CN110143602A - A kind of preparation method of beta-molecular sieve - Google Patents
A kind of preparation method of beta-molecular sieve Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of beta-molecular sieve.Step 1, it synthesizes Primogel: silicon source, silicon source, alkalinous metal source, water being mixed, stirred evenly, Primogel is synthesized；Silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkalinous metal source is with Na2O meter, synthesizes the material molar ratio of Primogel are as follows: SiO2/Al2O3=30~150:1, Na2O/SiO2=0.03~0.35:1, H2O/SiO2=3.0~50.0:1；Step 2, beta-molecular sieve crystal seed, crystal seed silica alumina ratio SiO microwave treatment Primogel: are added into Primogel made from step 12/Al2O3=20~100:1, additional amount are SiO by mass2Crystallization aqueous precursor gel is made after mixing with microwave heating treatment in the 3%~25% of quality；Step 3, crystallization: crystallization aqueous precursor gel obtained in step 2 is subjected to crystallization with microwave heating, reaction temperature is 140 DEG C~180 DEG C, and the reaction time is 4~20h, obtains beta-molecular sieve product.The molecular sieve that the method for the present invention obtains has lesser partial size, pore structure abundant, and channel is more unobstructed, may advantageously facilitate the progress of catalytic cracking and isomerization.
Description
Technical field
The invention belongs to the technical field of catalytic chemistry more particularly to a kind of synthetic methods of beta-molecular sieve.
Background technique
Beta-molecular sieve is by the oil company Mobil, the U.S. in the patented product USP3308069 of research and development in 1967.It is relatively early
Report beta-molecular sieve to have superior catalytic performance be later patents EP0159846 that Mobil company develops beta-molecular sieve,
EP0159847, disclosing beta-molecular sieve has excellent activity to cracking hydrocarbon and isomerization.Since the nineties, with to β points
The understanding of son sieve crystal structure, synthesis and catalytic performance research expansion rapidly to beta-molecular sieve, that goes on writing for pages and pages reports β points
Son sieve is adding hydrogen, cracking, isomerization, alkylation, alkene hydration, dewaxing and the petroleum refinings such as photocatalysis and petrochemical process
The excellent catalytic performance shown in numerous catalysis reactions.Since it is unique a kind of with three-dimensional 12-membered ring in the world at present
The silica-rich zeolite of pore canal system, it is close with Y molecular sieve on aperture, it is more superior than ZMS-5 molecular sieve in pore structure, it integrates
The advantages of Y and ZSM-5, and its silica alumina ratio can in the very big range modulation so that it acid can and be stablized
Property be controlled to a certain extent, this application for being it in functionalization catalytic cracking catalyst provides prerequisite.
Microwave is that a kind of wavelength is extremely short, electromagnetic wave of very high frequency, and wavelength 1mm-1m, frequency is in 300MHz-300GHz, position
Between infrared light and radio wave.Microwave frequency for heating is generally fixed to 2450MHz or 915MHz.Microwave heating
Basic principle are as follows: outside plus under alternating electromagnetic field effect, polar molecule polarizes and becomes with additional alternating electromagnetic field polarity in material
Friction more and is frequently turned to, electromagnetic energy thermal energy is made.Microwave heating has heating speed fast, uniform, and capacity usage ratio is high,
The features such as environmentally protective.Most more outstanding to be, microwave shows influence kinetics in synthesizing nano-porous material
With the ability of selectivity.
Conventional hydrothermal synthesis beta-molecular sieve generally uses organic formwork agent, for example, using tetraethyl ammonium hydroxide as template
Under conditions of, for generated time generally at 40 hours or more, the production time is longer, and production efficiency is lower.Especially because template
Dosage is larger, causes production cost very high, and the later period needs to carry out zeolite product to roast Template removal processing, can be right
Product structure damages, and the template of removing also would seriously pollute the environment.Template-free method synthesis of molecular sieve technology has important
Practical significance.
CN101249968 discloses a kind of method of organic-free template synthesis β zeolite, with silicon source, silicon source, sodium source, water
It is mixed with out Primogel, beta-molecular sieve crystal seed is then added, hydro-thermal reaction is carried out and has finally obtained beta-molecular sieve product.But
Since organic formwork agent is not added in system, only stablize by the more difficult maintenance reaction system of the structure-directing effect of crystal seed, as a result
Cause synthesis beta-molecular sieve phase region very narrow, real reaction condition control difficulty is larger, is relatively also easy to produce stray crystal.
In conclusion conventional hydrothermal synthesis beta-molecular sieve generally uses organic formwork agent, the production time is longer, especially
Since template dosage is larger, cause production cost very high, and the later period needs to carry out roasting stripper plate to zeolite product
Agent processing, can damage product structure, the template of removing also would seriously pollute the environment.It is now existing not to be added with additionally
Machine template synthesis beta-molecular sieve technology discloses, but due to using conventional hydrothermal synthesis mode, only makees by the structure directing of crystal seed
With more difficult maintenance reaction system stablize, as a result result in synthesis beta-molecular sieve phase region it is very narrow, real reaction condition control difficulty
It is larger, relatively it is also easy to produce stray crystal.
Therefore, Template-free method synthesis beta-molecular sieve is a kind of good Research Thinking, but how to control reaction system and stablize
Property and relax practical synthesis condition requirement, has prior meaning to subsequent actual production.
Summary of the invention
The main purpose of the present invention is to provide a kind of preparation method of beta-molecular sieve, the beta molecule obtained by the preparation method
It is smaller to sieve crystallite dimension, possesses higher crystallinity and more rich pore structure, and duct is more unobstructed.
In order to achieve the above object, the present invention provides a kind of preparation method of beta-molecular sieve, which includes:
Step 1, it synthesizes Primogel: silicon source, silicon source, alkalinous metal source, water being mixed, stirred evenly, synthesize initial solidifying
Glue；Silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkalinous metal source is with Na2O meter, synthesizes the material molar ratio of Primogel are as follows:
SiO2/Al2O3=30~150:1, Na2O/SiO2=0.03~0.35:1, H2O/SiO2=3.0~50.0:1；
Step 2, beta-molecular sieve crystal seed, crystal seed silicon microwave treatment Primogel: are added into Primogel made from step 1
Aluminium ratio SiO2/Al2O3=20~100:1, additional amount are SiO by mass2The 3%~25% of quality, after mixing with microwave
Heat treatment, heating temperature are 80 DEG C~120 DEG C, and heating time is 0.1~10h, and crystallization aqueous precursor gel is made；
Step 3, crystallization: crystallization aqueous precursor gel obtained in step 2 is subjected to crystallization with microwave heating, instead
Answering temperature is 140 DEG C~180 DEG C, and the reaction time is 4~20h, obtains beta-molecular sieve product.
The preparation method of beta-molecular sieve of the present invention, wherein the silicon source is preferably silochrom, White Carbon black and silicon
One or more of formed group of colloidal sol.
The preparation method of beta-molecular sieve of the present invention, wherein source of aluminium is preferably sodium metaaluminate, aluminum sulfate and intends
One or more of formed group of boehmite.
The preparation method of beta-molecular sieve of the present invention, wherein the alkalinous metal source is preferably sodium hydroxide.
The preparation method of beta-molecular sieve of the present invention, wherein the silica alumina ratio of the beta-molecular sieve crystal seed is preferably SiO2/
Al2O3=22~80, additional amount is preferably SiO in mass2The 5%~20% of quality.
The preparation method of beta-molecular sieve of the present invention, wherein the beta-molecular sieve crystal seed silica alumina ratio is more preferably
SiO2/Al2O3=23.5:1.
The preparation method of beta-molecular sieve of the present invention, wherein step 2 heating temperature is preferably 100 DEG C~120
DEG C, heating time is preferably 4~6h.
The preparation method of beta-molecular sieve of the present invention, wherein the step 3, reaction temperature are preferably 140 DEG C~170
DEG C, the reaction time is preferably 6~15h.
The preparation method of beta-molecular sieve of the present invention, wherein the Primogel preparation method of the step 1 is preferably,
Alkalinous metal source is soluble in water, 50~80 DEG C are warming up to, silicon source is added and stirs to whole dissolutions, is eventually adding silicon source, continues
It is uniformly mixing to obtain Primogel.
The preparation method of beta-molecular sieve of the present invention, wherein silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkalinous metal
Source is with Na2O meter, the material molar ratio for synthesizing Primogel are preferred are as follows: SiO2/Al2O3=30~95:1, Na2O/SiO2=0.07
~0.30:1, H2O/SiO2=3.5~22:1.
Beneficial effects of the present invention:
Conventional hydrothermal synthesis beta-molecular sieve is long there are the production time, template dosage is big, system water content is higher, and product is received
The low problem of rate.Beta-molecular sieve generated time is substantially reduced by the high thermal efficiency of microwave using method of the invention, and
And improve the yield and crystallinity of beta-molecular sieve.
More it is essential that present invention discover that microwave shows influence kinetics during synthesizing beta-molecular sieve
And the property of molecular sieve structure, molecular sieve obtained by the method for the present invention have lesser partial size, pore structure abundant, Er Qietong
Road is more unobstructed, may advantageously facilitate the progress of catalytic cracking and isomerization.
In addition, the present invention is conducive to beta-molecular sieve crystal seed in alkalinity at a lower temperature with microwave heating treatment Primogel
Under the conditions of rapid dispersion be with higher structure induce performance beta-molecular sieve crystallite, and tentatively generate molecular sieve nucleus, then exist
Crystallization is carried out with microwave heating under higher temperature, to realize crystal rapid growth, finally obtained beta-molecular sieve has high
Crystallinity and pore structure abundant.
Detailed description of the invention
Fig. 1 is the XRD spectra of beta-molecular sieve crystal seed；
Fig. 2 is the stereoscan photograph of synthetic material in embodiment 1；
Fig. 3 is the XRD spectra of synthetic material in embodiment 1
Fig. 4 is the XRD spectra of synthetic material in embodiment 2；
Fig. 5 is the XRD spectra of synthetic material in embodiment 3；
Fig. 6 is the XRD spectra of synthetic material in embodiment 4；
Fig. 7 is the XRD spectra of synthetic material in embodiment 5；
Fig. 8 is the XRD spectra of synthetic material in embodiment 6；
Fig. 9 is the XRD spectra of synthetic material in embodiment 8；
Figure 10 is the XRD spectra of synthetic material in embodiment 13；
Figure 11 is the XRD spectra of synthetic material in comparative example 1；
Figure 12 is the XRD spectra of synthetic material in comparative example 2；
Figure 13 is the stereoscan photograph of synthetic material in comparative example 4；
Figure 14 is the XRD spectra of synthetic material in comparative example 4；
Figure 15 is the XRD spectra of standard sample.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, should also wrap
Include other any well known changes in the scope of the present invention.In the following examples, the experimental methods for specific conditions are not specified,
Usually according to normal condition.
The main purpose of the present invention is to provide a kind of preparation methods of beta-molecular sieve, do not add organic formwork agent additionally
Meanwhile synthetic system is more stably and controllable, is easier to synthesize high-crystallinity beta-molecular sieve product, when also can further shorten synthesis
Between, it reduces environmental pollution.
A kind of preparation method of beta-molecular sieve provided by the invention, the preparation method include:
(1) it synthesizes Primogel: silicon source, silicon source, alkalinous metal source, water being mixed, stirred evenly, Primogel is synthesized；
Silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkalinous metal source is with Na2O meter, synthesizes the material molar ratio of Primogel are as follows: SiO2/
Al2O3=30~150, Na2O/SiO2=0.03~0.35, H2O/SiO2=3.0~50.0；It is preferred that are as follows: SiO2/Al2O3=30~
95:1, Na2O/SiO2=0.07~0.30:1, H2O/SiO2=3.5~22:1；
(2) beta-molecular sieve crystal seed, crystal seed sial microwave treatment Primogel: are added into Primogel made from step (1)
Compare SiO2/Al2O3=20~100, additional amount is SiO in silicon source by quality2The 3%~25% of effective mass, after mixing with
80 DEG C~120 DEG C of temperature, 0~10h of heating time, crystallization aqueous precursor gel is made in microwave heating treatment；
(3) crystallization: crystallization aqueous precursor gel obtained in step (2) is continued anti-with microwave heating progress crystallization
It answers, 140 DEG C~180 DEG C of temperature, 4~20h of heating time obtains beta-molecular sieve product.
The silicon source can be silochrom, White Carbon black or silica solution, other common raw materials can also be chosen, such as water glass
Glass etc..The silicon source can be sodium metaaluminate, aluminum sulfate or boehmite, can also choose other common raw materials, such as oxygen
Change aluminium etc..The alkalinous metal source can be sodium hydroxide.The water can be deionized water.
The preparation method of the Primogel, can be soluble in water by alkalinous metal source, is warming up to 50~80 DEG C, and aluminium is added
Source is stirred to whole dissolutions, and above-mentioned solution finally is added in silicon source, is stirred continuously until that Primogel is uniform.Described is initial solidifying
The material proportion of glue, SiO2/Al2O3Optional purpose is to synthesize different silica alumina ratio products in a big way；Na2O/SiO2、H2O/
SiO2Optional in a big way, water content can regulate and control gel sliminess, while appropriate adjustment alkalinous metal source being needed to add
Enter amount, to guarantee that pH of latex gel is basicly stable.
Particular/special requirement is not made to beta-molecular sieve crystal seed source in the present invention, can choose in institute, petroleum Petroleum Chemical Engineering Institute
The beta-molecular sieve of offer is as crystal seed, silica alumina ratio SiO2/Al2O3=23.5, XRD are as shown in Figure 1.Other sources can also be selected
Beta-molecular sieve as crystal seed, the silica alumina ratio SiO of crystal seed2/Al2O3=20~100, additional amount is SiO in silicon source by mass2Matter
The 3%~25% of amount.It is preferred that the silica alumina ratio SiO of crystal seed2/Al2O3=22~80, additional amount is preferably in silicon source by mass
SiO2The 5%~20% of quality.In the present invention in microwave treatment Primogel step, 80 DEG C~120 DEG C of microwave treatment temperature, add
Crystallization aqueous precursor gel is made in hot 0.1~10h of time；Preferred 100 DEG C~120 DEG C of temperature of microwave treatment, heating time 4~
6h.In crystallization step in the present invention, 140 DEG C~180 DEG C of microwave heating temperature, 4~20h of heating time obtains beta molecule
Sieve product；Preferred 140 DEG C~170 DEG C of microwave heating temperature, 6~15h of heating time.
Although microwave has been used for the synthesis of molecular sieve as a kind of heating means in the prior art, it is acted on
Heating efficiency is only improved, crystallization time is shortened.The present invention is found by experiment that microwave will affect β points to a certain extent
Son sieves the kinetics in synthesis process, and the pore structure of the beta-molecular sieve synthesized.In addition, crystallization is carried out using microwave method,
The material proportion of the crystallization method and synthesis of molecular sieve has complementary relevance, for example, the water content of synthetic system, mistake
Low water content will affect reaction mass transfer, and then influence the quality of product；And excessively high water content will lead to the excessive quilt of microwave
Aqueous medium absorbs, to influence effect of the microwave to unclassified stores, leads to the failure of Zeolite synthesis.Simultaneously as microwave is deposited
In the feature that instantaneous energy is concentrated, route of transmission is not easy to control, penetrability is limited, cause temperature control difficulty under microwave heating higher.β
Zeolite synthesis phase region is wider, and temperature fluctuation, dynamic or static crystallization state will not impact its product selectivity, institute
It is preferable that compatible degree is synthesized with beta-molecular sieve with microwave heating, and other synthesis phase regions are relatively narrow, there have to crystallization temperature and crystallization state to be severe
Desired molecular sieve is carved, the difficulty of microwave heating synthesis can be greatly improved.
More, during beta-molecular sieve study on the synthesis, discovery directly carries out microwave heating crystallization to Primogel, and effect is not
It is especially desirable.The present invention with microwave heating treatment Primogel, is conducive to beta-molecular sieve crystal seed in alkaline item at a lower temperature
Under part rapid dispersion be with higher structure induce performance beta-molecular sieve crystallite, and tentatively generate molecular sieve nucleus, then compared with
Crystallization is carried out with microwave heating under high-temperature, to realize crystal rapid growth, finally obtained beta-molecular sieve has high knot
Brilliant degree and pore structure abundant.
The raw materials used in the present invention are as follows:
Silicon source: silochrom, silica solution (solid content 30%), White Carbon black；
Silicon source: NaAlO2(sodium metaaluminate), Al2(SO4)2·18H2O (Patent alum)；
Crystal seed: beta-molecular sieve is provided by middle petroleum Petroleum Chemical Engineering Institute；
Other: deionized water, NaOH (sodium hydroxide).
Phase Analysis: material phase analysis is carried out to sample using powder x-ray diffraction (XRD) technology, with known phase
External standard is made to beta-molecular sieve (commercially available Nankai's catalyst plant beta-molecular sieve product) standard sample of crystallinity, with characteristic diffraction peak area
Relative ratio determine the relative crystallinity of each sample.
Material phase analysis instrument: Dutch Panaco X-Pert Pro type X-ray powder diffraction instrument.
Material phase analysis determination condition: CuK ray, pipe pressure is 40kV, tube current 40mA, and the scanning range for measuring crystal phase is
5~40 °, scanning speed is 4 °/min.
Scanning electron microscope: field emission scanning electron microscope FEI NanoSEM450.
BET analysis: the full-automatic specific surface area of Mike's 2460MP type and lacunarity analysis instrument.
Technical solution of the present invention will be further elaborated by specific embodiment below.
Embodiment 1
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 1.80g is added, stirs
It mixes uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 4h, crystallization forerunner is made
Body gel.Then it carries out microwave heating and carries out crystallization, control 170 DEG C of temperature, reaction time 10h.Reaction terminates, to product
Washing and drying treatment is carried out, x-ray diffraction characterization is carried out, product crystallinity is shown in Table 1.It is scanned Electronic Speculum, BET analysis, knot
Fruit is shown in Table 2.
Embodiment 2
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 0.75g is added, stirs
It mixes uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 4h, crystallization forerunner is made
Body gel.Then it carries out microwave heating and carries out crystallization, control 170 DEG C of temperature, reaction time 10h.Reaction terminates, to product
Washing and drying treatment is carried out, x-ray diffraction characterization is carried out, product crystallinity is shown in Table 1.
Embodiment 3
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 3g is added, stirring is equal
It is even, Primogel is made.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 4h, it is solidifying that crystallization presoma is made
Glue.Then it carries out microwave heating and carries out crystallization, control 170 DEG C of temperature, reaction time 10h.Reaction terminates, and carries out to product
Washing and drying treatment, carries out x-ray diffraction characterization, and product crystallinity is shown in Table 1.
Embodiment 4
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.40g sodium hydroxide, stirring and dissolving is added.It is added
2.00g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 1.20g is added, stirs
It mixes uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 4h, crystallization forerunner is made
Body gel.Then it carries out microwave heating and carries out crystallization, control 170 DEG C of temperature, reaction time 10h.Reaction terminates, to product
Washing and drying treatment is carried out, x-ray diffraction characterization is carried out, product crystallinity is shown in Table 1.
Embodiment 5
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.54g sodium hydroxide, stirring and dissolving is added.It is added
0.86g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 3g is added, stirring is equal
It is even, Primogel is made.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 4h, it is solidifying that crystallization presoma is made
Glue.Then it carries out microwave heating and carries out crystallization, control 170 DEG C of temperature, reaction time 10h.Reaction terminates, and carries out to product
Washing and drying treatment, carries out x-ray diffraction characterization, and product crystallinity is shown in Table 1.
Embodiment 6
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.85g sodium hydroxide, stirring and dissolving is added.It is added
0.40g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 3.75g is added, stirs
It mixes uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 4h, crystallization forerunner is made
Body gel.Then it carries out microwave heating and carries out crystallization, control 170 DEG C of temperature, reaction time 10h.Reaction terminates, to product
Washing and drying treatment is carried out, x-ray diffraction characterization is carried out, product crystallinity is shown in Table 1.
Embodiment 7
In the container of the water-bath at 70 DEG C, 12.70g deionized water is added, 0.44g sodium hydroxide, stirring and dissolving is added.It is added
1.84g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 1.80g is added, stirs
It mixes uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 4h, crystallization forerunner is made
Body gel.Then it carries out microwave heating and carries out crystallization, control 170 DEG C of temperature, reaction time 10h.Reaction terminates, to product
Washing and drying treatment is carried out, x-ray diffraction characterization is carried out, product crystallinity is shown in Table 1.
Embodiment 8
In the container of the water-bath at 70 DEG C, 5g silica solution is added, 17.50g deionized water is added, 6.15g sodium hydroxide is added,
Stirring and dissolving.1.13g aluminum sulfate, stirring and dissolving is added.The beta-molecular sieve crystal seed of 0.45g is added, stirs evenly, is made initial solidifying
Glue.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 4h, crystallization aqueous precursor gel is made.Then it carries out micro-
Wave heating carries out crystallization, controls 170 DEG C of temperature, reaction time 20h.Reaction terminates, and carries out washing and drying treatment to product,
X-ray diffraction characterization is carried out, product crystallinity is shown in Table 1.
Embodiment 9
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 1.80g is added, stirs
It mixes uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 10h, crystallization forerunner is made
Body gel.Then it carries out microwave heating and carries out crystallization, control 170 DEG C of temperature, reaction time 4h.Reaction terminates, to product
Washing and drying treatment is carried out, x-ray diffraction characterization is carried out, product crystallinity is shown in Table 1.
Embodiment 10
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 1.80g is added, stirs
It mixes uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 0.1h, before crystallization is made
Drive body gel.Then it carries out microwave heating and carries out crystallization, control 170 DEG C of temperature, reaction time 20h.Reaction terminates, to production
Product carry out washing and drying treatment, carry out x-ray diffraction characterization, and product crystallinity is shown in Table 1.
Embodiment 11
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.1.80g beta-molecular sieve crystal seed, stirring is added
Uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 80 DEG C of temperature, handles 10h, crystallization presoma is made
Gel.Then it carries out microwave heating and carries out crystallization, control 160 DEG C of temperature, reaction time 20h.Reaction terminates, to product into
Row washing and drying treatment, carries out x-ray diffraction characterization, and product crystallinity is shown in Table 1.
Embodiment 12
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.1.80g beta-molecular sieve crystal seed, stirring is added
Uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 2h, crystallization presoma is made
Gel.Then it carries out microwave heating and carries out crystallization, control 170 DEG C of temperature, reaction time 10h.Reaction terminates, to product into
Row washing and drying treatment, carries out x-ray diffraction characterization, and product crystallinity is shown in Table 1.
Embodiment 13
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.1.80g beta-molecular sieve crystal seed, stirring is added
Uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 120 DEG C of temperature, handles 6h, crystallization presoma is made
Gel.Then it carries out microwave heating and carries out crystallization, control 140 DEG C of temperature, reaction time 20h.Reaction terminates, to product into
Row washing and drying treatment, carries out x-ray diffraction characterization, and product crystallinity is shown in Table 1.
Embodiment 14
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 1.80g is added, stirs
It mixes uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 80 DEG C of temperature, handles 6h, crystallization presoma is made
Gel.Then it carries out microwave heating and carries out crystallization, control 180 DEG C of temperature, reaction time 8h.Reaction terminates, to product into
Row washing and drying treatment, carries out x-ray diffraction characterization, and product crystallinity is shown in Table 1.
Embodiment 15
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 1.80g is added, stirs
It mixes uniformly, Primogel is made.Microwave treatment is carried out to Primogel, controls 100 DEG C of temperature, handles 3h, crystallization forerunner is made
Body gel.Then it carries out microwave heating and carries out crystallization, control 140 DEG C of temperature, reaction time 15h.Reaction terminates, to product
Washing and drying treatment is carried out, x-ray diffraction characterization is carried out, product crystallinity is shown in Table 1.
Comparative example 1
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 3.00g is added, stirs
It mixes uniformly, Primogel is made.Conventional hydrothermal synthesis is carried out to Primogel, controls 120 DEG C of temperature, 4h is reacted, then controls
170 DEG C of temperature, reaction time 10h.Reaction terminates, and carries out washing and drying treatment to product, carries out x-ray diffraction characterization, knot
Fruit shows that product has more modenite.It is compared with embodiment 3, it can be seen that in material proportion, crystallization temperature, crystallization time item
In the identical situation of part, microwave heating is more advantageous to the selectivity of beta-molecular sieve product, is more favorable to improve crystallization of molecular sieves
Degree.
Comparative example 2
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 1.80g is added, stirs
It mixes uniformly, Primogel is made.Conventional hydrothermal synthesis is carried out to Primogel, controls 120 DEG C of temperature, 4h is reacted, then controls
170 DEG C of temperature, reaction time 10h.Reaction terminates, and carries out washing and drying treatment to product, carries out x-ray diffraction characterization, knot
Fruit shows that product has a large amount of modenites.It is compared with embodiment 1, it can be seen that in material proportion, crystallization temperature, crystallization time item
In the identical situation of part, microwave heating is more advantageous to the selectivity of beta-molecular sieve product (especially in architecture directed agents-crystalline substance
When kind additive amount is less), it is more favorable to improve molecular sieve crystallinity.
Comparative example 3
In the container of the water-bath at 70 DEG C, 28.43g deionized water is added, 0.42g sodium hydroxide, stirring and dissolving is added.It is added
1.65g sodium metaaluminate, stirring and dissolving.15.00g silochrom is added, stirs evenly.The beta-molecular sieve crystal seed of 1.80g is added, stirs
It mixes uniformly, Primogel is made.Microwave heating is directly carried out to Primogel and carries out crystallization, controls 170 DEG C of temperature, reaction
Time 10h.Reaction terminates, and carries out washing and drying treatment to product, carries out x-ray diffraction characterization, the results showed that product is nothing
Approved product.
Under the conditions of having template, pre- crystallization stage be not it is very necessary, beta-molecular sieve can be synthesized, without add template
Under the conditions of agent, structure-directing effect only is played by crystal seed, crystal seed is substantially also the beta-molecular sieve with more complete crystal structure,
Structure-directing effect itself is not high, it is necessary to pre- crystallization stage further occurrence of the crystal seed under microwave heating be allowed to decompose and divide
It dissipates, to improve its structure-directing effect, finally can just obtain higher crystallinity beta-molecular sieve.
Comparative example 4
In 70 DEG C of water-baths, 11.00g deionized water is added, 13.00g tetraethyl ammonium hydroxide solution is added, stirring is equal
It is even.0.31g sodium hydroxide is added, 1.85g sodium metaaluminate, stirring and dissolving is added.15.00g silochrom is added, stirs evenly.
0.30g beta-molecular sieve crystal seed is added, stirs evenly, Primogel is made.Conventional hydrothermal synthesis, control temperature are carried out to Primogel
160 DEG C of degree reacts 40h.Reaction terminates, and carries out washing and drying treatment to product, carries out x-ray diffraction characterization, the results showed that
Product is the beta-molecular sieve product with higher crystallinity.It is scanned Electronic Speculum, BET analysis, the results are shown in Table 2.As it can be seen that conventional water
Thermal synthesis beta-molecular sieve average crystal particle diameter is 500nm, much larger than the 50nm of microwave synthesis, while micropore specific area and micropore
Hole, which holds, is respectively less than microwave synthesis.
Table 1 is embodiment and comparative example relative crystallinity calculated result
Table 2 is that embodiment 1 and 4 crystal size of comparative example analyze result to when BET
The present invention is not add template synthesis of molecular sieve technology, though crystal seed has certain structure-directing effect, completely
Replacing template to carry out synthesis of molecular sieve with crystal seed has more highly difficult, it is poor to be especially easy to produce stray crystal, product crystallinity.
The present invention is directed to realize product without stray crystal, the higher mesh of crystallinity to improve crystal seed structure-directing effect after microwave heating treatment
's.Calculating standard sample used by relative crystallinity has higher crystallinity, but the sample is to add organic formwork agent
Method synthesis, the production cost is very high.Although some embodiment acquired results relative crystallinities of the present invention are slightly not as good as standard sample
Product, but synthesis cost itself will be far below standard sample, therefore still have certain application value.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (10)
1. a kind of preparation method of beta-molecular sieve, which is characterized in that the preparation method includes:
Step 1, it synthesizes Primogel: silicon source, silicon source, alkalinous metal source, water being mixed, stirred evenly, Primogel is synthesized；Silicon
Source is with SiO2Meter, silicon source is with Al2O3Meter, alkalinous metal source is with Na2O meter, synthesizes the material molar ratio of Primogel are as follows: SiO2/
Al2O3=30~150:1, Na2O/SiO2=0.03~0.35:1, H2O/SiO2=3.0~50.0:1；
Step 2, beta-molecular sieve crystal seed, crystal seed silica alumina ratio microwave treatment Primogel: are added into Primogel made from step 1
SiO2/Al2O3=20~100:1, additional amount are SiO by mass2The 3%~25% of quality, after mixing with microwave heating
Processing, heating temperature are 80 DEG C~120 DEG C, and heating time is 0.1~10h, and crystallization aqueous precursor gel is made；
Step 3, crystallization aqueous precursor gel obtained in step 2 crystallization: is subjected to crystallization, reaction temperature with microwave heating
Degree is 140 DEG C~180 DEG C, and the reaction time is 4~20h, obtains beta-molecular sieve product.
2. the preparation method of beta-molecular sieve according to claim 1, which is characterized in that the silicon source is silochrom, white carbon
One or more of black and formed group of silica solution.
3. the preparation method of beta-molecular sieve according to claim 1, which is characterized in that source of aluminium is sodium metaaluminate, sulfuric acid
One or more of aluminium and the formed group of boehmite.
4. the preparation method of beta-molecular sieve according to claim 1, which is characterized in that the alkalinous metal source is hydroxide
Sodium.
5. the preparation method of beta-molecular sieve according to claim 1, which is characterized in that the silica alumina ratio of the beta-molecular sieve crystal seed
For SiO2/Al2O3=22~80, additional amount is SiO in mass2The 5%~20% of quality.
6. the preparation method of beta-molecular sieve according to claim 5, which is characterized in that the beta-molecular sieve crystal seed silica alumina ratio is
SiO2/Al2O3=23.5:1.
7. the preparation method of beta-molecular sieve according to claim 1, which is characterized in that step 2 heating temperature is 100
DEG C~120 DEG C, heating time is 4~6h.
8. the preparation method of beta-molecular sieve according to claim 1, which is characterized in that the step 3, reaction temperature 140
DEG C~170 DEG C, the reaction time is 6~15h.
9. the preparation method of beta-molecular sieve according to claim 1, which is characterized in that prepared by the Primogel of the step 1
Method is, alkalinous metal source is soluble in water, is warming up to 50~80 DEG C, and silicon source is added and stirs to whole dissolutions, is eventually adding silicon
Source is persistently uniformly mixing to obtain Primogel.
10. the preparation method of beta-molecular sieve according to claim 1, which is characterized in that silicon source is with SiO2Meter, silicon source with
Al2O3Meter, alkalinous metal source is with Na2O meter, synthesizes the material molar ratio of Primogel are as follows: SiO2/Al2O3=30~95:1,
Na2O/SiO2=0.07~0.30:1, H2O/SiO2=3.5~22:1.
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