CN106698463B - A method of synthesis nano-ZSM-5 molecular sieve - Google Patents
A method of synthesis nano-ZSM-5 molecular sieve Download PDFInfo
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Abstract
The invention discloses a kind of methods of 5 molecular sieves of synthesis nanometer ZSM, the synthetic method is that inorganic base, water, template, silicon source, silicon source are mixed to get gel first, ultrasonication after gel is mixed with macropore carbon, then under the conditions of 50~100 DEG C stir process to viscous pasty state, then dry until moisture evaporating completely, it is reloaded into reactor and quantitative watertight reactor is added and carry out crystallization, 5 molecular sieves of nanometer ZSM are obtained after being roasted in oxygen or air atmosphere after obtained solid product filtration washing drying.Synthetic method of the present invention can synthesize 5 molecular sieves of nanometer ZSM in the case of low consumption of template agent, and not only crystallinity is high, but also be free of other Crystal impurities.
Description
Technical field
The present invention relates to a kind of nano-ZSM-5 molecular sieve synthetic method, specifically a kind of high efficiency, low cost synthesis is received
The method of metrical scale ZSM-5 molecular sieve belongs to molecular sieve catalytic material synthesis field.
Background technology
Zeolite molecular sieve with high-specific surface area, good heat and hydrothermal stability, appropriate acidity due to enriching uniform
Micropore, the performances such as surface nature is adjustable are widely used as catalyst, adsorbent, ion-exchanger and new function material.
Currently, the zeolite crystal size industrially used is generally micron order.With the poor quality increasingly of oil quality upgrading and crude oil
The shortcomings that change, microsized zeolite, also gradually amplifies, and the inside diffusional resistance such as substance is excessive, catalytic activity deficiency etc..Little crystal grain is outstanding
It is nano molecular sieve can solve these problems just.Generally nano molecular sieve crystal size is limited within 100nm, by
It is minimum in the crystal grain of nano zeolite, so that external surface area is obviously increased, intracrystalline pore road shortens, and exposed aperture is increased, to make it
With higher reactivity, stronger effect adsorption capacity, those are difficult to happen because diffusion-limited or reactant or
Product molecule size is reacted with zeolite aperture adjoining dimensions, and nano molecular sieve shows more preferably superiority.
Nano molecular sieve is generally prepared using conventional hydrothermal crystallizing synthetic method, relative to the preparation of conventional micron zeolite,
It is big to synthesize difficulty, and is difficult to that product is collected by filtration, causes production cost high, is not easy large-scale production.Nano zeolite is influenced to close
At factor it is very much, including Template Types and dosage, the property of the raw materials such as silicon source silicon source, plastic mode, crystallization method etc. because
Element can all influence the size of zeolite crystal granularity.Such as Lianhui Ding are in " Nanocrystalline zeolite beta:
The effect of template agent on crystal size”（Materials Research Bulletin,
2007,42：584–590）Article in, it is noted that the synthetic method of a kind of nanometer of Beta molecular sieve.It is used in the synthetic method
Silicon source be exactly pure metallic aluminum, metallic aluminium must be in tetraethyl ammonium hydroxide solution by dissolving in advance, using plastic, most
Hydrothermal crystallizing synthesizes Beta zeolites afterwards.But the crystal size of synthetic product is only in TEAOH/SiO2（Molar ratio）It is higher than
It is just in nanoscale range when 0.6, the Beta zeolites of micron level are can only obtain less than 0.6.
The microwave synthesis method of patent CN1730391A nanometer silicate basic hole materials, technical characteristic are in microwave
The zeolite product of nanoscale is synthesized in environment.The advantages of this method is that generated time is short, but disadvantage is but very prominent, is exactly
This special installation of microwave must be used, causes synthesis cost excessively high；And it there is no in current zeolite compound probability industrialized
The industrial prospect of microwave equipment, this technology is very remote.
A kind of synthetic methods of low silica-alumina ratio beta zeolite of patent CN101205072A, technical characteristic are to be with beta zeolites
Initial feed, then mixed according to a certain percentage with silicon source, template etc., finally synthesize the beta zeolite products of nanoscale.
A nanometer beta zeolites are prepared since this method must use a large amount of routine beta zeolites as raw material, synthesis cost is non-
Chang Anggui；If counting conventional beta zeolites synthesis step in, operating process is just more cumbersome.
In addition there are some patented technologies, boiled using additive is added in the synthetic system of zeolite to synthesize nanometer beta
Stone.Such as 6827924 Process for the preparation of nanocrystalline zeolite of patent US
Beta discloses the synthetic method of a kind of nanometer of beta zeolite, is mainly characterized by synthetic system and is free of alkali metal ion, template
Agent is tetraethyl ammonium hydroxide, and additive used is the organic matters such as toxic methanol, toluene.
A kind of method for preparing nanometer high specific surface Beta zeolite of patent CN101717092A is mainly characterized by reacting
Alkali metal chloride is introduced in system, especially introduces the organic solvent additives such as the methanol of severe toxicity, therefore easily jeopardize behaviour
Make the health and safety of personnel.
A kind of synthetic methods of beta zeolite in small crystal grain of patent CN1324762A, there are three technical characteristics, first, silicon source used
For Bio-sil, second is that EPE polyol EPE or lubricating oil etc. are added in the reaction system, third, using different temperatures
Segmentation crystallization method.
A kind of preparation methods of nano molecular sieve of patent CN101182004A, technical characteristic is synthesis material in addition to using
Conventional silicon and aluminum source outside organic formwork agent, also uses distillate, surfactant etc. is used as additive, can synthesize small
In the beta zeolites of 100nm.But this method can increase nano zeolite product due to the use of the additive of the viscosity such as distillate
The difficulty of separation can undoubtedly cause the rising of production cost.
P.R.Hari Prasad Raoa are in " Crystallization of high silica BEA by dry gel
conversion”（Applied Catalysis A:General, 1998,166：97-103）Article in, closed using gas phase
Cheng Laifa nanometers of Beta molecular sieves, specific operating procedure are：According to 0.014~0.092Na2O：20~100SiO2：0~
0.033A12O3：White carbon, aluminum sulfate, water and tetraethyl ammonium hydroxide are uniformly mixed by 0.16~0.5TEAOH molar ratios, then
Dry glue is made by drying.Then dry glue is placed on to the top of special synthesis reactor, the lower part of reactor is placed on a small quantity
Water, dry glue and water do not contact with each other, and finally synthesize Beta molecular sieves under heating conditions.In the synthetic method,
TEAOH：SiO2Under=0.2 or so conditions of mixture ratios, Beta sized zeolite particles about 60nm；Sized zeolite particles can be remote under other conditions of mixture ratios
Higher than nanoscale.
A kind of preparation methods of nano lamellar ZSM-5 zeolite molecular sieve of patent CN103043681A, using micro emulsion method liquid system
Standby nano-sized ZSM-5 zeolite.Preparation process is：Zeolite precursor liquid solution is prepared according to the ratio, by prepared zeolite precursor liquid solution
It is mixed with W/O microemulsions according to a certain percentage with oil phase, surfactant, cosurfactant, then static crystallization, synthesizes
It is 30nm or so ZSM-5 zeolite to go out molecular sieve thickness of thin layer.But the effect of this method is also poor, in high temperature crystallization process
In, synthesized gel rubber is also easy the constraint that high temperature warm-up movement breaks through microemulsion, leads to the generation of bulky grain molecular sieve.
There are many nano molecular screen method at present, but there are still many problems to need to solve in building-up process.One of them
It is that consumption of template agent needed for synthesis is excessive, the excessively high problem of synthesis cost.Although the template dosage that some technologies provide
Ratio range it is very wide, but be verified by experiments when low template dosage, the scale of synthetic product often exceeds nanometer
Scale.Also some technologies synthesize nano zeolite using the method for additive, but can bring environmental pollution again and jeopardize people
The problem of body health.In addition, nano molecular sieve product is difficult to solve the problem of collection.Since nanocrystal grain size is too small, it is difficult to
It is collected using conventional filtration method as common micro molecular sieve, generally requires and collected using centrifugal process, this is greatly improved again
The production cost of nano molecular sieve.
Invention content
For the deficiency of existing nano molecular sieve technology, especially template dosage be excessive and what product was difficult to collect asks
Topic, the present invention provide a kind of method of synthesis nano-ZSM-5 molecular sieve, can effectively reduce the dosage of organic formwork agent, adopt
Product is collected with traditional filtering method, substantially reduces the synthesis cost of nano molecular sieve.
The present invention provides a kind of method of synthesis nano-ZSM-5 molecular sieve, and the crystal structure of molecular sieve is ZSM-5 molecules
Sieve, is free of other Crystal impurities, and crystal size is less than 100nm, the described method comprises the following steps：
（1）It is first that inorganic base is soluble in water, template is added after to be dissolved, adds silicon source, waits for that silicon source dissolving is complete
After silicon source is added, obtain gel after mixing, the molar ratio of material is 0.5~4Na2O:30~120SiO2:Al2O3:
1000~2000H2O:5~20 templates；
（2）By step（1）10~60min of ultrasonication after obtained gel is mixed with macropore carbon, then 50~100
Stir process is then dry under the conditions of 80~180 DEG C to viscous pasty state under the conditions of DEG C, until moisture evaporating completely；
（3）By step（2）Obtained mixture is packed into reactor, adds quantitative water, and then closed reactor carries out
Crystallization, reaction temperature are 150~240 DEG C, and the reaction time is 25~100h；
（4）By step（3）Obtained solid product filtration washing drying, after then being roasted in oxygen or air atmosphere
To nano-ZSM-5 molecular sieve.
In the synthetic method of nano-ZSM-5 molecular sieve of the present invention, step（1）Described in inorganic base be NaOH, KOH,
It is one or more in LiOH；Silicon source is one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate；Silicon source is white carbon
It is one or more in black, silica gel, Ludox or waterglass；Template be tetrapropylammonium hydroxide, n-butylamine, ethylenediamine or oneself
Diamines.
The present invention synthesizes in the method for nano-ZSM-5 molecular sieve, step（1）Described in molar ratio of material be 1~
3.5Na2O:40~100SiO2:A12O3:1200~1800H2O:7~15 templates.
The present invention synthesizes in the method for nano-ZSM-5 molecular sieve, step（2）Middle macropore carbon is a kind of micron-sized carbon materials
Material, grain size are 0.5~100 μm, preferably 1~70 μm, and the aperture of the macropore carbon is 20~150nm, preferably 25~
110nm, more preferably 30~110nm.
The present invention synthesizes in the method for nano-ZSM-5 molecular sieve, step（2）Described in macropore carbon method is prepared by the following procedure
It obtains：（a）Calcium carbonate is mixed with lye, then the stir process at 50~90 DEG C filters, the solid matter being obtained by filtration exists
1~3h is heat-treated at 300~500 DEG C；（b）It will be through step（a）Treated, and calcium carbonate is mixed with water and glucide, stirring 10
After~60min, 1~10h of ultrasonication；（c）By step（b）Obtained solution at 50~100 DEG C stir process to solution
It is then dry at 50~80 DEG C in viscous pasty state, be finally placed in nitrogen atmosphere at 700~1000 DEG C charing process 3~
10h；（d）By step（c）Obtained substance is uniformly mixed with acid solution, and 1~10h is handled at 50~200 DEG C, is washed out dry
It is dry；（e）By step（d）Obtained substance in a nitrogen atmosphere, in 700~1000 DEG C of 3~10h of high-temperature process, obtains macropore carbon.
In the carbon materials preparation method for material, step（a）Described in calcium carbonate be nano-calcium carbonate, the nano-calcium carbonate
Grain size is 30~50nm.The lye is sodium hydroxide, one or both of potassium hydroxide, the concentration of lye is 0.01~
The mass ratio of 0.1mol/L, calcium carbonate and lye is 1：5~1：50, preferably 1：10~1：20.
In the carbon materials preparation method for material, step（b）Described in glucide be sucrose, one kind in glucose or two
Kind, calcium carbonate, glucide, water mass ratio be 0.1~2：1：10~33, preferably 0.2~1：1：13~26.
In the carbon materials preparation method for material, step（c）Described in charing process carried out in nitrogen atmosphere, nitrogen flow rate
For 10~50mL/min, preferably 15~40 mL/min.The charing process heating rate is 1~10 DEG C/min, with constant
Heating rate heats up.The charing process handles 4~8h at 800~950 DEG C.
In the carbon materials preparation method for material, step（d）Described in acid solution be hydrochloric acid or nitric acid, the quality of acid solution is dense
Degree is 20~60%.
In the carbon materials preparation method for material, step（d）Described in treatment conditions be at 100~180 DEG C processing 2~
7h.To be washed with distilled water, the drying is dry 5~15h at 100~140 DEG C for the washing.
In the carbon materials preparation method for material, step（e）Described in high-temperature process carried out in nitrogen atmosphere, nitrogen flow rate
For 10~50mL/min, preferably 15~40 mL/min.The high-temperature process heating rate is 1~10 DEG C/min, with constant
Heating rate heats up.
The present invention synthesizes in the method for nano-ZSM-5 molecular sieve, step（2）The weight ratio of middle macropore carbon and gel butt is
1:1.5~0.1, preferably 1:1.2~0.2.
The present invention synthesizes in the method for nano-ZSM-5 molecular sieve, step（2）Described in ultrasonic treatment time be 20~
40min；Stir process temperature is 60~90 DEG C；The drying temperature is 100~150 DEG C.
The present invention synthesizes in the method for nano-ZSM-5 molecular sieve, step（3）Middle material mol ratio is：0.5~4Na2O:
30~120SiO2:A12O3:20~240H2O:5~20 templates, preferably 1~3.5Na2O:40~100SiO2:A12O3:40~
200H2O:7~15 templates.
The present invention synthesizes in the method for nano-ZSM-5 molecular sieve, step（3）Described in crystallization temperature be 170~200
DEG C, the reaction time is 30~60h.
The present invention synthesizes in the method for nano-ZSM-5 molecular sieve, step（4）Described in washing to be washed with distilled water, institute
It is dry 5~15h at 100~140 DEG C to state dry, is roasted to 1~5h of roasting at 300~600 DEG C.
Compared with prior art, the synthetic method of nano-ZSM-5 molecular sieve provided by the invention has the following advantages：
（1）Synthetic method provided by the invention can synthesize nano-ZSM-5 in the case of low consumption of template agent
Molecular sieve, not only crystallinity is high, but also is free of other Crystal impurities.
（2）In the method for the present invention, synthesized gel rubber is mixed with special macropore carbon, gel is limited in the nanometer of macropore carbon
Crystallization is carried out in duct, so that the size of molecular sieve crystal is limited within the scope of nanoscale.Also, due to receiving
Rice molecular sieve is in the constraint of macropore carbon, and the bulky grain of micron level is formed with macropore carbon, so that it may with using conventional filtering
Operate the product collection mode avoided to wash the impurity such as unreacted raw material using such highly energy-consuming is centrifuged.It is described
The porous of macropore carbon is most important, and when aperture is excessive, gel is in macropore duct since high temperature warm-up movement is easy when crystallization
The crystallization into the free space outside macropore carbon is fled from the constraint for being detached from duct, is formed larger crystal molecular sieve, can not be synthesized cashier
Rice molecular sieve.
（3）In the method for the present invention, step（2）Described in processing method be to stir in a heated condition, make in mixture
Moisture slow evaporation, until solution becomes viscous pasty state；Then processing is further dried again, is a kind of drying of dynamic and quiet
The combination of state drying.Due to, there are larger density variation, being easy to happen phenomenon of phase separation between macropore carbon and synthesized gel rubber.Such as
Fruit just has most of synthesized gel rubber and cannot be introduced into inside the duct of macropore carbon in such a way that conventional static state is dry.In crystalline substance
Change in reaction process, this partial gel can crystallization be that big crystal grain or close glue are linked togather in the free space outside macropore carbon
Small particle molecular sieve can not finally synthesize the uniform nano molecular sieve product of crystal scale.
（4）In the method for the present invention, using the calcium carbonate through base extraction and heat treatment as hard template, required for can obtaining
Carbon material, using the method for the present invention pre-process calcium carbonate, the Surface electric property of calcium carbonate can be made to change, promote one
Divide the calcium carbonate of monodisperse form to assemble, makes several calcium carbonate particles assemble to form miniature coherent condition, in order to be formed
Template needed for macropore duct.And the surface area of material is reduced finally by high-temperature process is carried out to carbon material, reaches tune
The effect for saving surface area and pore structure, can also improve the mechanical strength of material.
Description of the drawings
Fig. 1 is the XRD spectra for the nano-ZSM-5 molecular sieve that embodiment 1 obtains.
Fig. 2 is the TEM photos for the nano-ZSM-5 molecular sieve that embodiment 1 obtains.
Fig. 3 is the XRD spectra for the nano-ZSM-5 molecular sieve that comparative example 2 obtains.
Fig. 4 is the TEM photos for the nano-ZSM-5 molecular sieve that comparative example 2 obtains.
Specific implementation mode
The ZSM-5 molecular sieve synthetic method of the present invention is described in detail below by specific embodiment, but not
It is confined to embodiment.Sial raw material, acid, alkali and solvent for being used in the embodiment of the present invention etc. are analysis pure chemistry reagent, institute
It is 40nm or so with the granularity of calcium carbonate.
Embodiment 1
The preparation of macropore carbon material：
（a）150g calcium carbonate is mixed with 5000mL 0.05mol/L sodium hydroxide solutions, 2h is stirred under the conditions of 70 DEG C；
Then it is filtered, obtained solid sample dry 2.5h under the conditions of 500 DEG C；
（b）To step（a）7000mL distilled water and 300g sucrose are added in obtained calcium carbonate, stirs ultrasound after 30min
Wave handles 5h.
（c）By step（b）The solution of preparation is placed in 70 DEG C of stirred in water bath processing, and moisture evaporation to solution is made to become sticky
State；Then dry under the conditions of 70 DEG C；Finally sample is placed in tube furnace, is passed through nitrogen, nitrogen flow rate 20mL/min；
With 11 DEG C/min from room temperature to 900 DEG C, constant temperature 5h；
（d）By step（c）Obtained substance is uniformly mixed with the hydrochloric acid solution of 5000mL 50%, under the conditions of 140 DEG C at
6h is managed, neutrality is finally washed with water to, dry 10h under the conditions of 100 DEG C,
（e）By step（d）Obtained sample is placed in tube furnace, is passed through nitrogen, nitrogen flow rate 30mL/min；With 5 DEG C/
Min is warming up to 900 DEG C, constant temperature 5h prepares carbon material.
Embodiment 2
（1）It takes 0.12 g sodium hydroxides to be dissolved in 40mL distilled water, adds the tetrapropylammonium hydroxide of 10 mL 25%
In, stir 30 min.0.5 g sodium aluminates are subsequently added into, 30 min are stirred.It is slowly added 7 g white carbons again, stirs 30 min.
（2）By step（1）Obtained synthesized gel rubber is mixed with the macropore carbon prepared by 7.5g embodiments 1, ultrasonication
30min；Then under the conditions of 60 DEG C stir process to viscous pasty state；Then dry under the conditions of 110 DEG C, until moisture steams completely
Hair.
（3）It then will be by step（2）Gained mixture is placed in reactor, adds 9 mL water.Then closed reactor,
Reactor is placed in 180 DEG C of crystallization 50h in baking oven.Then dry under the conditions of 100 DEG C by solid product filtration washing to neutrality
10h, finally 500 DEG C of roasting 3h, gained sample number into spectrum are CL1 in air atmosphere, and gained sample XRD spectra and TEM photos are such as
Shown in Fig. 1 and Fig. 2, it is pure nano-ZSM-5 molecular sieve, is free of other impurity, properties of samples is shown in Table 1.
Embodiment 3
（1）It takes 0.15 g sodium hydroxides to be dissolved in 43mL distilled water, adds the tetrapropylammonium hydroxide of 7 mL 25%
In, stir 30 min.0.55 g sodium aluminates are subsequently added into, 30 min are stirred.It is slowly added 7 g white carbons, stirring 30 again
min。
（2）By step（1）Obtained synthesized gel rubber is mixed with the macropore carbon prepared by 10g embodiments 1, ultrasonication
30min；Then under the conditions of 70 DEG C stir process to viscous pasty state；Then dry under the conditions of 120 DEG C, until moisture steams completely
Hair.
（3）It then will be by step（2）Gained mixture is placed in reactor, adds 10 mL water.Then confined reaction
Reactor is placed in 200 DEG C of crystallization 35h in baking oven by device.Then by solid product filtration washing to neutrality, under the conditions of 100 DEG C
Dry 10h, finally 500 DEG C of roasting 3h in air atmosphere, gained sample number into spectrum are CL2, are pure nano-ZSM-5 molecule
Sieve, is free of other impurity, and properties of samples is shown in Table 1.
Embodiment 4
（1）It takes 0.2 g sodium hydroxides to be dissolved in 40mL distilled water, adds the tetrapropylammonium hydroxide of 5 mL 25%
In, stir 30 min.0.8 g sodium aluminates are subsequently added into, 30 min are stirred.It is slowly added 8 g white carbons again, stirs 20 min.
（2）By step（1）Obtained synthesized gel rubber is mixed with the macropore carbon prepared by 11g embodiments 1, ultrasonication
30min；Then under the conditions of 60 DEG C stir process to viscous pasty state；Then dry under the conditions of 110 DEG C, until moisture steams completely
Hair.
（3）It then will be by step（2）Gained mixture is placed in reactor, adds 12 mL water.Then confined reaction
Reactor is placed in 190 DEG C of crystallization 50h in baking oven by device.Then by solid product filtration washing to neutrality, under the conditions of 100 DEG C
Dry 10h, finally 500 DEG C of roasting 3h in air atmosphere, gained sample number into spectrum are CL3, are pure nano-ZSM-5 molecule
Sieve, is free of other impurity, and properties of samples is shown in Table 1.
Embodiment 5
（1）It takes 0.25 g sodium hydroxides to be dissolved in 35mL distilled water, adds the tetrapropylammonium hydroxide of 15 mL 25%
In, stir 30 min.0.5 g sodium aluminates are subsequently added into, 30 min are stirred.It is slowly added 12 g white carbons, stirring 30 again
min。
（2）By step（1）Obtained synthesized gel rubber is mixed with the macropore carbon prepared by 15g embodiments 1, ultrasonication
25min；Then under the conditions of 65 DEG C stir process to viscous pasty state；Then dry under the conditions of 130 DEG C, until moisture steams completely
Hair.
（3）It then will be by step（2）Gained mixture is placed in reactor, adds 20 mL water.Then confined reaction
Reactor is placed in 180 DEG C of crystallization 55h in baking oven by device.Then by solid product filtration washing to neutrality, under the conditions of 100 DEG C
Dry 10h, finally 500 DEG C of roasting 3h in air atmosphere, gained sample number into spectrum are CL4, are pure nano-ZSM-5 molecule
Sieve, is free of other impurity, and properties of samples is shown in Table 1.
Comparative example 1
According to conventional hydrothermal synthetic method, 0.12 g sodium hydroxides is taken to be dissolved in 30mL distilled water, adds 20 mL 25%
TPAOH in, stir 30 min.0.5 g sodium aluminates are subsequently added into, 30 min are stirred.It is slowly added 7 g white carbons again, stirs
30 min.It is then charged into closed reactor, 180 DEG C of 50 h of crystallization in baking oven.Then by products therefrom supercentrifuge
Multiple centrifuge washing is to neutrality（Conventional filtration operation can not carry out）.Then dry 10h under the conditions of 100 DEG C, finally in air
500 DEG C of roasting 3h in atmosphere, gained sample number into spectrum are CL5, are nano-ZSM-5 molecular sieve, properties of samples is shown in Table 1.
Comparative example 2
According to the material proportion of embodiment 2, does not stir dry link and carry out contrast experiment.
（1）It takes 0.12 g sodium hydroxides to be dissolved in 40mL distilled water, adds the tetrapropylammonium hydroxide of 10 mL 25%
In, stir 30 min.0.5 g sodium aluminates are subsequently added into, 30 min are stirred.It is slowly added 7 g white carbons again, stirs 30 min.
（2）By step（1）Obtained synthesized gel rubber is mixed with the macropore carbon prepared by 7.5g embodiments 1, ultrasonication
30min；Then dry under the conditions of 110 DEG C, until moisture evaporating completely.
（3）It then will be by step（2）Gained mixture is placed in reactor, adds 9 mL water.Then closed reactor,
Reactor is placed in 180 DEG C of crystallization 50h in baking oven.Then dry under the conditions of 100 DEG C by solid product filtration washing to neutrality
10h, finally 500 DEG C of roasting 3h, gained sample number into spectrum are CL6 in air atmosphere, and gained sample XRD spectra and TEM photos are such as
It is ZSM-5 molecular sieve shown in Fig. 3 and Fig. 4, but crystal particle diameter is unevenly distributed, and has both been contained the small crystals less than 100nm, has also been wrapped
Containing the big crystal taken measurements greatly more than 100nm, properties of samples is shown in Table 1.
Comparative example 3
According to the material proportion of embodiment 2, there is the dry link of stirring but carry out contrast experiment that macropore carbon is not added.
（1）It takes 0.12 g sodium hydroxides to be dissolved in 40mL distilled water, adds the tetrapropylammonium hydroxide of 10 mL 25%
In, stir 30 min.0.5 g sodium aluminates are subsequently added into, 30 min are stirred.It is slowly added 7 g white carbons again, stirs 30 min.
（2）By step（1）Obtained synthesized gel rubber ultrasonication 30min；Then stir process is extremely under the conditions of 60 DEG C
Viscous pasty state；Then dry under the conditions of 110 DEG C, until moisture evaporating completely.
（3）It then will be by step（2）Gained mixture is placed in reactor, adds 9 mL water.Then closed reactor,
Reactor is placed in 180 DEG C of crystallization 50h in baking oven.Then dry under the conditions of 100 DEG C by solid product filtration washing to neutrality
10h, finally 500 DEG C of roasting 3h in air atmosphere, gained sample number into spectrum are CL7, and gained sample is ZSM-5 molecular sieve, but brilliant
Body scale is more than 100nm, is not belonging to nano molecular sieve, properties of samples is shown in Table 1.
Table 1 is properties of samples obtained by embodiment and comparative example
Note：It is reference that the relative crystallinity that table 1 is given, which is with the crystallinity of CL1,.
Claims (26)
1. a kind of method of synthesis nano-ZSM-5 molecular sieve, the crystal structure of molecular sieve is ZSM-5 molecular sieve, without other
Crystal impurity, crystal size are less than 100nm, the described method comprises the following steps：
（1）It is first that inorganic base is soluble in water, template is added after to be dissolved, adds silicon source, adds after silicon source dissolving completely
Enter silicon source, obtain gel after mixing, the molar ratio of material is 0.5~4Na2O:30~120SiO2:Al2O3:1000~
2000H2O:5~20 templates；
（2）By step（1）10~60min of ultrasonication after obtained gel is mixed with macropore carbon, then in 50~100 DEG C of items
Stir process is then dry under the conditions of 80~180 DEG C to viscous pasty state under part, until moisture evaporating completely, the macropore carbon
The method of being prepared by the following procedure obtains：（a）Calcium carbonate is mixed with lye, then the stir process at 50~90 DEG C filters, filtering
Obtained solid matter is heat-treated 1~3h at 300~500 DEG C；（b）It will be through step（a）Treated calcium carbonate and water and sugar
Substance mixes, after stirring 10~60min, 1~10h of ultrasonication；（c）By step（b）Obtained solution is at 50~100 DEG C
Lower stir process to solution is in viscous pasty state, then dry at 50~80 DEG C, is finally placed in nitrogen atmosphere 700~1000
3~10h of charing process at DEG C；（d）By step（c）Obtained substance is uniformly mixed with acid solution, and 1 is handled at 50~200 DEG C
~10h, is washed out drying；（e）By step（d）Obtained substance in a nitrogen atmosphere, in 700~1000 DEG C of high-temperature process 3
~10h obtains macropore carbon；
（3）By step（2）Obtained mixture is packed into reactor, adds quantitative water, and then closed reactor carries out crystallization
Reaction, reaction temperature are 150~240 DEG C, and the reaction time is 25~100h；
（4）By step（3）Obtained solid product filtration washing drying, is received after then being roasted in oxygen or air atmosphere
Rice ZSM-5 molecular sieve.
2. according to the method for claim 1, it is characterised in that：Step（1）Described in inorganic base be NaOH, KOH, LiOH
In it is one or more；Silicon source is one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate；Silicon source be White Carbon black,
It is one or more in silica gel, Ludox or waterglass；Template be tetrapropylammonium hydroxide, n-butylamine, ethylenediamine or oneself two
Amine.
3. according to the method for claim 1, it is characterised in that：Step（1）Described in molar ratio of material be 1~3.5Na2O:
40~100SiO2:A12O3:1200~1800H2O:7~15 templates.
4. according to the method for claim 1, it is characterised in that：Step（2）Middle macropore carbon is a kind of micron-sized carbon material,
Grain size is 0.5~100 μm, and the aperture of the macropore carbon is 20~150nm.
5. according to the method described in claim 1 or 4, it is characterised in that：Step（2）Middle macropore carbon is a kind of micron-sized carbon materials
Material, grain size are 1~70 μm, and the aperture of the macropore carbon is 25~110nm.
6. according to the method for claim 5, it is characterised in that：Step（2）Described in macropore carbon aperture be 30~
110nm。
7. according to the method for claim 1, it is characterised in that：Step（a）Described in calcium carbonate be nano-calcium carbonate, it is described
The grain size of nano-calcium carbonate is 30~50nm.
8. according to the method for claim 1, it is characterised in that：Step（a）Described in lye be sodium hydroxide, potassium hydroxide
One or both of, the concentration of lye is 0.01~0.1mol/L.
9. according to the method for claim 1, it is characterised in that：Step（a）The mass ratio of middle calcium carbonate and lye is 1：5~
1：50.
10. according to the method described in claim 1 or 9, it is characterised in that：Step（a）The mass ratio of middle calcium carbonate and lye is
1：10~1：20.
11. according to the method for claim 1, it is characterised in that：Step（b）Described in glucide be sucrose, glucose
One or both of.
12. according to the method for claim 1, it is characterised in that：Step（b）The mass ratio of middle calcium carbonate, glucide, water
It is 0.1~2：1：10~33.
13. according to the method described in claim 1 or 12, it is characterised in that：Step（b）The matter of middle calcium carbonate, glucide, water
Amount is than being 0.2~1：1：13~26.
14. according to the method for claim 1, it is characterised in that：Step（c）Described in charing process in nitrogen atmosphere
It carries out, nitrogen flow rate is 10~50mL/min.
15. according to the method described in claim 1 or 14, it is characterised in that：Step（c）Described in charing process in nitrogen gas
It is carried out in atmosphere, nitrogen flow rate is 15~40 mL/min.
16. according to the method for claim 14, it is characterised in that：Step（c）Described in charing process heating rate be 1~
It 10 DEG C/min, is heated up with constant heating rate, the charing process handles 4~8h at 800~950 DEG C.
17. according to the method for claim 1, it is characterised in that：Step（d）Described in acid solution be hydrochloric acid or nitric acid,
The mass concentration of acid solution is 20~60%.
18. according to the method for claim 1, it is characterised in that：Step（d）Described in treatment conditions be 100~180
2~7h is handled at DEG C.
19. according to the method for claim 1, it is characterised in that：Step（e）Described in high-temperature process in nitrogen atmosphere
It carries out, nitrogen flow rate is 10~50mL/min, and the high-temperature process heating rate is 1~10 DEG C/min, with constant heating speed
Rate heats up.
20. according to the method for claim 19, it is characterised in that：The nitrogen flow rate is 15~40 mL/min.
21. according to the method for claim 1, it is characterised in that：Step（2）The weight ratio of middle macropore carbon and gel butt is
1:1.5~0.1.
22. according to the method described in claims 1 or 21, it is characterised in that：Step（2）The weight of middle macropore carbon and gel butt
Than being 1:1.2~0.2.
23. according to the method for claim 1, it is characterised in that：Step（2）Described in ultrasonic treatment time be 20~
40min；Stir process temperature is 60~90 DEG C；The drying temperature is 100~150 DEG C.
24. according to the method for claim 1, it is characterised in that：Step（3）Middle material mol ratio is 0.5~4Na2O:30
~120SiO2:A12O3:20~240H2O:5~20 templates.
25. according to the method described in claims 1 or 24, it is characterised in that：Step（3）Middle material mol ratio be 1~
3.5Na2O:40~100SiO2:A12O3:40~200H2O:7~15 templates.
26. according to the method for claim 1, it is characterised in that：Step（3）Described in crystallization temperature be 170~200
DEG C, the reaction time is 30~60h.
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