CN106276963B - A kind of synthetic method of metal-ZSM molecular sieve - Google Patents
A kind of synthetic method of metal-ZSM molecular sieve Download PDFInfo
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- CN106276963B CN106276963B CN201610624243.1A CN201610624243A CN106276963B CN 106276963 B CN106276963 B CN 106276963B CN 201610624243 A CN201610624243 A CN 201610624243A CN 106276963 B CN106276963 B CN 106276963B
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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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/365—Type ZSM-8; Type ZSM-11; ZSM 5/11 intermediate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The present invention provides a kind of synthetic method of metal ZSM molecular sieve, belongs to molecule synthesis technical field.Raw material alkali metal hydroxide, the material containing element silicon and/or the material containing aluminium element, template and water are uniformly mixed to obtain mixed liquor by this method；Mixed liquor is loaded into liner and carries out pre- crystallization for the stainless steel crystallizing kettle of polytetrafluoro；After the product gel cooling of pre- crystallization, the material containing aluminium element, source metal (M) are added thereto；Then proceed to crystallization for a period of time, crystallization product is roasted after deionized water washing and drying and removes template agent removing, up to the ZSM products containing metal.This method cost is relatively low, and preparation process is simple, is adapted to industrialized production.
Description
Technical field
The present invention relates to molecule synthesis technical field, particularly relates to a kind of synthetic method of metal-ZSM molecular sieve.
Background technology
Transition metal modified molecular sieve is because the double-function catalyzing performance with metal and molecular sieve, in catalytic field table
Reveal important effect, especially metal-modified shape-selective molecular sieve ZSM-5 or ZSM-11 is for extending it in catalytic field
It is important using having the function that.Wherein, the ZSM-11 and ZSM-5 that Zn, Ga are modified embody good aromatizing low-carbon paraffin
Activity；The ZSM-5 that Co, Cu are modified is to CO selective reductions CH4Show good activity；The ZSM-5 and ZSM- that Cu is modified
11 can be by atmosphere pollution NO or N2O efficiently decomposes generation N2；The ZSM-5 that Co is modified can also be applied to ethene ammonia oxygen
Change forms acetonitrile；ZSM-5 then shows good activity after being modified by Fe in ethanol liquid hydrocarbon reaction.Prepare gold
The common method of category-molecular sieve is the method for dipping or ion exchange.Wherein, by infusion process introduce metal species often
The surface of molecular sieve is only distributed in, i.e. the outer species of skeleton, pickup excessively also results in the blocking of molecular sieve pore passage.Compared to it
Under, using ion-exchange process, part metals ion can be entered in framework of molecular sieve, become species in skeleton, but
There is the metal species that a part is not introduced into skeleton.It will be appreciated that the ion exchange capacity of molecular sieve is limited
, therefore, the molecular sieve using ion-exchange preparation high metal content is relatively difficult, generally requires repeatedly to be exchanged and high
Temperature roasting, not only increases the cost of preparation, and the cycle is long, efficiency is low, and can be to crystal knot after repeatedly roasting
Structure produces certain destruction.The higher molecular sieve catalyst of load capacity in order to obtain, has researcher by the salt or oxygen of metal
Compound is with having the carrier of high-ratio surface (such as：Molecular sieve) carry out it is dry-mixed after through heating, i.e., solid phase diffusion process reality
Existing metal component is in the scattered of carrier surface.But this method needs to carry out the high-temperature roasting of long period, metal component exists
The distribution of molecular sieve surfaces externally and internally is difficult to control, and be easy to cause the passage of active component.In order to improve efficiency, there is scholar's proposition
A kind of method that microwave-assisted solid-state reaction prepares the Cu-ZSM molecular sieves with higher load amount.That is, first by molecular sieve and alkali
Metal ion solution carries out ion exchange and obtains the ZSM molecular sieve containing alkali metal, is then mixed and added into second with copper acetate again
Alcohol heated by microwave carries out obtaining the Cu-ZSM-11 molecular sieve catalysts of high load amount after solid state ion exchange.It is worth noting
, whether infusion process also or ion-exchange containing in metallic catalyst of obtaining, the metal ion of introducing be all difficult into
Enter into the skeleton structure of molecular sieve.To make full use of the activity of metallic element and molecular sieve pore passage structure to be brought at the same time
Shape selectivity, be introduced directly into the synthesis process metal ion be it is a kind of it is the most direct preparation the molecular sieve containing metal ion
The method of skeleton.Metal species are present in framework of molecular sieve, not only have preferable dispersiveness, also with stronger stabilization
Property.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of synthetic method of metal-ZSM molecular sieve.
This method specifically comprises the following steps：
(1) raw material alkali metal hydroxide, the material containing element silicon, template and water are uniformly mixed to obtain mixed liquor；
(2) mixed liquor obtained in step (1) is loaded into liner and carries out pre- crystallization for the stainless steel crystallizing kettle of polytetrafluoro；
(3) by after the product gel cooling of pre- crystallization in step (2), source metal M is added thereto, and selectively add
Material containing aluminium element, strong stirring 2h；
(4) product in step (3) is continued into crystallization for a period of time, by crystallization product after deionized water washing and drying,
2-6h is roasted at 550 DEG C in Muffle furnace, removes template agent removing, obtains the ZSM products containing metal.
Wherein, the material containing aluminium element can also introduce in step (1) in step (3), correspondingly, in step (3)
After pre- crystallization product gel cooling, source metal M is added thereto.
Step (3) also can be：After the product gel cooling of pre- crystallization in step (2), add contain aluminium element thereto
Material, obtain mixed gel load liner for polytetrafluoro stainless steel crystallizing kettle carry out crystallization for a period of time；After taking out cooling,
Source metal M is added thereto；Wherein, crystallization condition is crystallization 2-24h at 60-200 DEG C.
Wherein, alkali metal hydroxide in building-up process, the material containing aluminium element, the material containing element silicon, source metal M,
The amount proportioning of the material of template and water is 1.0-25：0-4.0：0.1-8.0：12-1000：0.325-9：240-10000；Its
In, the dosage of the material containing element silicon is with SiO2To count, the dosage of alkali metal hydroxide is with Y2O is counted, and template is the tetrabutyl
Ammonium, dosage is with (TBA)2O is counted；The dosage of material containing aluminium element is with Al2O3To count；The dosage of source metal M is with MOxTo count.
Preferably, alkali metal hydroxide, the material containing element silicon, the material containing aluminium element, source metal M, template with
And the amount proportioning of the material of water is 1.5-12：0-2.0：1-4.0：35-800：0.5-3：1000-5000.
The condition of pre- crystallization is crystallization 4-72h at 60-120 DEG C in step (2).Or pre- crystallization condition is prior to 60-120
Crystallization 4-72h at DEG C, then the crystallization 2-36h at 140-200 DEG C.
The crystallization condition for continuing crystallization in step (4) is crystallization 6-60h at 140-200 DEG C.
The cooling means of crystallizing kettle is one or both of air-cooled and water cooling after pre- crystallization terminates in step (3).
Material containing element silicon includes one or both of Ludox, waterglass, ethyl orthosilicate, white carbon, silica gel
And the mixing of the above；Alkali metal hydroxide for one or both of sodium hydroxide, lithium hydroxide and potassium hydroxide and more than
Mixing；Template mixes for one or both of tetrabutylammonium bromide or tetrabutylammonium hydroxide；Material containing aluminium element
Mixing including one or both of aluminum sulfate, sodium aluminate, aluminum nitrate, aluminium chloride, aluminium isopropoxide and the above；Source metal M bags
Include transition metal or thulium；The transition metal includes one in zinc, copper, iron, cobalt, nickel, manganese etc.
Kind, thulium includes one kind in lanthanum, cerium etc..
The ZSM products containing metal obtained in step (4) have the granule-morphology feature of polycrystalline self assembly, and have
The compound multi-stage artery structure of micropore-mesopore.
The above-mentioned technical proposal of the present invention has the beneficial effect that：
In such scheme, using the premise of cheap silicon source, silicon source, transition metal source and a small amount of organic formwork agent
Under, obtain having the ZSM-11 containing transition metal of micropore-mesopore composite construction brilliant by fractional crystallization one-step synthesis
Phase.Compared with traditional ion-exchange (ion exchange in solution, solid state ion exchange) and infusion process, transition metal master
If realizing that it enters in framework of molecular sieve structure by being introduced into a certain stage of building-up process, this avoids above-mentioned tradition
The problem of last handling process step is numerous and diverse in method, metallic element consumption high (ion exchange process).By control silicon source and
Time that transition metal/thulium source introduces and order control final products Molecular Sieve Morphology and pore structure property
Change.Compared with the prior art discloses the preparation method of the ZSM containing metal of preparation, ZSM containing metal provided by the invention points
Son sieve preparation process is simple, and cost is relatively low, is adapted to industrialized production.
Brief description of the drawings
Fig. 1 is the XRD spectra of Zn-ZSM-11 prepared by embodiment 1 in the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of the ZSM-11 containing different metal prepared by 1-8 of the embodiment of the present invention；
Fig. 3 is the graph of pore diameter distribution containing ZnZSM-11 prepared by 1-5 of the embodiment of the present invention；
Fig. 4 is the graph of pore diameter distribution of the ZSM-11 containing Zn, Fe, Cu and Mn prepared by embodiment 5-8 in the present invention.
Embodiment
To make the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with attached drawing and tool
Body embodiment is described in detail.
The present invention provides a kind of synthetic method of metal-ZSM molecular sieve, concretely comprises the following steps：(1) by raw material alkali metal hydrogen
Oxide, the material containing element silicon, template and water are uniformly mixed to obtain mixed liquor；
(2) mixed liquor obtained in step (1) is loaded into liner and carries out pre- crystallization for the stainless steel crystallizing kettle of polytetrafluoro；
(3) by after the product gel cooling of pre- crystallization in step (2), source metal M is added thereto, and selectively add
Material containing aluminium element, strong stirring 2h；
(4) product in step (3) is continued into crystallization for a period of time, by crystallization product after deionized water washing and drying,
2-6h is roasted at 550 DEG C in Muffle furnace, removes template agent removing, obtains the ZSM products containing metal.
Wherein, the material containing aluminium element can also introduce in step (1) in step (3), correspondingly, in step (3)
After pre- crystallization product gel cooling, source metal M is added thereto.
Wherein, step (3) also can be：After the product gel cooling of pre- crystallization in step (2), add contain aluminium thereto
The material of element, obtains mixed gel loading liner and carries out crystallization for a period of time for the stainless steel crystallizing kettle of polytetrafluoro；Take out cold
But after, source metal M is added thereto.Wherein, crystallization condition is crystallization 2-24h at 60-200 DEG C.
It is explained with reference to specific embodiment.
Embodiment 1
(1) under conditions of stirring, following working solution is prepared：Mixture I：By 13.28g Ludox (40%SiO2,
60%H2O, the same below) be uniformly mixed with 10g deionized waters；Solution II：1.43g tetrabutylammonium bromide and 5g deionized waters are mixed
Close uniform；Solution III：0.97g aluminum sulfate and 3g deionized waters are configured to homogeneous solution；Solution IV：By 1.56g sodium hydroxides
It is uniformly mixed with 5g deionized waters；
Under conditions of being stirred continuously, mixture I is uniformly mixed with solution II, III and IV, strong stirring 2h.
(2) obtained gel is placed in the stainless steel crystallizing kettle with polytetrafluoro liner, sealing is placed on to be mixed up in advance
In the baking oven of temperature, the crystallization 24h at 90 DEG C.
(3) preparation work solution V under agitation：0.81g zinc sulfate and 2g deionized waters are configured to uniformly molten
Liquid.The product gel of pre- crystallization in step (2) is cooled to room temperature.Under conditions of stirring, solution V is slowly added into, is continued strong
Power stirs 1-2h.
(4) gel for obtaining step (3) is placed in the stainless steel crystallizing kettle with polytetrafluoro liner, and sealing is placed on
In the baking oven for mixing up temperature in advance, continue crystallization 24h at 170 DEG C.The ratio between amount of material of final reacting mixture is：
12.0Na2O:1.0Al2O3:2.0ZnO:65SiO2:1.6(TBA)2O:1300H2O.After reaction kettle cooling, by solid and mother liquor point
From solid is washed to neutrality through deionized water, in atmosphere after 120 DEG C of dryings, is removed template through 550 DEG C of roasting 3h, is obtained
Molecular screen material original powder.Final powder product is through X-ray diffraction analysis, as a result such as Fig. 1；Its pattern is measured with scanning electron microscope such as
The pattern of nanocrystalline accumulation shown in Fig. 2 b, 8 μm or so of its granularity；The experiment of low temperature nitrogen adsorption desorption measures micropore-mesopore aperture
Distribution is as shown in Figure 3b.
Embodiment 2
The preparation method and dosage of five kinds of working solutions are the same as embodiment 1.
(1) under conditions of being stirred continuously, mixture I is uniformly mixed with solution II and IV, strong stirring 2h.
(2) obtained gel is placed in the stainless steel crystallizing kettle with polytetrafluoro liner, sealing is placed on to be mixed up in advance
In the baking oven of temperature, the crystallization 24h at 90 DEG C.
(3) product gel of pre- crystallization in step (2) is cooled to room temperature.Under conditions of stirring, it is slowly added into molten
Liquid III, strong stirring 0.5h, are then slowly added to solution V, continue strong stirring 1-2h.
(4) gel for obtaining step (3) is placed in the stainless steel crystallizing kettle with polytetrafluoro liner, and sealing is placed on
In the baking oven for mixing up temperature in advance, continue crystallization 24h at 170 DEG C.After reaction kettle cooling, solid is separated with mother liquor, solid
Washed through deionized water to neutrality, in atmosphere after 120 DEG C of dryings, remove template through 550 DEG C of roasting 3h, obtain molecular sieve material
Expect original powder.Final powder product coincide substantially through X-ray diffraction analysis, its result with Fig. 1, its pattern is measured with scanning electron microscope
The granule-morphology that nanometer rods as shown in Figure 2 c are sequentially arranged in the same direction, 3 μm or so of its granularity；Low temperature nitrogen adsorption desorption is real
Test obtains micropore-mesopore pore-size distribution as shown in Figure 3c.
Embodiment 3
The preparation method and dosage of five kinds of working solutions are the same as embodiment 1.
(1) under conditions of being stirred continuously, mixture I is uniformly mixed with solution II and IV, strong stirring 2h.
(2) obtained gel is placed in the stainless steel crystallizing kettle with polytetrafluoro liner, sealing is placed on to be mixed up in advance
In the baking oven of temperature, the crystallization 24h at 90 DEG C.
(3) product gel of pre- crystallization in step (2) is cooled to room temperature.Under conditions of stirring, it is slowly added into molten
Liquid III, strong stirring 2h are placed in the stainless steel crystallizing kettle with polytetrafluoro liner, and sealing is placed on mixes up temperature in advance
In baking oven, the crystallization 12h at 170 DEG C.Then take out and be cooled to room temperature.Under conditions of stirring, solution V is slowly added to, strength
Stir 2h.
(4) gel for obtaining step (3) is placed in the stainless steel crystallizing kettle with polytetrafluoro liner, and sealing is placed on
In the baking oven for mixing up temperature in advance, continue crystallization 24h at 170 DEG C.After reaction kettle cooling, solid is separated with mother liquor, solid
Washed through deionized water to neutrality, in atmosphere after 120 DEG C of dryings, remove template through 550 DEG C of roasting 3h, obtain molecular sieve material
Expect original powder.Final powder product coincide substantially through X-ray diffraction analysis, its result with Fig. 1, its pattern is measured with scanning electron microscope
The spheric granules pattern that nanometer rods as shown in Figure 2 d are sequentially arranged in the same direction, 2.5 μm or so of its grain；Cryogenic nitrogen aspiration takes off
Attached experiment measures micropore-mesopore pore-size distribution as shown in Figure 3d.
Embodiment 4
The preparation method and dosage of five kinds of working solutions are the same as embodiment 1.
(1) under conditions of being stirred continuously, mixture I is uniformly mixed with solution II and IV, strong stirring 2h.
(2) obtained gel is placed in the stainless steel crystallizing kettle with polytetrafluoro liner, sealing is placed on to be mixed up in advance
In the baking oven of temperature, crystallization 24h is after continuation crystallization 6h at 170 DEG C at 90 DEG C..
(3) product gel of pre- crystallization in step (2) is cooled to room temperature.Under conditions of stirring, it is slowly added into molten
Liquid III, strong stirring 0.5h, are then slowly added to solution IV, continue strong stirring 1-2h.
(4) gel for obtaining step (3) is placed in the stainless steel crystallizing kettle with polytetrafluoro liner, and sealing is placed on
In the baking oven for mixing up temperature in advance, continue crystallization 24h at 170 DEG C.After reaction kettle cooling, solid is separated with mother liquor, solid
Washed through deionized water to neutrality, in atmosphere after 120 DEG C of dryings, remove template through 550 DEG C of roasting 3h, obtain molecular sieve material
Expect original powder.Final powder product coincide substantially through X-ray diffraction analysis, its result with Fig. 1；Its pattern is measured with scanning electron microscope
The granule-morphology that acicular nanocrystalline as shown in Figure 2 e is sequentially arranged in the same direction, 2 μm or so of its granularity；Cryogenic nitrogen aspiration takes off
Attached experiment measures micropore-mesopore pore-size distribution as shown in Figure 3 e.
Comparative example 1
Under conditions of stirring, following working solution is prepared：
The preparation method and dosage of five kinds of working solutions are the same as embodiment 1.
Under conditions of being stirred continuously, mixture I and solution II, III, IV are slowly uniformly mixed, strong stirring 0.5h,
Solution IV is then added, continues strong stirring 1-2h.Primogel is placed in the stainless steel crystallizing kettle with polytetrafluoro liner,
Sealing is placed in the baking oven for mixing up temperature in advance, and crystallization 24h, which is placed at 170 DEG C, at 90 DEG C continues crystallization 24h.Reaction kettle
After cooling, solid is separated with mother liquor, solid is washed to neutrality, in atmosphere after 120 DEG C of dryings, through 550 DEG C through deionized water
Roast 3h and remove template, obtain molecular screen material original powder.Final powder product is through X-ray diffraction analysis, its result and Fig. 1
Substantially it coincide；The pattern of the nanocrystalline accumulation of its pattern as shown in Figure 2 a is measured with scanning electron microscope, 10 μm or so of its granularity；Low temperature
The experiment of nitrogen adsorption desorption measures micropore-mesopore pore-size distribution as shown in Figure 3a.
The pore-size distribution of embodiment 1-4 and the molecular screen material prepared by comparison example 1 is as shown in Fig. 2, illustrate not
With influence of the preparation method to holes of products structural property.
Embodiment 5
Under conditions of stirring, following working solution is prepared：
Mixture I：13.28g Ludox, 1.50g sodium hydroxides, 1.43g tetrabutylammonium bromide and 23g deionized waters are mixed
Close uniform；
Solution II：0.81g zinc sulfate and 2g deionized waters are configured to homogeneous solution.
Mixture I strong stirrings 2h is placed in the stainless steel crystallizing kettle with polytetrafluoro liner, sealing is placed on pre-
In the baking oven for first mixing up temperature, take out and be cooled to room temperature after crystallization 24h at 90 DEG C.Under conditions of stirring, it is slowly added into molten
Liquid II, strong stirring 2h.Obtained gel is placed in the stainless steel crystallizing kettle with polytetrafluoro liner, sealing is placed in advance
In the baking oven for mixing up temperature, continue crystallization 24h at 170 DEG C.The ratio between amount of material of final reacting mixture is：
12.0Na2O:2.0ZnO:65SiO2:1.6(TBA)2O:1300H2O.After reaction kettle cooling, solid is separated with mother liquor, solid warp
Deionized water is washed to neutrality, in atmosphere after 120 DEG C of dryings, is removed template through 550 DEG C of roasting 3h, is obtained molecular screen material
Original powder.Final powder product coincide substantially through X-ray diffraction analysis, its result with Fig. 1；Its pattern is measured with scanning electron microscope such as
The American football shape granule-morphology that acicular nanocrystalline shown in Fig. 2 f is sequentially arranged in the same direction, 4 μm or so of its granularity.
Embodiment 6
Other raw material proportionings of the present embodiment and technological process with embodiment 5, unlike：Source metal is changed into sulfuric acid
It is ferrous.The XRD feature spectral peaks of ZSM-11 molecular sieves are presented in obtained product；Pattern such as Fig. 2 g are the ball of acicular nanometer rod self assembly
Shape particle, granularity are 2.5 μm or so；The experiment of low temperature nitrogen adsorption desorption measures micropore-mesopore pore-size distribution as shown in Figure 4 b.
Embodiment 7
Other raw material proportionings of the present embodiment and technological process with embodiment 5, unlike：Source metal is changed into sulfuric acid
Copper.The XRD feature spectral peaks of ZSM-11 molecular sieves are presented in obtained product；Pattern such as Fig. 2 h are the cube of polycrystalline self assembly
Grain, granularity are 3 μm or so；The experiment of low temperature nitrogen adsorption desorption measures micropore-mesopore pore-size distribution as illustrated in fig. 4 c.
Embodiment 8
Other raw material proportionings of the present embodiment and technological process with embodiment 5, unlike：Source metal is changed into sulfuric acid
Manganese.The XRD feature spectral peaks of ZSM-11 molecular sieves are presented in obtained product, and pattern such as Fig. 2 i are the cube of polycrystalline self assembly
Grain, granularity are 4 μm or so；The experiment of low temperature nitrogen adsorption desorption measures micropore-mesopore pore-size distribution as shown in figure 4d.
The raw material type of embodiment 9-16, proportioning and technological process are as shown in the table：
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, some improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (7)
- A kind of 1. synthetic method of metal-ZSM molecular sieve, it is characterised in that：Include the following steps：(1) raw material alkali metal hydroxide, the material containing element silicon, template and water are uniformly mixed to obtain mixed liquor；(2) mixed liquor obtained in step (1) is loaded into liner and carries out pre- crystallization for the stainless steel crystallizing kettle of polytetrafluoro；(3) by after the product gel cooling of pre- crystallization in step (2), the material containing aluminium element is added thereto, is mixed Gel loads liner and carries out crystallization for a period of time for the stainless steel crystallizing kettle of polytetrafluoro；After taking out cooling, metal is added thereto Source M；Wherein, crystallization condition is crystallization 2-24h at 60-200 DEG C；(4) product in step (3) is continued into crystallization for a period of time, by crystallization product after deionized water washing and drying, in horse 2-6h not is roasted at 550 DEG C in stove, removes template agent removing, obtains the ZSM products containing metal；Alkali metal hydroxide, the material containing aluminium element, the material containing element silicon, source metal M, template in the building-up process And the amount proportioning of the material of water is 1.0-25：0-4.0：0.1-8.0：12-1000：0.325-9：240-10000；Wherein, contain The dosage of the material of element silicon is with SiO2To count, the dosage of alkali metal hydroxide is with Y2O is counted, and template is tetrabutylammonium, dosage With (TBA)2O is counted；The dosage of material containing aluminium element is with Al2O3To count；The dosage of source metal M is with MOxTo count；Wherein, containing aluminium member The material of element is not 0.
- 2. the synthetic method of metal-ZSM molecular sieve according to claim 1, it is characterised in that：The alkali metal hydroxide Thing, the material containing aluminium element, the material containing element silicon, source metal M, the amount proportioning of material of template and water are 1.5-12： 0-2.0：1-4.0：35-800：0.5-3：1000-5000, wherein, the material containing aluminium element is not 0.
- 3. the synthetic method of metal-ZSM molecular sieve according to claim 1, it is characterised in that：It is pre- in the step (2) The condition of crystallization is crystallization 4-72h at 60-120 DEG C.
- 4. the synthetic method of metal-ZSM molecular sieve according to claim 1, it is characterised in that：It is pre- in the step (2) Crystallization condition be prior to 60-120 DEG C at crystallization 4-72h, then the crystallization 2-36h at 140-200 DEG C；The step (4) relaying The crystallization condition of continuous crystallization is crystallization 6-60h at 140-200 DEG C.
- 5. the synthetic method of metal-ZSM molecular sieve according to claim 1, it is characterised in that：It is pre- in the step (3) The cooling means of crystallizing kettle is one or both of air-cooled and water cooling after crystallization terminates.
- 6. the synthetic method of metal-ZSM molecular sieve according to claim 1, it is characterised in that：The thing containing element silicon Matter includes the mixing of one or both of Ludox, waterglass, ethyl orthosilicate, white carbon, silica gel and the above；Alkali metal hydrogen Oxide is the mixing of one or both of sodium hydroxide, lithium hydroxide and potassium hydroxide and the above；Template is the tetrabutyl One or both of ammonium bromide or tetrabutylammonium hydroxide mix；Material containing aluminium element includes aluminum sulfate, sodium aluminate, nitric acid The mixing of one or both of aluminium, aluminium chloride, aluminium isopropoxide and the above.
- 7. the synthetic method of metal-ZSM molecular sieve according to claim 1, it is characterised in that：In the step (4) The ZSM products containing metal arrived have the granule-morphology feature of polycrystalline self assembly, and with the compound multi-stage porous of micropore-mesopore Road structure.
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