CN106698452A - Method for synthesizing nano-Beta molecular sieve - Google Patents
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Abstract
The invention discloses a method for synthesizing a nano-Beta molecular sieve. The method comprises the following steps: firstly, preparing a structure-directing agent; then mixing inorganic base, water, an aluminum source and a silicon source to obtain a gel; mixing the gel with macroporous carbon and then carrying out ultrasonic treatment; stirring at a temperature of 50-100 DEG C to be in a viscous state; drying until the water is completely evaporated; charging into a reactor and adding to a quantitative water-tight reactor for crystallization; filtering, washing and drying an obtained solid product, and then calcinating in oxygen or air atmosphere to obtain the nano-Beta molecular sieve. The method provided by the invention can synthesize the nano-Beta molecular sieve without template agent, so that the nano-Beta molecular sieve not only has high crystallinity, but also does not contain other crystal impurities.
Description
Technical field
The present invention relates to a kind of method for synthesizing nanometer Beta molecular sieves, the method that specifically a kind of high efficiency, low cost synthesizes nanoscale Beta molecular sieves belongs to molecular sieve catalytic material synthesis field.
Background technology
Due to high-specific surface area, good heat and hydrothermal stability, the acidity of appropriateness enrich homogeneous micropore to zeolite molecular sieve, the performance such as surface nature is adjustable, are widely used as catalyst, adsorbent, ion-exchanger and new function material.At present, the zeolite crystal size generally micron order for industrially using.As oil quality upgrading and the in poor quality increasingly of crude oil, the shortcoming of microsized zeolite are also progressively amplified, the inside diffusional resistance of such as material is excessive, catalysis activity deficiency etc..Especially nano molecular sieve can solve these problems to little crystal grain just.Typically nano molecular sieve crystal size is limited within 100nm, because the crystal grain of nano zeolite is minimum, external surface area is set substantially to increase, shorten in intracrystalline pore road, expose aperture to increase, so as to make it have reactivity higher, stronger effect adsorption capacity, be difficult to occur because diffusion-limited for those or reactant or product molecule size and zeolite aperture adjoining dimensions reaction, nano molecular sieve shows more preferably superiority.
Nano molecular sieve is typically prepared using conventional hydrothermal crystallizing synthetic method, and relative to the preparation of conventional micron zeolite, synthesis difficulty is big, and is difficult to that product is collected by filtration, and causes production cost high, is difficult large-scale production.The factor of influence nano zeolite synthesis is a lot, including Template Types and consumption, the property of the raw material such as silicon source silicon source, plastic mode, and the factor such as crystallization method can all influence the size of zeolite crystal granularity.Such as Lianhui
Ding etc. is 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 a kind of nanometer of synthetic method of Beta molecular sieves.Silicon source used is exactly pure metallic aluminum in the synthetic method, and metallic aluminium must be in tetraethyl ammonium hydroxide solution by dissolving in advance, then by plastic, last hydrothermal crystallizing synthesizes Beta zeolites.But the crystal size of synthetic product is only in TEAOH/SiO2（Mol ratio）Nanoscale scope is just in during higher than 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, its technical characteristic is the zeolite product for synthesizing nanoscale in microwave environment.The advantage of the method is short generated time, but shortcoming is but very prominent, is exactly that must use this special installation of microwave, causes synthesis high cost；And industrialized microwave equipment is there is no in current zeolite compound probability, the industrial prospect of this technology is very remote.
A kind of synthetic methods of low silica-alumina ratio beta zeolite of patent CN101205072A, its technical characteristic is, with beta zeolites as initial feed, then to mix according to a certain percentage with silicon source, template etc., finally synthesizes the beta zeolite products of nanoscale.Because the method must use substantial amounts of conventional beta zeolites that a nanometer beta zeolites are prepared as raw material, therefore synthesis cost is very expensive；If counting conventional beta zeolites synthesis step in, its operating process is just more cumbersome.
There are some patented technologies in addition, a nanometer beta zeolites are synthesized using additive is added in the synthetic system of zeolite.Such as the Process for the preparation of nanocrystalline of patent US 6827924
Zeolite beta, disclose a kind of nanometer of synthetic method of beta zeolites, and it is mainly characterized by synthetic system without alkali metal ion, and template is tetraethyl ammonium hydroxide, and additive used is the organic matters such as poisonous methyl alcohol, toluene.
A kind of method for preparing nanometer high specific surface Beta zeolite of patent CN101717092A, it is mainly characterized by introducing alkali metal chloride in reaction system, the organic solvent additives such as the methyl alcohol of severe toxicity are particularly introduced, therefore easily jeopardizes the health and safety of operating personnel.
A kind of synthetic methods of beta zeolite in small crystal grain of patent CN1324762A, its technical characteristic has three, and one is that silicon source used is Bio-sil, and two is that EPE polyol EPE or lubricating oil etc. are added in reaction system, and three is using the segmentation crystallization method of different temperatures.
A kind of preparation methods of nano molecular sieve of patent CN101182004A, its technical characteristic is synthesis material except using conventional silicon and aluminum source, outside organic formwork agent, also using distillate, surfactant etc. can synthesize the beta zeolites less than 100nm as additive.But the method can increase the difficulty of nano zeolite product separation due to the additive for having used distillate etc. sticky, 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, using vapor- phase synthesis come method nanometer Beta molecular sieves, specific operating procedure is：According to 0.014~0.092Na2O：20~100SiO2：0~0.033A12O3：Be well mixed for white carbon, aluminum sulfate, water and tetraethyl ammonium hydroxide by 0.16~0.5TEAOH molar ratios, and drying is made dry glue.Then dry glue is placed on the top of special synthesis reactor, a small amount of water is placed in the bottom of reactor, and dry glue and water are not contacted with each other, and Beta molecular sieves are finally synthesized under conditions of heating.In the synthetic method, in TEAOH：SiO2Under=0.2 or so conditions of mixture ratios, Beta sized zeolite particles about 60nm；Sized zeolite particles can be far above nanoscale under other conditions of mixture ratios.
A kind of preparation methods of nano lamellar ZSM-5 zeolite molecular sieve of patent CN103043681A, nano-sized ZSM-5 zeolite is prepared using micro emulsion method liquid.Preparation process is：Zeolite precursor liquid solution is prepared by proportioning, the zeolite precursor liquid solution that will be prepared is mixed with W/O microemulsions according to a certain percentage with oil phase, surfactant, cosurfactant, then static crystallization, it is 30nm or so ZSM-5 zeolite to synthesize molecular sieve thickness of thin layer.But the effect of this method is also poor, in high temperature crystallization process, also easy high temperature warm-up movement breaks through the constraint of microemulsion to synthesized gel rubber, causes the generation of bulky grain molecular sieve.
Current nano molecular screen method is a lot, but many problems are still suffered from building-up process to be needed to solve.One of them is that consumption of template agent is excessive needed for synthesis, synthesizes the problem of high cost.Although the ratio range of the template consumption that some technologies are given is very wide, it is verified by experiments when low template consumption, the yardstick of synthetic product often exceeds nanoscale.Also some technologies synthesize nano zeolite using the method for additive, but can bring environmental pollution again and jeopardize the problem of health.Further, the problem that nano molecular sieve product is collected is difficult to solve.Because nanocrystal particle diameter is too small, it is difficult to be collected using conventional filtration method as common micro molecular sieve, generally requires and collected using centrifugal process, this substantially increases the production cost of nano molecular sieve again.
The content of the invention
For the deficiency of existing nano molecular sieve technology, especially template consumption is excessive and product is difficult to the problem collected, the present invention provides a kind of method for synthesizing nanometer Beta molecular sieves, can be with organic-free template synthesis of molecular sieve, product is collected using traditional filtering method, the synthesis cost of nano molecular sieve is substantially reduced.
The present invention provides a kind of nanometer of synthetic method of Beta molecular sieves, and the crystal structure of molecular sieve is Beta molecular sieves, and without other Crystal impurities, its crystal size is less than 100nm, the described method comprises the following steps：
（1）Beta molecular sieves are added in aqueous slkali, wherein aqueous slkali and the solid mass ratio of the liquid of Beta molecular sieves is 0.01~0.1：1, after stirring mixing, 0.5~8.0h is processed under airtight condition under the conditions of 80~180 DEG C, gained suspension product is structure directing agent；
（2）By inorganic base, silicon source, silicon source and water according to 6~35Na of mol ratio2O:25~120SiO2:A12O3:600~3500H2The ratio mixing of O, is subsequently adding step（1）The structure directing agent for obtaining is well mixed；
（3）By step（2）The gel for obtaining mix with macropore carbon after 10~60min of ultrasonication, then stir process to viscous pasty state, is then dried, until moisture evaporating completely under the conditions of 80~180 DEG C under the conditions of 50~100 DEG C；
（4）By step（3）The mixture for obtaining loads reactor, adds quantitative water, and then closed reactor carries out crystallization, and reaction temperature is 80~180 DEG C, and the reaction time is 10~96h；
（5）By step（4）The solid product filtration washing for obtaining is dried, and a nanometer Beta molecular sieves are obtained after being then calcined in oxygen or air atmosphere.
In the method for present invention synthesis nanometer Beta molecular sieves, step（1）Middle Beta molecular sieves are routine Beta molecular sieves, its SiO2/A12O3Mol ratio is 10~100.
In the method for present invention synthesis nanometer Beta molecular sieves, step（1）Middle aqueous slkali is the mixed solution of one or more in NaOH, KOH and LiOH aqueous solution, and the concentration of the aqueous slkali is 0.1~5 mol/L, preferably 0.5~2 mol/L.
In the method for present invention synthesis nanometer Beta molecular sieves, step（1）Middle aqueous slkali is 0.03~0.06 with the solid mass ratio of the liquid of Beta molecular sieves：1, after stirring mixing, 2.0~4.0h is processed under airtight condition under the conditions of 100~140 DEG C, gained suspension product is structure directing agent.
In the method for present invention synthesis nanometer Beta molecular sieves, step（2）Described in inorganic base be one or more in NaOH, KOH, LiOH；Silicon source is one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate；Silicon source is one or more in White Carbon black, silica gel, Ludox or waterglass.
In the method for present invention synthesis nanometer Beta molecular sieves, step（2）Described in molar ratio of material be 8~30Na2O:30~100SiO2:A12O3:800~3000H2O。
In the method for present invention synthesis nanometer Beta molecular sieves, step（2）Described in structure directing agent addition in terms of Beta molecular sieves and step（2）Middle added silicon source is with SiO2The mass ratio of meter is 0.005~0.06：1, preferably 0.01~0.04：1.
In the method for present invention synthesis nanometer Beta molecular sieves, step（3）Middle macropore carbon is a kind of micron-sized carbon material, and particle diameter is 0.5~100 μm, and preferably 1~70 μm, the aperture of the macropore carbon is 20~150nm, more preferably preferably 25~110nm, 30~110nm.
In the method for present invention synthesis nanometer Beta molecular sieves, step（3）Described in macropore carbon method be prepared by the following procedure obtain：（a）Calcium carbonate is mixed with alkali lye, then the stir process at 50~90 DEG C filters, the solid matter being filtrated to get is heat-treated 1~3h at 300~500 DEG C；（b）Will be through step（a）Calcium carbonate after treatment mixes with water and glucide, after 10~60min of stirring, 1~10h of ultrasonication；（c）By step（b）The solution for obtaining stir process to solution at 50~100 DEG C is in viscous pasty state, is then dried at 50~80 DEG C, is finally placed in nitrogen atmosphere 3~10h of charing process at 700~1000 DEG C；（d）By step（c）The material for obtaining is well mixed with acid solution, and 1~10h is processed at 50~200 DEG C, is washed out drying；（e）By step（d）The material for obtaining 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 particle diameter of the nano-calcium carbonate is 30~50nm.The alkali lye is one or two in NaOH, potassium hydroxide, and the concentration of lye is 0.01~0.1mol/L, and the mass ratio of calcium carbonate and alkali 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, glucose in one or two, 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 be 10~50mL/min, preferably 15~40 mL/min.The charing process heating rate is 1~10 DEG C/min, is heated up with constant heating rate.Described charing process processes 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 mass concentration of acid solution is 20~60%.
In the carbon materials preparation method for material, step（d）Described in treatment conditions be at 100~180 DEG C treatment 2~7h.It is described washing be with distillation water washing, the drying be at 100~140 DEG C dry 5~15h.
In the carbon materials preparation method for material, step（e）Described in high-temperature process carried out in nitrogen atmosphere, nitrogen flow rate be 10~50mL/min, preferably 15~40 mL/min.The high-temperature process heating rate is 1~10 DEG C/min, is heated up with constant heating rate.
In the method for present invention synthesis nanometer Beta molecular sieves, step（3）Middle macropore carbon is 1 with the weight ratio of gel butt:1.5~0.1, preferably 1:1.2~0.2.
In the method for present invention synthesis nanometer Beta molecular sieves, step（3）Described in ultrasonic treatment time be 20~40min；Stir process temperature is 60~90 DEG C；Described drying temperature is 100~150 DEG C.
In the method for present invention synthesis nanometer Beta molecular sieves, step（4）Middle material mol ratio is：4~10Na2O:25~120SiO2:A12O3:15~300H2O, preferably 3~8Na2O:30~100SiO2:A12O3:
20~200H2O。
In the method for present invention synthesis nanometer Beta molecular sieves, step（4）Described in crystallization temperature be 100~150 DEG C, the reaction time be 20~80h.
In the method for present invention synthesis nanometer Beta molecular sieves, step（4）Described in washing be with distillation water washing, the drying be at 100~140 DEG C dry 5~15h, at being roasted to 300~600 DEG C be calcined 1~5h.
Compared with prior art, the method for the synthesis nanometer Beta molecular sieves that the present invention is provided has advantages below：
（1）The synthetic method that the present invention is provided can synthesize a nanometer Beta molecular sieves under the conditions of inorganic template agent, and not only crystallinity is high, and without other Crystal impurities.Structure directing agent prepared by the inventive method, the secondary structure of the Beta zeolites containing a large amount of high activities and other feature cage units.Guide effect is played in the nucleus that these secondary structure units can be grown with other feature cage units directly as Beta molecular sieves, or growth with very strong inducing action to Beta molecular sieves.Compared with directly crystal seed is made using Beta molecular sieves, the guide effect of structure directing agent of the present invention is stronger, it is possible to substitute organic formwork agent, and the Beta molecular sieves of high-crystallinity are synthesized under conditions of organic-free template.
（2）In the inventive method, synthesized gel rubber is mixed with special macropore carbon, gel is limited in the nano pore of macropore carbon carries out crystallization, the size of molecular sieve crystal is limited in the range of nanoscale.Also, because nano molecular sieve is in the constraint of macropore carbon, with the bulky grain that macropore carbon forms micron level, it is possible to wash the impurity such as unreacted raw material using conventional filter operation, it is to avoid use the product collection mode of highly energy-consuming as centrifugation.The porous of the macropore carbon is most important, when aperture is excessive, crystallization in the free space that gel is fled to outside macropore carbon in crystallization in macropore duct due to the constraint that high temperature warm-up movement is easily separated from duct, forms larger crystal molecular sieve, it is impossible to synthesize nano molecular sieve.
（3）In the inventive method, step（2）Described in processing method be to stir in a heated condition, make the moisture slow evaporation in mixture, until solution is changed into viscous pasty state；Then treatment is further dried again, is that a kind of dynamic is dried and static dry combination.Due to there is larger density variation between macropore carbon and synthesized gel rubber, phenomenon of phase separation is susceptible to.If using conventional static dry mode, just having most of synthesized gel rubber and cannot be introduced into inside the duct of macropore carbon.During crystallization, this partial gel can be big crystal grain or the tight viscous small particle molecular sieve being linked togather in crystallization in the free space outside macropore carbon, cannot finally synthesize the homogeneous nano molecular sieve product of crystal yardstick.
（4）In the inventive method, using through base extraction and the calcium carbonate being heat-treated as hard template, required carbon material can be obtained, calcium carbonate is pre-processed using the inventive method, the Surface electric property of calcium carbonate can be made to change, promote the calcium carbonate of a part of single dispersing form to assemble, make several calcium carbonate particles assemble to form miniature coherent condition, in order to form the template needed for macropore duct.And the surface area of material is reduced finally by high-temperature process is carried out to carbon material, the effect of regulation surface area and pore structure is reached, the mechanical strength of material can also be improved.
Brief description of the drawings
Fig. 1 is the XRD spectra of the nanometer Beta molecular sieves that embodiment 1 is obtained.
Fig. 2 is the TEM photos of the nanometer Beta molecular sieves that embodiment 1 is obtained.
Fig. 3 is the XRD spectra of the nanometer Beta molecular sieves that comparative example 2 is obtained.
Fig. 4 is the TEM photos of the nanometer Beta molecular sieves that comparative example 2 is obtained.
Specific embodiment
The method of synthesis Beta molecular sieves of the present invention is described in detail below by specific embodiment, but is not limited 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, and the granularity of calcium carbonate used is 40nm or so.
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 filtered, the solid sample for obtaining dries 2.5h under the conditions of 500 DEG C；
（b）To step（a）7000mL distilled water and 300g sucrose, ultrasonication 5h after stirring 30min are added in the calcium carbonate for obtaining.
（c）By step（b）The solution of preparation is placed in 70 DEG C of stirred in water bath treatment, moisture evaporation to solution is changed into viscous pasty state；Then dried under the conditions of 70 DEG C；Finally sample is placed in tube furnace, nitrogen is passed through, nitrogen flow rate is 20mL/min；With 11 DEG C/min from room temperature to 900 DEG C, constant temperature 5h；
（d）By step（c）The material for obtaining is well mixed with the hydrochloric acid solution of 5000mL 50%, and 6h is processed under the conditions of 140 DEG C, is finally washed with water to neutrality, and 10h is dried under the conditions of 100 DEG C,
（e）By step（d）The sample for obtaining is placed in tube furnace, is passed through nitrogen, and nitrogen flow rate is 30mL/min；900 DEG C are warming up to 5 DEG C/min, constant temperature 5h prepares carbon material.
Embodiment 2
（1）Take 4g
Beta molecular sieves, the NaOH solution 100mL of 1mol/L are placed in beaker, in 30min is stirred under room temperature condition, are transferred in a closed reactor, 120 DEG C for the treatment of 4h in baking oven.Gained suspension is structure directing agent, stand-by.
（2）Take 2.5 g NaOH, 0.5 g sodium aluminates to be placed in 50 mL distilled water, be stirred vigorously until all dissolving.7 g white carbons are slowly added again, are stirred vigorously 30
min.It is subsequently adding on 2.5mL and walks made structure directing agent, is stirred vigorously 30
min。
（3）By step（2）The synthesized gel rubber for obtaining mixes with the macropore carbon prepared by 8g embodiments 1, ultrasonication 30min；Then under the conditions of 60 DEG C stir process to viscous pasty state；Then dried under the conditions of 110 DEG C, until moisture evaporating completely.
（4）Then just step（3）Gained mixture is placed in reactor, adds 5 mL water.Then closed reactor, 140 DEG C of crystallization 50h in baking oven are placed in by reactor.Then by solid product filtration washing to neutrality, 10h is dried under the conditions of 100 DEG C, last 500 DEG C of roasting 3h in air atmosphere, gained sample number into spectrum is CL1, gained sample XRD spectra and TEM photos are as depicted in figs. 1 and 2, it is pure nanometer Beta molecular sieves, without other impurity, properties of samples is shown in Table 1.
Embodiment 3
（1）Take 4g
Beta molecular sieves, the NaOH solution 80mL of 1mol/L are placed in beaker, in 30min is stirred under room temperature condition, are transferred in a closed reactor, 125 DEG C for the treatment of 4h in baking oven.Gained suspension is structure directing agent, stand-by.
（2）Take 2 g NaOH, 0.6 g sodium aluminates to be placed in 50 mL distilled water, be stirred vigorously until all dissolving.5.7 g white carbons are slowly added again, are stirred vigorously 30
min.It is subsequently adding on 2.5mL and walks made structure directing agent, is stirred vigorously 30
min。
（3）By step（2）The synthesized gel rubber for obtaining mixes with the macropore carbon prepared by 8g embodiments 1, ultrasonication 30min；Then under the conditions of 70 DEG C stir process to viscous pasty state；Then dried under the conditions of 120 DEG C, until moisture evaporating completely.
（4）Then just step（3）Gained mixture is placed in reactor, adds 20 mL water.Then closed reactor, 150 DEG C of crystallization 45h in baking oven are placed in by reactor.Then by solid product filtration washing to neutrality, 10h is dried under the conditions of 100 DEG C, finally 500 DEG C of roasting 3h in air atmosphere, gained sample number into spectrum is CL2, is pure nanometer Beta molecular sieves, and without other impurity, properties of samples is shown in Table 1.
Embodiment 4
（1）Take 5g
Beta molecular sieves, the NaOH solution 100mL of 1mol/L are placed in beaker, in 25min is stirred under room temperature condition, are transferred in a closed reactor, 130 DEG C for the treatment of 3.5h in baking oven.Gained suspension is structure directing agent, stand-by.
（2）Take 2.5 g NaOH, 0.45 g sodium aluminates to be placed in 50 mL distilled water, be stirred vigorously until all dissolving.8 g silica gel are slowly added again, are stirred vigorously 30
min.It is subsequently adding on 3.5mL and walks made structure directing agent, is stirred vigorously 30
min。
（3）By step（2）The synthesized gel rubber for obtaining mixes with the macropore carbon prepared by 15g embodiments 1, ultrasonication 30min；Then under the conditions of 60 DEG C stir process to viscous pasty state；Then dried under the conditions of 110 DEG C, until moisture evaporating completely.
（4）Then just step（3）Gained mixture is placed in reactor, adds 12 mL water.Then closed reactor, 150 DEG C of crystallization 80h in baking oven are placed in by reactor.Then by solid product filtration washing to neutrality, 10h is dried under the conditions of 100 DEG C, finally 500 DEG C of roasting 3h in air atmosphere, gained sample number into spectrum is CL3, is pure nanometer Beta molecular sieves, and without other impurity, properties of samples is shown in Table 1..
Embodiment 5
（1）Take 3g
Beta molecular sieves, the NaOH solution 100mL of 1mol/L are placed in beaker, in 30min is stirred under room temperature condition, are transferred in a closed reactor, 115 DEG C for the treatment of 4h in baking oven.Gained suspension is structure directing agent, stand-by.
（2）Take 3 g NaOH, 0.6 g sodium aluminates to be placed in 50 mL distilled water, be stirred vigorously until all dissolving.7.5 g white carbons are slowly added again, are stirred vigorously 30
min.It is subsequently adding on 5mL and walks made structure directing agent, is stirred vigorously 30
min。
（3）By step（2）The synthesized gel rubber for obtaining mixes with the macropore carbon prepared by 10g embodiments 1, ultrasonication 25min；Then under the conditions of 65 DEG C stir process to viscous pasty state；Then dried under the conditions of 130 DEG C, until moisture evaporating completely.
（4）Then just step（3）Gained mixture is placed in reactor, adds 12 mL water.Then closed reactor, 140 DEG C of crystallization 65h in baking oven are placed in by reactor.Then by solid product filtration washing to neutrality, 10h is dried under the conditions of 100 DEG C, finally 500 DEG C of roasting 3h in air atmosphere, gained sample number into spectrum is CL4, is pure nanometer Beta molecular sieves, and without other impurity, properties of samples is shown in Table 1.
Comparative example 1
According to conventional hydrothermal synthetic method, take 0.8 g NaOH and be dissolved in 100
In mL TEAOH, 1.5 g sodium aluminates of rear addition completely to be dissolved are stirred vigorously until all dissolving.24 g white carbons are slowly added again, are stirred vigorously 3h.It is then charged into reactor, closed reactor, reactor is placed in 140 DEG C of crystallization 60h in baking oven.Then by the products therefrom multiple centrifuge washing of supercentrifuge to neutrality（Conventional filtration operation cannot be carried out）.Then 10h is dried under the conditions of 100 DEG C, finally 500 DEG C of roasting 3h in air atmosphere, gained sample number into spectrum is CL5, and the nanometer Beta molecular sieves for being, properties of samples is shown in Table 1.
Comparative example 2
According to the material proportion of embodiment 2, not having stirring to dry link carries out contrast experiment.
（1）Take 4g Beta molecular sieves, the NaOH solution 100mL of 1mol/L is placed in beaker, in 30min is stirred under room temperature condition, be transferred in a closed reactor, 120 DEG C for the treatment of 4h in baking oven.Gained suspension is structure directing agent, stand-by.
（2）Take 2.5 g NaOH, 0.5 g sodium aluminates to be placed in 50 mL distilled water, be stirred vigorously until all dissolving.7 g white carbons are slowly added again, are stirred vigorously 30
min.It is subsequently adding on 2.5mL and walks made structure directing agent, is stirred vigorously 30
min。
（3）By step（2）The synthesized gel rubber for obtaining mixes with the macropore carbon prepared by 8g embodiments 1, ultrasonication 30min；Then dried under the conditions of 110 DEG C, until moisture evaporating completely.
（4）Then just step（3）Gained mixture is placed in reactor, adds 5 mL water.Then closed reactor, 140 DEG C of crystallization 50h in baking oven are placed in by reactor.Then by solid product filtration washing to neutrality, 10h is dried under the conditions of 100 DEG C, last 500 DEG C of roasting 3h in air atmosphere, gained sample number into spectrum is CL6, and gained sample XRD spectra and TEM photos are Beta molecular sieves as shown in Figure 3 and Figure 4, but crystal particle diameter skewness, both containing the small crystals less than 100nm, also comprising 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 stirring to dry link but do not add the macropore carbon to carry out contrast experiment.
（2）Take 2.5 g NaOH, 0.5 g sodium aluminates to be placed in 50 mL distilled water, be stirred vigorously until all dissolving.7 g white carbons are slowly added again, are stirred vigorously 30
min.It is subsequently adding on 2.5mL and walks made structure directing agent, is stirred vigorously 30
min。
（3）By step（2）The synthesized gel rubber for obtaining mixes with the macropore carbon prepared by 8g embodiments 1, ultrasonication 30min；Then under the conditions of 60 DEG C stir process to viscous pasty state；Then dried under the conditions of 110 DEG C, until moisture evaporating completely.
（4）Then just step（3）Gained mixture is placed in reactor, adds 5 mL water.Then closed reactor, 140 DEG C of crystallization 50h in baking oven are placed in by reactor.Then by solid product filtration washing to neutrality, 10h is dried under the conditions of 100 DEG C, finally 500 DEG C of roasting 3h in air atmosphere, gained sample number into spectrum is CL7, and gained sample is Beta molecular sieves, but crystal yardstick is more than 100nm, nano molecular sieve is not belonging to, properties of samples is shown in Table 1.
Table 1 is embodiment and comparative example gained Beta molecular sieve properties
Note：The relative crystallinity that table 1 is given is the crystallinity with CL1 as reference.
Claims (23)
1. it is a kind of synthesize nanometer Beta molecular sieves method, the crystal structure of molecular sieve be Beta molecular sieves, without other Crystal impurities, its crystal size be less than 100nm, the described method comprises the following steps：
（1）Beta molecular sieves are added in aqueous slkali, wherein aqueous slkali and the solid mass ratio of the liquid of Beta molecular sieves is 0.01~0.1：1, after stirring mixing, 0.5~8.0h is processed under airtight condition under the conditions of 80~180 DEG C, gained suspension product is structure directing agent；
（2）By inorganic base, silicon source, silicon source and water according to 6~35Na of mol ratio2O:25~120SiO2:A12O3:600~3500H2The ratio mixing of O, is subsequently adding step（1）The structure directing agent for obtaining is well mixed；
（3）By step（2）The gel for obtaining mix with macropore carbon after 10~60min of ultrasonication, then stir process to viscous pasty state, is then dried, until moisture evaporating completely under the conditions of 80~180 DEG C under the conditions of 50~100 DEG C；
（4）By step（3）The mixture for obtaining loads reactor, adds quantitative water, and then closed reactor carries out crystallization, and reaction temperature is 80~180 DEG C, and the reaction time is 10~96h；
（5）By step（4）The solid product filtration washing for obtaining is dried, and a nanometer Beta molecular sieves are obtained after being then calcined in oxygen or air atmosphere.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Middle aqueous slkali is the mixed solution of one or more in NaOH, KOH and LiOH aqueous solution, and the concentration of the aqueous slkali is 0.1~5 mol/L, preferably 0.5~2 mol/L.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）Middle Beta molecular sieves are routine Beta molecular sieves, its SiO2/A12O3Mol ratio is 10~100.
4. in accordance with the method for claim 1, it is characterised in that：Step（1）Middle aqueous slkali is 0.03~0.06 with the solid mass ratio of the liquid of Beta molecular sieves：1.
5. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in inorganic base be one or more in NaOH, KOH, LiOH；Silicon source is one or more in sodium aluminate, aluminum sulfate, aluminium chloride, aluminum nitrate；Silicon source is one or more in White Carbon black, silica gel, Ludox or waterglass.
6. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in molar ratio of material be 8~30Na2O:30~100SiO2:A12O3:800~3000H2O。
7. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in structure directing agent addition in terms of Beta molecular sieves and step（2）Middle added silicon source is with SiO2The mass ratio of meter is 0.005~0.06：1, preferably 0.01~0.04：1.
8. in accordance with the method for claim 1, it is characterised in that：Step（3）Middle macropore carbon is a kind of micron-sized carbon material, and particle diameter is 0.5~100 μm, and preferably 1~70 μm, the aperture of the macropore carbon is 20~150nm, more preferably preferably 25~110nm, 30~110nm.
9. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in macropore carbon method be prepared by the following procedure obtain：（a）Calcium carbonate is mixed with alkali lye, then the stir process at 50~90 DEG C filters, the solid matter being filtrated to get is heat-treated 1~3h at 300~500 DEG C；（b）Will be through step（a）Calcium carbonate after treatment mixes with water and glucide, after 10~60min of stirring, 1~10h of ultrasonication；（c）By step（b）The solution for obtaining stir process to solution at 50~100 DEG C is in viscous pasty state, is then dried at 50~80 DEG C, is finally placed in nitrogen atmosphere 3~10h of charing process at 700~1000 DEG C；（d）By step（c）The material for obtaining is well mixed with acid solution, and 1~10h is processed at 50~200 DEG C, is washed out drying；（e）By step（d）The material for obtaining in a nitrogen atmosphere, in 700~1000 DEG C of 3~10h of high-temperature process, obtains macropore carbon.
10. in accordance with the method for claim 9, it is characterised in that：Step（a）Described in calcium carbonate be nano-calcium carbonate, the particle diameter of the nano-calcium carbonate is 30~50nm.
11. in accordance with the method for claim 9, it is characterised in that：Step（a）Described in alkali lye be NaOH, potassium hydroxide in one or two, the concentration of lye be 0.01~0.1mol/L.
12. in accordance with the method for claim 9, it is characterised in that：Step（a）Middle calcium carbonate is 1 with the mass ratio of alkali lye：5~1：50, preferably 1：10~1：20.
13. in accordance with the method for claim 9, it is characterised in that：Step（b）Described in glucide be sucrose, glucose in one or two.
14. in accordance with the method for claim 9, it is characterised in that：Step（b）Middle calcium carbonate, glucide, the mass ratio of water are 0.1~2：1：10~33, preferably 0.2~1：1：13~26.
15. in accordance with the method for claim 9, it is characterised in that：Step（c）Described in charing process carried out in nitrogen atmosphere, nitrogen flow rate be 10~50mL/min, preferably 15~40 mL/min.
16. in accordance with the method for claim 14, it is characterised in that：Step（c）Described in charing process heating rate be 1~10 DEG C/min, heated up with constant heating rate, described charing process processes 4~8h at 800~950 DEG C.
17. in accordance with the method for claim 9, 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. in accordance with the method for claim 9, it is characterised in that：Step（d）Described in treatment conditions be at 100~180 DEG C treatment 2~7h.
19. in accordance with the method for claim 9, it is characterised in that：Step（e）Described in high-temperature process carried out in nitrogen atmosphere, nitrogen flow rate is 10~50mL/min, and preferably 15~40 mL/min, the high-temperature process heating rate is 1~10 DEG C/min, is heated up with constant heating rate.
20. in accordance with the method for claim 1, it is characterised in that：Step（3）Middle macropore carbon is 1 with the weight ratio of gel butt:1.5~0.1, preferably 1:1.2~0.2.
21. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in ultrasonic treatment time be 20~40min；Stir process temperature is 60~90 DEG C；Described drying temperature is 100~150 DEG C.
22. in accordance with the method for claim 1, it is characterised in that：Step（4）Middle material mol ratio is：4~10Na2O:25~120SiO2:A12O3:15~300H2O, preferably 3~8Na2O:30~100SiO2:A12O3:
20~200H2O。
23. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in crystallization temperature be 100~150 DEG C, the reaction time be 20~80h.
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| CN110143602A (en) * | 2018-02-13 | 2019-08-20 | 中国石油天然气股份有限公司 | A kind of preparation method of beta-molecular sieve |
| CN110156037A (en) * | 2018-02-13 | 2019-08-23 | 中国石油天然气股份有限公司 | A kind of preparation method of beta-molecular sieve |
| CN110668459A (en) * | 2019-10-25 | 2020-01-10 | 吉林大学 | Nano Beta molecular sieve with wider silicon-aluminum ratio range and preparation method thereof |
| CN112624147A (en) * | 2021-01-13 | 2021-04-09 | 江苏国瓷新材料科技股份有限公司 | Method for green synthesis of nanocrystalline Beta molecular sieve |
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