3) step (2) gained mixture is carried out to separation and washing;
(4) zeolite after the resulting alkaline purification of step (3) is mixed according to a certain ratio with acid solution, under room temperature, stir 5～60 min, then stir process 0.5～7 h at 40～150 ℃;
(5) products therefrom that step (4) obtains passes through separation, washs and be drying to obtain mesoporous-microporous zeolite molecular sieve.
2. according to preparation method claimed in claim 1, it is characterized in that, the micro-pore zeolite described in step (1) is selected from β zeolite, mordenite, ZSM-22 zeolite, ZSM-5 zeolite and MCM-22 zeolite.
3. according to the preparation method described in claim 1 or 2, it is characterized in that, the silica alumina ratio scope of the micro-pore zeolite that step (1) is described is 10～200.
4. according to preparation method claimed in claim 3, it is characterized in that, the silica alumina ratio scope of described micro-pore zeolite is 10～50.
5. according to the method for preparation claimed in claim 1, it is characterized in that, the alkaline solution described in step (1) is selected from NaOH, KOH and the LiOH aqueous solution, and the concentration of alkaline solution is 0.1～7 mol/L.
6. according to preparation method claimed in claim 1, it is characterized in that, stir 10～60min after adding alkaline solution in step (1).
7. according to preparation method claimed in claim 1, it is characterized in that, its alkali purification temp in step (2) is 40～120 ℃, and the treatment time is 2～4h.
8. according to preparation method claimed in claim 1, it is characterized in that, described lower molecular weight organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol and acetone.
9. according to preparation method claimed in claim 1, it is characterized in that, the liquid-solid ratio of described acid solution and micro-pore zeolite is 20～100 mL/g, and the concentration of acid solution is 0.1～3mol/L.
10. according to preparation method claimed in claim 1, it is characterized in that, described acid solution is one or more in sulfuric acid, hydrochloric acid and salpeter solution.
11. according to preparation method claimed in claim 1, it is characterized in that, described in step (4), acid-treated temperature is 50～120 ℃, and the treatment time is 2～5h.
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