CN100567152C - Magadiite/ZSM-5 coexisting material and synthetic method thereof - Google Patents
Magadiite/ZSM-5 coexisting material and synthetic method thereof Download PDFInfo
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- CN100567152C CN100567152C CNB2007100390905A CN200710039090A CN100567152C CN 100567152 C CN100567152 C CN 100567152C CN B2007100390905 A CNB2007100390905 A CN B2007100390905A CN 200710039090 A CN200710039090 A CN 200710039090A CN 100567152 C CN100567152 C CN 100567152C
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Abstract
The present invention relates to a kind of Magadiite/ZSM-5 coexisting material and synthetic method thereof, mainly be to solve single, the uncontrollable problem of bore dia of prior art synthetic aperture of porous material distribution.The present invention is by adopting in ZSM-5 molecular screen material building-up process, control the nucleation and the process of growth of molecular sieve well, prepared a kind of Magadiite/ZSM-5 coexisting material, Symbiont phase adjustable ratio wherein, synthetic Magadiite/ZSM-5 coexisting material adopts the composition that comprises following molar relationship: nSiO
2: Al
2O
3, n=50 in the formula～1000 is characterized in that described Magadiite/ZSM-5 coexisting material has two kinds of Symbiont phases, its XRD diffracting spectrum is 15.73 ± 0.1, and 11.14 ± 0.1,9.97 ± 0.1,7.74 ± 0.1,5.14 ± 0.1,3.86 ± 0.05,3.66 ± 0.05,3.45 ± 0.05,3.30 there is the peaked technical scheme of d-spacing at ± 0.05,3.14 ± 0.1 dust places, have solved the problems referred to above preferably.This Magadiite/ZSM-5 coexisting material can be used in the industrial production of methanol dehydration preparing ethylene and propylene.
Description
Technical field
The present invention relates to a kind of Magadiite/ZSM-5 coexisting material and synthetic method thereof.
Background technology
ZSM-5 molecular sieve porous material is applied in field of petrochemical industry widely owing to have good shape selective catalysis performance and thermostability preferably.But, can not handle complicated component because ZSM-5 molecular screen material aperture is evenly single, bore dia is difficult for regulated at will.Magadiite is the two-dimensional layered structure material, its laminate is made up of electronegative Si-0 tetrahedron, thereby has a thermostability preferably, Magadiite has some typical propertieies of charged layer structure material, for example to the absorption of water and some small molecules polarity organic molecules, interlayer has the hydration sodium ion that can be exchanged, has swelling property preferably between the laminate, the little proton that arrives be can hold and polymer equimolecular or group arrived greatly, Na-magadiite can be converted into the H-magadiite solid peracid of crystalline state, and these character have promoted Magadiite in the application aspect cationite and catalyzer.The regularity of Magadiit layer structure and interlamellar spacing controllability make it become the catalytic material that broad prospect of application is arranged in the catalytic field.Contain the Magadiite/ZSM-5 coexisting material of two kinds of components, contain multi-stage artery structure, the aperture is adjustable, can handle molecular diameter complex component not of uniform size, and can bring into play their concerted catalysis effect.
Document CN1565967A, CN1565970A report adopts ZSM-5 molecular sieve or mordenite as crystal seed, adds respectively in the resulting solution of mordenite or ZSM-5 molecular sieve, has synthesized the mixed crystal material of ZSM-5 and mordenite.Its catalytic effect is better than the effect of two kinds of molecular sieve mechanically mixing, but needs to add different crystal seeds in the building-up process as inductor, also needs to add fluorochemical in addition, and building-up process is comparatively complicated.
Document CN1393403 report adopts the method for segmentation crystallization to synthesize middle mesoporous-microporous composite molecular sieve composition, is used for heavy oil upgrading.Synthetic method is to prepare the reaction mixture gel of synthetic microporous molecular sieve earlier, under 30～300 ℃ of conditions, carry out the crystallization of fs then, after the crystallization 3～300 hours, the pH value of adjusting reaction mixture is 9.5～12, and the synthetic used template of mesoporous molecular sieve of adding, and then at 30～170 ℃ from depressing the hydrothermal crystallizing that carries out subordinate phase, crystallization time is 15～480 hours, mesoporous-microporous composite molecular sieve composition in obtaining, but the building-up process of molecular sieve needs the segmentation crystallization, and the pH value also will be regulated in the centre, and synthetic method is also comparatively complicated.
Document CN03133557.8 has reported and has synthesized the composite structure molecular sieve with TON and two kinds of structures of MFI under the static conditions, this molecular sieve has added a spot of crystal seed and salt in the preparation gelation process, control suitable crystallization parameter, can obtain the molecular sieve of two kinds of crystal formation different ratioss, silica alumina ratio obtains the reaction process that composite molecular screen of the present invention can be used for mixture such as petroleum fractions greater than 50 on the lattice of molecular sieve.Building-up process of the present invention also needs to add crystal seed and salt.
Document CN1583562 has reported a kind of double-micropore zeolites molecular sieve and preparation method, it is characterized in that adopting orderly synthesis method, tentatively synthesizes y-type zeolite by certain material proportion earlier; After it is mixed with the tetraethyl-amine bromide solution that is dissolved with ammoniacal liquor, adding a certain amount of silicon sol at last more fully stirs and makes it even, in 130 ℃～140 ℃ following crystallization 4～7 days, obtain having the composite zeolite molecular sieve of the two microvoid structures of Y/ β, this method is also similar with the segmentation crystallization.
Document CN1632115 report utilizes the self-assembling method of biological enzyme at Magadiite stratified material interlayer, prepared a kind of layered silicate interlayer fixed biological enzyme nano composite material, this nano composite material is similar to the structure of sandwich, the phyllosilicate nano particle keeps original structure constant as enzyme immobilization carrier, and myohaemoglobin and oxyphorase are fixed between the silicate laminate.This material catalytic activity in organic solvent is higher than biological enzyme freely.The document does not relate to the symbiosis problem of Magadiite material and in the application of other catalytic fields.
Summary of the invention
The problem that one of technical problem to be solved by this invention is that prior art synthetic aperture of porous material is single, bore dia can not regulated at will.A kind of new Magadiite/ZSM-5 coexisting material is provided, and this Magadiite/ZSM-5 coexisting material has multi-stage artery structure, the characteristics that the aperture can be regulated; Two of technical problem to be solved by this invention is the problems that do not relate to above-mentioned Magadiite/ZSM-5 coexisting material preparation method in the prior art, and a kind of preparation method of new Magadiite/ZSM-5 coexisting material is provided.
In order one of to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of Magadiite/ZSM-5 coexisting material comprises the composition of following molar relationship: nSiO
2: Al
2O
3, n=50 in the formula～1000, wherein said Magadiite/ZSM-5 coexisting material has two kinds of Symbionts of ZSM-5 molecular sieve and Magadiite mutually, its XRD diffracting spectrum is 15.73 ± 0.1,11.14 ± 0.1,9.97 ± 0.1,7.74 ± 0.1,5.14 ± 0.1,3.86 ± 0.05,3.66 ± 0.05,3.45 ± 0.05,3.30 there is d-spacing maximum value at ± 0.05,3.14 ± 0.1 dust places.
In the technique scheme, nSiO
2: Al
2O
3The preferable range of n is n=100～1000 in the formula, Symbiont phase adjustable ratio in the Magadiite/ZSM-5 coexisting material.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of synthetic method of Magadiite/ZSM-5 coexisting material may further comprise the steps:
(1) silicon source, aluminium source, alkali source and water are mixed;
(2) SiO to contain in the silicon source
2Weight is benchmark, adds an amount of crystal seed in above-mentioned mixing solutions, and amount of seed is SiO
20.01～20% of weight, crystal seed are SiO
2/ Al
2O
3Mol ratio is 10～200 the crystal grain that contains the ZSM-5 presoma amorphous substance in 1～500 nanometer;
(3) reaction mixture with molar ratio computing is: SiO
2/ Al
2O
3=50～2000, Na
2O/SiO
2=0.02～8, H
2O/SiO
2=10～500, the pH value of regulator solution is between 8～14;
(4) the above-mentioned reaction mixture that will mix is put into airtight autoclave at 80～220 ℃, crystallization 8～200 hours;
(5) crystallization is good product takes out, and washing is filtered, and after the drying, makes the Magadiite/ZSM-5 coexisting material; Wherein used silicon source is to be selected from least a in organosilicon, soft silica, silicon sol, silica gel, diatomite or the water glass; Used aluminium source is at least a in the oxide compound of the oxyhydroxide that is selected from aluminate, meta-aluminate, aluminium salt, aluminium, aluminium or the aluminiferous mineral; Used alkali source is to be selected from least a in the alkali-metal oxyhydroxide.
In the technique scheme, reaction mixture is with molar ratio computing, and preferable range is: SiO
2/ Al
2O
3=100～1000, Na
2O/SiO
2=0.1～4, H
2O/SiO
2=20～300, the crystal seed preferred version is SiO
2/ Al
2O
3Mol ratio is 20～100 the crystal grain that contains the ZSM-5 presoma amorphous substance in 10～400 nanometers; Be SiO in the amount of seed preferable range raw material
20.1～10% of weight; The preferred version of used dilute acid soln is at least a in dilute hydrochloric acid, dilute sulphuric acid, rare nitric acid or the dilute phosphoric acid, and the preferable range of regulating the pH value is between 9～14; The crystallization temperature preferable range is 100～200 ℃, and the crystallization time preferable range is 10～60 hours.
The synthetic method concrete operations of Magadiite/ZSM-5 coexisting material are, get silicon source, alkali source and the aluminium source of aequum by material proportion, make solution with dissolved in distilled water respectively, then two kinds of solution are mixed, the powerful stirring, stir after 30 minutes and regulate the pH value in 10～13 scopes, supply distilled water again with dilute alkaline soln.Colloidal sol is put into autoclave, control required temperature, crystallization was taken out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours after 10～100 hours, can obtain described Magadiite/ZSM-5 coexisting material.
The present invention is because the condition that has adopted suitable two or more things of while to grow mutually, regulate and be fit to the pH value scope that related thing is grown mutually, control is fit to the silica alumina ratio and the crystallization temperature of growth, under hydrothermal condition, can in mixed sols, induce the crystal seed of two kinds of thing phases simultaneously, in the environment that is fit to their growths, generated this Magadiite/ZSM-5 coexisting material then, and Magadiite is a layer columnar structure, can be by introducing big positively charged ion at interlayer, promptly by the poroid material of the constitutionally stable two dimension of pillared formation, with suitable column-supporting agent pillared after, specific surface area increases, the duct size adjustable, and a large amount of available Bronsted and Lewis catalytic sites are provided.Not only made things convenient for reactant near catalytic active site, and layer and duct size have also improved the selectivity of catalyzed reaction.Because the surface of Magadiite/ZSM-5 coexisting material has than big difference with interface, acidity and specific surface and the simple mutually mechanical blended of thing, contain multistage pore canal, so catalytic performance is preferably arranged, can handle the different mixture material of molecular diameter, can be used for having obtained better technical effect in the industrial production of methanol dehydration preparing ethylene and propylene.
Description of drawings
Fig. 1 is the XRD diffracting spectrum of synthetic Magadiite/ZSM-5 coexisting material;
Fig. 2 is the scanning electron microscope picture of synthetic Magadiite/ZSM-5 coexisting material.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Getting 1137 gram Starsos is dissolved in the 1800 gram deionized waters.In addition 133.4 gram Tai-Ace S 150 are dissolved in the 350 gram deionized waters, add in the sodium silicate solution under stirring.The mixed evenly back of solution is stirred and is added 158 gram quadrols down, and it is 11 that the pH value is regulated with 30% sulphuric acid soln in the back that stirs, and continues then to be stirred to evenly, carries out conventional hydrothermal crystallizing 15 hours under 150 ℃.Product after washing 130 ℃ dry 4 hours down, 550 ℃ of following roastings 3 hours promptly get crystal seed required for the present invention, remember and make M1.
[embodiment 2]
Method and content according to embodiment 1 is provided change the Tai-Ace S 150 add-on into 13.3 grams, make crystal seed required for the present invention, are designated as M2.
[embodiment 3]
Get 33.3 gram Starsos, become solution A, get the silicon sol of 57.4 grams 40% with 100 gram dissolved in distilled water, make solution B with 100 gram distilled water, get 0.48 gram Tai-Ace S 150, make solution C, respectively A and C solution are slowly poured in the B solution with 20 ml distilled waters, the powerful stirring, add 2.6 gram sodium hydroxide, and then add 1.2 gram ZSM-5 crystal seed M1, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: Na: H
2O=1: 0.005: 0.6: 40, mixing solutions is put into autoclave, 180 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make the Magadiite/ZSM-5 coexisting material, the XRD diffracting spectrum as shown in Figure 1,15.73 ± 0.1,11.14 ± 0.1,9.97 ± 0.1,7.74 ± 0.1,5.14 ± 0.1,3.86 ± 0.05,3.66 ± 0.05,3.45 there is d-spacing maximum value at ± 0.05,3.30 ± 0.05,3.14 ± 0.1 dust places.With the XRD diffraction quantitatively as can be known in the coexisting material ZSM-5 quality percentage composition be 40.6%, Magadiite content is 59.4%, the scanning electron microscope picture as shown in Figure 2.
[embodiment 4～7]
According to the method for embodiment 3, use M2 to be crystal seed, raw materials used as shown in table 4, the pH difference of control solution synthesizes the Magadiite/ZSM-5 coexisting material respectively, sees Table 1.D-spacing maximum value data is all identical with embodiment 3 in the XRD diffracting spectrum, and the ratio of Magadiite and ZSM-5 sees Table 3 in the coexisting material.
Table 1
| Embodiment | The pH value of solution value | Sample number into spectrum |
| Embodiment 4 | 8 | FH-4 |
| |
9 | FH-5 |
| Embodiment 6 | 13 | FH-6 |
| Embodiment 7 | 14 | FH-7 |
[embodiment 8～14]
According to the method for embodiment 3, raw materials used as shown in table 4, the different mole proportionings of control solution, synthetic Magadiite/ZSM-5 coexisting material sees Table 2 respectively.D-spacing maximum value data is all identical with embodiment 3 in the XRD diffracting spectrum, and the ratio of Magadiite and ZSM-5 sees Table 3 in the coexisting material.
Table 2
| Embodiment | Solution mole proportioning | Sample number into spectrum |
| Embodiment 8 | Si∶Al∶Na∶H 2O＝1∶0.001∶0.01∶40 | FH-8 |
| Embodiment 9 | Si∶Al∶Na∶H 2O＝1∶0.01∶0.8∶100 | FH-9 |
| |
Si∶Al∶Na∶H 2O＝1∶0.04∶1∶500 | FH-10 |
| Embodiment 11 | Si∶Al∶Na∶H 2O＝1∶0.005∶0.4∶10 | FH-11 |
| Embodiment 12 | Si∶Al∶Na∶H 2O＝1∶0.004∶4∶40 | FH-12 |
| Embodiment 13 | Si∶Al∶Na∶H 2O＝1∶0.005∶2∶200 | FH-13 |
| Embodiment 14 | Si∶Al∶Na∶H 2O＝1∶0.05∶3∶20 | FH-14 |
[embodiment 15～17]
According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, and crystallization temperature is set to 80 ℃ respectively; 130 ℃ and 220 ℃, synthesized the Magadiite/ZSM-5 coexisting material respectively, be designated as FH-15, FH-16 and FH-17.D-spacing maximum value data is all identical with embodiment 3 in the XRD diffracting spectrum, and the ratio of Magadiite and ZSM-5 sees Table 3 in the coexisting material.
[embodiment 18～21]
According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, and crystallization time is controlled to be 8 hours respectively; 20 hours; 100 hours and 200 hours, synthesized the Magadiite/ZSM-5 coexisting material respectively, be designated as FH-18, FH-19, FH-20 and FH-21.D-spacing maximum value data is all identical with embodiment 3 in the XRD diffracting spectrum, and the ratio of Magadiite and ZSM-5 sees Table 3 in the coexisting material.
[embodiment 22～25]
According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, adds M1 crystal seed amount and is respectively 0.01%; 0.1%; 10% and 20%, synthesized the Magadiite/ZSM-5 coexisting material respectively, be designated as FH-22, FH-23, FH-24 and FH-25, d-spacing maximum value data is all identical with embodiment 3 in the XRD diffracting spectrum, and the ratio of Magadiite and ZSM-5 sees Table 3 in the coexisting material.
Table 3
| Sample number into spectrum | Magadiite content (weight %) | ZSM-5 content (weight %) |
| FH-4 | 30.5 | 69.5 |
| FH-5 | 36.4 | 63.6 |
| FH-6 | 62.2 | 37.8 |
| FH-7 | 75.5 | 24.5 |
| FH-8 | 86.2 | 13.8 |
| FH-9 | 35.7 | 64.3 |
| FH-10 | 18.6 | 81.4 |
| FH-11 | 74.3 | 25.7 |
| FH-12 | 88.4 | 11.6 |
| FH-13 | 70.2 | 29.8 |
| FH-14 | 25.3 | 74.7 |
| FH-15 | 17.8 | 82.2 |
| FH-16 | 36.0 | 64.0 |
| FH-17 | 78.8 | 21.2 |
| FH-18 | 63.2 | 26.8 |
| FH-19 | 56.9 | 43.1 |
| FH-20 | 45.1 | 54.9 |
| FH-21 | 40.3 | 59.7 |
| FH-22 | 95.4 | 4.6 |
| FH-23 | 90.9 | 9.1 |
| FH-24 | 24.7 | 75.3 |
| FH-25 | 8.5 | 91.5 |
Table 4
| Sample number into spectrum | The silicon source | The aluminium source | Alkali source | Acid |
| FH-4 | Starso | Tai-Ace |
Sodium hydroxide | Dilute sulphuric acid |
| FH-5 | Silicon sol | Sodium metaaluminate | Sodium hydroxide | Dilute hydrochloric acid |
| FH-6 | Silica gel | Bauxite | Sodium hydroxide | Oxalic acid |
| FH-7 | Diatomite | Aluminium hydroxide, colloidal sol | Sodium hydroxide | Acetate |
| FH-8 | Water glass | Pseudo-boehmite | Sodium hydroxide | Dilute hydrochloric acid |
| FH-9 | Silicon sol | Sodium aluminate | Sodium hydroxide | Dilute sulphuric acid |
| FH-10 | Tetraethoxy | Tai-Ace |
Sodium hydroxide | Dilute hydrochloric acid |
| FH-11 | Silicon sol | Aluminum nitrate | Sodium hydroxide | Dilute hydrochloric acid |
| FH-12 | Soft silica | Aluminum chloride | Sodium hydroxide | Dilute sulphuric acid |
| FH-13 | Silicon sol | Sodium aluminate | Sodium hydroxide | Dilute sulphuric acid |
| FH-14 | Starso, silicon sol | Tai-Ace |
Sodium hydroxide | Dilute sulphuric acid, dilute hydrochloric acid |
| FH-15 | Tetraethoxy, silicon sol | Tai-Ace |
Sodium hydroxide, potassium hydroxide | Dilute sulphuric acid |
| FH-16 | Tetraethoxy | Sodium metaaluminate, Tai-Ace |
Potassium hydroxide, sodium hydroxide | Dilute sulphuric acid, dilute hydrochloric acid |
| FH-17 | Tetraethoxy | Sodium metaaluminate | Potassium hydroxide | Rare nitric acid |
| FH-18 | Water glass | Tai-Ace |
Sodium hydroxide | Rare nitric acid |
| FH-19 | Tetraethoxy | Sodium metaaluminate, Tai-Ace |
Sodium hydroxide | Rare nitric acid |
| FH-20 | Water glass | Sodium aluminate | Potassium hydroxide, sodium hydroxide | Rare nitric acid |
| FH-21 | Silica gel | Sodium aluminate | Sodium hydroxide | Rare nitric acid |
| FH-22 | Soft silica | Sodium aluminate | Sodium hydroxide | Rare nitric acid |
| FH-23 | Silica gel | Sodium aluminate | Sodium hydroxide | Rare nitric acid |
| FH-24 | Silica gel | Sodium aluminate | Sodium hydroxide | Dilute sulphuric acid |
| FH-25 | Silicon sol | Sodium aluminate | Sodium hydroxide | Dilute sulphuric acid |
[embodiment 26]
Get embodiment 3 synthetic coexisting materials, carry out ammonium exchange 3 hours at 90 ℃ with 5 weight % ammonium nitrate solutions.Product after filtration, washing, 130 ℃ down after dry 3 hours, repeat an ammonium exchange again, after filtration, washing, 130 ℃ be down after dry 3 hours, 550 ℃ of following roastings 3 hours, make the Hydrogen coexisting material, then compressing tablet, break into pieces, sieve, it is standby to get 20～40 purpose particles.With methyl alcohol was raw material, is 12 millimeters fixed-bed reactor with diameter, 450 ℃, mass space velocity 1 hour
-1, water/oil quality is to check and rate under the condition of 0.02MPa than 3: 1, pressure, the ethene mass yield reaches 21.18%, the propylene mass yield reaches 28.37%, ethene and propylene diene quality total recovery are 49.56%, have obtained better technical effect.
[embodiment 27]
Get embodiment 3 synthetic coexisting materials, the method for pressing embodiment 26 makes the Hydrogen coexisting material.Get wherein 10 gram Hydrogen coexisting materials, put into the TBAH solution of 200 milliliter of 0.05 mol, use ultra-sonic oscillation 30 minutes, suction filtration is put into 110 ℃ of bakings of baking oven 3 hours then.Coexisting material behind the worth intercalation is measured its specific surface, bore dia and pore volume, measurement result such as table 5 with nitrogen temperature programmed desorption(TPD) device.
[embodiment 28]
Method by embodiment 26 prepares Hydrogen Magadiite/ZSM-5 coexisting material, measures its specific surface, bore dia and pore volume by the method for embodiment 27, and the result is as shown in table 5.
Table 5
| Embodiment | Sample type | Specific surface area (rice 2/ gram) | Pore volume (rice 3/ gram) | Mean pore size (nanometer) |
| Embodiment 27 | Magadiite/ZSM-5 behind the intercalation | 512.29 | 0.2841 | 3.12 |
| Embodiment 28 | Hydrogen Magadiite/ZSM-5 | 438.83 | 0.2474 | 2.04 |
Claims (7)
1, a kind of Magadiite/ZSM-5 coexisting material comprises the composition of following molar relationship: nSiO
2: Al
2O
3, n=50 in the formula～1000 is characterized in that described material has two kinds of Symbionts of ZSM-5 molecular sieve and Magadiite mutually, its XRD diffracting spectrum is 15.73 ± 0.1,11.14 ± 0.1,9.97 ± 0.1,7.74 ± 0.1,5.14 ± 0.1,3.86 ± 0.05,3.66 ± 0.05,3.45 ± 0.05,3.30 there is d-spacing maximum value at ± 0.05,3.14 ± 0.1 dust places.
2, Magadiite/ZSM-5 coexisting material according to claim 1 is characterized in that n=100～1000.
3, the synthetic method of Magadiite/ZSM-5 coexisting material according to claim 1 may further comprise the steps:
(1) silicon source, aluminium source, alkali source and water are mixed;
(2) SiO to contain in the silicon source
2Weight is benchmark, adds an amount of crystal seed in above-mentioned mixing solutions, and amount of seed is SiO in the raw material
20.01～20% of weight, crystal seed are SiO
2/ Al
2O
3Mol ratio is 10～200 the crystal grain that contains the ZSM-5 presoma amorphous substance in 1～500 nanometer;
(3) reaction mixture with molar ratio computing is: SiO
2/ Al
2O
3=50～2000, Na
2O/SiO
2=0.02～8, H
2O/SiO
2=10～500, the pH value of using the diluted acid regulator solution is between 8～14;
(4) the above-mentioned reaction mixture that will mix is put into airtight autoclave at 80～220 ℃, crystallization 8～200 hours;
(5) crystallization is good product takes out, and after washing, filtration and drying, makes the Magadiite/ZSM-5 coexisting material; Wherein used silicon source is selected from least a in organosilicon, soft silica, silicon sol, silica gel, diatomite or the water glass; Used aluminium source is selected from least a in the oxide compound of oxyhydroxide, aluminium of aluminate, meta-aluminate, aluminium salt, aluminium or the aluminiferous mineral; Used alkali source is selected from least a in the alkali-metal oxyhydroxide.
4, the synthetic method of Magadiite/ZSM-5 coexisting material according to claim 3 is characterized in that reaction mixture with molar ratio computing is: SiO
2/ Al
2O
3=100～1000, Na
2O/SiO
2=0.1～4, H
2O/SiO
2=20～300, amount of seed is SiO in the raw material
20.1～10% of weight.
5, the synthetic method of Magadiite/ZSM-5 coexisting material according to claim 3 is characterized in that used dilute acid soln is at least a in dilute hydrochloric acid, dilute sulphuric acid, rare nitric acid or the dilute phosphoric acid, and regulating the pH value is between 9～14.
6, the synthetic method of Magadiite/ZSM-5 coexisting material according to claim 3 is characterized in that described crystal seed is SiO
2/ Al
2O
3Mol ratio is 20～100 the crystal grain that contains the ZSM-5 presoma amorphous substance in 10～400 nanometers.
7, the synthetic method of Magadiite/ZSM-5 coexisting material according to claim 3 is characterized in that crystallization temperature is 100～200 ℃, and crystallization time is 10～60 hours.
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