CN105858672B - A method of synthesis Silicalite-1 - Google Patents
A method of synthesis Silicalite-1 Download PDFInfo
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- CN105858672B CN105858672B CN201510037363.7A CN201510037363A CN105858672B CN 105858672 B CN105858672 B CN 105858672B CN 201510037363 A CN201510037363 A CN 201510037363A CN 105858672 B CN105858672 B CN 105858672B
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Abstract
The invention discloses a kind of methods for synthesizing Silicalite-1 molecular sieve, comprising the following steps: (1) is uniformly mixed silicon source, structure directing agent, mineralizer and water, obtaining mol ratio is OH‑: SiO2: R:F:H2O=(0.05-5): 1:(0.05-0.39): (0.05-5): the reaction mixture of (2-100), wherein the molal quantity of R representative structure directed agents, F represent the molal quantity of mineralizer；The structure directing agent is selected from least one of tetraethyl ammonium hydroxide, tetraethylammonium bromide, etamon chloride, tetraethyl ammonium fluoride, tetraethyl ammonium iodide and triethylamine；(2) reaction mixture that step (1) obtains is gone in the closed container of pressure resistance, and crystallization 0.5-60 days at 80-200 DEG C of temperature and self-generated pressure, obtains crystallization product；(3) crystallization product that recycling step (2) obtains.By above-mentioned synthetic method, the present invention can synthesize that crystal grain is intact, uniform Silicalite-1 molecular sieve under the action of new structure directed agents.
Description
Technical field
The present invention relates to a kind of synthetic methods of Silicalite-1 molecular sieve.
Background technique
ZSM-5 is that Mobil company develops in 1970s, the molecular sieve with MFI topological structure.It has ten yuan of two dimension
Ring cellular structure, wherein [100] direction is the straight hole road that aperture is 0.51 × 0.55 nanometer, and [010] direction is then that aperture is
0.53 × 0.56 nanometer of sinusoidal duct.The Si/Al ratio of ZSM-5 can change within the scope of Silicon-rich and total silicon, have preferable
Controllability.
Since with special two-dimentional ten-ring cellular structure and acid catalytic property, ZSM-5 has become most important molecule
Sieve one of catalysis material.Currently, ZSM-5 molecular sieve is widely used to catalytic cracking, alkylation, isomerization and methanol-to-olefins
Etc. the fields such as petrochemical industries, coal chemical industry and fine chemistry industry.Therefore, the synthesis with modification of ZSM-5 is also always molecular sieve art
One of research hotspot.
Wherein, Silicalite-1 is the silica zeolite with MFI topological structure.Since skeleton is without aluminium atom,
Silicalite-1 has better thermal stability, stronger hydrophobicity and oleophylic performance.Therefore, Silicalite-1 is being catalyzed
With separate in all have biggish application potential.Further, since there is wider synthesis material ratio range, and its synthetic system
The influence of middle no aluminium and other inorganic ions, the synthesis process of Silicalite-1 are research Zeolite synthesis mechanism, regulation
The important evidence of crystallinity, granular size, the distribution of particles of molecular sieve etc..Based on this, the study on the synthesis of Silicalite-1 is
One important directions of ZSM-5 Series Molecules sieve synthesis.
By the difference of structure directing agent used, the synthesis of Silicalite-1 is broadly divided into: (1) with tetrapropylammonium hydroxide
Three kinds of methods of new template agent are used using 4-propyl bromide as template and (3) for template, (2).Wherein, E.Flanigen
Deng (Nature, 1978,271:512-516.) report first using tetrapropylammonium hydroxide as template, in the composition of crystallization system
For TPA+:SiO2:H2Under the conditions of O=2:48:1, crystallization temperature are 100~200 DEG C etc., it is prepared for by hydrothermal crystallizing
Silicalite-1.Hereafter, the study on the synthesis of Silicalite-1 is also largely using tetrapropylammonium hydroxide as structure directing
Agent.(Microporous Mesoporous Mater, 2012,155:56-64.) is with 4 third for example, A.Rivas-Cardona etc.
Base ammonium hydroxide is template, using ethyl orthosilicate as silicon source, and has investigated the chemical composition and electricity of molecular sieve precursor solution
The relationship of conductance, pH and distribution of particles, to deepen the understanding to Silicalite-1 nucleation and crystallization；B.Tokay etc.
(Microporous Mesoporous Mater, 2012,148:43-52.) using tetrapropylammonium hydroxide as template, with positive silicon
Acetoacetic ester is silicon source, the method for having studied regulation Silicalite-1 granular size.
Although tetrapropylammonium hydroxide is the most important structure directing agent for synthesizing Silicalite-1, still there is document
Report carries out the synthesis of Silicalite-1 using 4-propyl bromide as template, this method need to be using sodium hydroxide as alkali source or with fluorine
Ion is mineralizer.(Microporous Mesoporous Mater, 2000,39:117-123.) report for example, C.Shao etc.
Using white carbon black as silicon source, 4-propyl bromide be template, NaOH is alkali source, becomes SiO in the group of crystallization system2:TPABr:
NaOH:H2Under the conditions of O=1:0.2:0.5:30, crystallization temperature are 180 DEG C and crystallization time is 3~15 days etc., benzene has been investigated
Influence of the addition of glycol to Silicalite-1 granular size；S.Lee etc. (Microporous Mesoporous Mater,
It 2005,86:268-276.) is alkali source by template, NaOH of 4-propyl bromide, in SiO2:TPABr:NaOH:H2O=1:
Under the conditions of 0.1:0.2:25, crystallization temperature are 160 DEG C etc., the synthesis of Silicalite-1 in cationic emulsion has been investigated；
T.Kida etc. (Ceram Int, 2004,30:727-732.) is Fluorine source by structure directing agent, ammonium fluoride of 4-propyl bromide,
The Silicalite-1 of bulky grain is prepared within the temperature range of 150~200 DEG C；J.Lin etc. (Langmuir, 2005,21:
Using 4-propyl bromide as structure directing agent, silica gel be then 2117-2120.) silicon source, ammonium fluoride is Fluorine source, in SiO2:TPABr:
NH4OH:H2Under the conditions of O=1:0.2:1:40, crystallization temperature are 180 DEG C and crystallization time is 6 days etc., water-in-oil type is had studied
The Morphological control of Silicalite-1 in emulsion.
In the research of new template agent synthesis Silicalite-1, (the Microporous Mesoporous such as H.Ishii
Mater, 2011,139:158-163.) report that using using tetramethyl disiloxane is bridge chain, using tetrapropyl amine as end moieties
Double quaternary ammonium bases are template, mould silicon ratio is 0.4, water silicon ratio 40, crystallization temperature are 150 DEG C, crystallization time is the items such as 18 days
The Silicalite-1 with unique morphology and micro-structure is prepared under part.
To sum up, it can successfully be prepared by template of tetrapropylammonium hydroxide, 4-propyl bromide or double quaternary ammonium bases
Silica zeolite with MFI structure.It is real when wherein, using tetrapropylammonium hydroxide and 4-propyl bromide as structure directing agent
Border is the structure-directing effect of the tetrapropyl ammonium radical ion generated using its ionization.And double quaternary ammonium bases used in document report
Also with the structure of tetrapropyl ammonium in (Microporous Mesoporous Mater, 2011,139:158-163.) molecule.Cause
This, the synthesis reality of current molecular sieve Silicalite-1 reported in the literature is carried out under the guiding role of tetrapropyl ammonium
, temporarily have no synthesis of the template with other structures for Silicalite-1.
Summary of the invention
The object of the present invention is to provide a kind of method for synthesizing Silicalite-1, which has used new structure
Directed agents have synthesized the complete Silicalite-1 molecular sieve of crystal form.
To achieve the goals above, the present invention provides a kind of method for synthesizing Silicalite-1 molecular sieve, including following
Step:
(1) silicon source, structure directing agent, mineralizer and water are uniformly mixed, obtaining mol ratio is OH-: SiO2: R:F:H2O
=(0.05-5): 1:(0.05-0.39): (0.05-5): the reaction mixture of (2-100), wherein R is represented in reaction mixture
The molal quantity of structure directing agent, F represent the molal quantity of mineralizer；The structure directing agent be selected from tetraethyl ammonium hydroxide,
At least one of tetraethylammonium bromide, etamon chloride, tetraethyl ammonium fluoride, tetraethyl ammonium iodide and triethylamine；
(2) reaction mixture that step (1) obtains is gone in the closed container of pressure resistance, and in 80-200 DEG C of temperature and
Crystallization 0.5-60 days under self-generated pressure, obtain crystallization product；
(3) crystallization product that recycling step (2) obtains.
The synthetic method of Silicalite-1 molecular sieve provided by the invention is to be led under alkaline condition using new structure
Synthesize that crystal grain is intact, uniform Silicalite-1 molecular sieve to agent.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is that the method (embodiment 1) of synthesis Silicalite-1 molecular sieve according to the invention obtains
The XRD spectra of Silicalite-1 molecular sieve.
Fig. 2 is that the method (embodiment 1) of synthesis Silicalite-1 molecular sieve according to the invention obtains
Scanning electron microscope (SEM) photo of Silicalite-1 molecular sieve.
Fig. 3 is that the method (embodiment 3) of synthesis Silicalite-1 molecular sieve according to the invention obtains
Scanning electron microscope (SEM) photo of Silicalite-1 molecular sieve.
Fig. 4 is that the method (embodiment 5) of synthesis Silicalite-1 molecular sieve according to the invention obtains
Scanning electron microscope (SEM) photo of Silicalite-1 molecular sieve.
Fig. 5 is that the method (embodiment 6) of synthesis Silicalite-1 molecular sieve according to the invention obtains
Scanning electron microscope (SEM) photo of Silicalite-1 molecular sieve.
Fig. 6 is that the method (embodiment 7) of synthesis Silicalite-1 molecular sieve according to the invention obtains
Scanning electron microscope (SEM) photo of Silicalite-1 molecular sieve.
Fig. 7 is that the method (embodiment 8) of synthesis Silicalite-1 molecular sieve according to the invention obtains
Scanning electron microscope (SEM) photo of Silicalite-1 molecular sieve.
Fig. 8 is that the method (embodiment 9) of synthesis Silicalite-1 molecular sieve according to the invention obtains
Scanning electron microscope (SEM) photo of Silicalite-1 molecular sieve.
Fig. 9 is according to the prior art (Microporous Mesoporous Mater, 2012,155:56-64.) with 4 third
Base ammonium hydroxide is that the SEM for the Silicalite-1 molecular sieve that the synthetic method (comparative example 1) of structure directing agent is prepared shines
Piece.
Figure 10 is according to according to the prior art (Microporous Mesoporous Mater, 2000,39:117-123.)
The Silicalite-1 molecular sieve being prepared using 4-propyl bromide as the synthetic method (comparative example 2) of structure directing agent
SEM photograph.
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of method for synthesizing Silicalite-1 molecular sieve, comprising the following steps:
(1) silicon source, structure directing agent, mineralizer and water are uniformly mixed, obtaining mol ratio is OH-: SiO2: R:F:H2O
=(0.05-5): 1:(0.05-0.39): (0.05-5): the reaction mixture of (2-100), wherein R is represented in reaction mixture
The molal quantity of structure directing agent, F represent the molal quantity of mineralizer；The structure directing agent be selected from tetraethyl ammonium hydroxide,
At least one of tetraethylammonium bromide, etamon chloride, tetraethyl ammonium fluoride, tetraethyl ammonium iodide and triethylamine；
(2) reaction mixture that step (1) obtains is gone in the closed container of pressure resistance, and in 80-200 DEG C of temperature and
Crystallization 0.5-60 days under self-generated pressure, obtain crystallization product；
(3) crystallization product that recycling step (2) obtains.
It is preferred according the present invention, that the molar ratio of reaction mixture is OH in the step (1)-: SiO2: R:F:
H2O=(0.10-3): 1:(0.10-0.35): (0.1-3): (5-50)；Further preferably OH-: SiO2: R:F:H2O=
(0.15-1.5): 1:(0.15-0.30): (0.15-2): (10-30).
According to the present invention, silicon source used in the step (1) can be synthesis well-known to those skilled in the art
Silicon source commonly used by Silicalite-1 molecular sieve, the present invention are not particularly limited it, such as the silicon source can be estersil
At least one of (organosilicon acid esters), solid silicone, white carbon black and silica solution, silica solution therein are preferably that alkaline silicon is molten
Glue, the alkali in alkaline silica sol are also used as at least part of OH simultaneously-Source；In order to avoid the hetero atom in silicon source such as boron or aluminium
For equal trivalent heteroatoms on the issuable influence of the crystallization of Silicalite-1 molecular sieve, silicon source described in step (1) is preferred
Impurity content few at least one of estersil, solid silicone and the white carbon black for dioxide-containing silica height；Further preferably
At least one of estersil and white carbon black, wherein the general formula of described estersil are as follows:
In formula, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkyl,
Such as: R1, R2, R3 and R4 respectively can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or tertiary fourth
Base, wherein it is preferred that R1、R2、R3And R4It is methyl or ethyl.
According to the present invention, structure directing agent used in the step (1) is preferably tetraethyl ammonium hydroxide and three second
At least one of amine.
According to the present invention, mineralizer used in the step (2) is the alkali metal containing lithium, sodium, potassium, rubidium and cesium ion
At least one of compound；Preferably containing the compound of sodium, sodium chloride, sodium fluoride, sodium bromide, sodium iodide, hydrogen-oxygen can be
Change at least one of sodium, sodium carbonate and sodium bicarbonate；Preferably at least one of sodium chloride, sodium fluoride and sodium hydroxide.
According to the present invention, common water when water used in the step (1) can be synthesis of molecular sieve, in order to avoid
Heteroatomic introducing, the present invention in preferably deionized water.
According to the present invention, silicon source, structure directing agent, mineralizer and water described in the step (1) can be according to normal
Rule method is uniformly mixed to get the reaction mixture.
A kind of preferred embodiment of the invention are as follows: in step (1), can first mix silicon source, structure directing agent and water
Mineralizer is added after closing uniformly and obtains mixture, then by the mixture and is heated to 20-100 DEG C, heating time 0.1-48
Hour；It is further preferably heated to 30-90 DEG C, heating time is 2-24 hours.
According to the present invention, the crystallization condition in the step (2) is preferred are as follows: crystallization temperature is 100-180 DEG C, when crystallization
Between be 3-30 days.
According to the present invention, the crystallization in the step (2) can be in a static condition or under the conditions of dynamic agitation into
Row；It is uniformly mixed for guarantee crystallization system and obtains uniform crystallization product, crystallization process is optimized under the conditions of dynamic agitation
It carries out；It advanced optimizes to carry out dynamic crystallization under the mixing speed of 300-800r/min.
According to the present invention, the recovery method in the step (3) can be conventional absorption method, such as can be by step (2)
Obtained crystallization product obtains dry crystallization product after filtration, washing and drying；Dry temperature can be 60-180 DEG C,
The dry time can be 0.5-24 hours, further preferably are as follows: dry temperature can be 90-130 DEG C, and the dry time can
Think 2-12 hours.
According to the present invention, which can also include the following steps (4): by step (3) recycling crystallization product into
Row calcination process, to remove the structure directing agent in molecular sieve pore passage.
According to the present invention, the condition of calcination process described in the step (4) may is that maturing temperature is 400-800
DEG C, calcining time is 1-16 hours.
It below will the present invention will be described in detail by specific embodiment.In following embodiment and comparative example, X is penetrated
The crystalline phase figure of line diffraction (XRD) is to measure to obtain with Philips Panalytical X'pert, test condition are as follows: Cu target, K α
Radiation, Ni filter plate, super detector, tube voltage 30KV, tube current 40mA；The shape appearance figure of scanning electron microscope (SEM) is
It is measured with the S4800 of Hitachi company, acceleration voltage 20KV, environmental scanning.
Embodiment 1
Under the mixing speed of 400r/min, by ethyl orthosilicate, tetraethyl ammonium hydroxide, sodium hydroxide, sodium fluoride and
After mixing, the mol ratio for obtaining mixture is OH to deionized water-: SiO2: R:F:H2O=0.5:1:0.2:0.8:15, with
Gained mixture is transferred in closed pressure vessel afterwards.
Under the stirring condition of 400r/min, crystallization system is warming up to 150 DEG C, constant temperature 6 days, obtain at autogenous pressures
The mixture of crystallization product；This mixture is filtered, after being washed with water several times；It, will be dry in 110 DEG C of at a temperature of drying 6h
The original powder for the Silicalite-1 molecular sieve not roasted after mixture grinding uniformly；Finally, 550 DEG C at a temperature of it is right
The original powder of Silicalite-1 molecular sieve carries out calcination process, and calcining time 4h obtains Silicalite-1 molecular sieve, X
The crystalline phase figure of x ray diffraction (XRD) is as shown in Figure 1, the pattern result of scanning electron microscope (SEM) is as shown in Figure 2.
Embodiment 2
Under the mixing speed of 400r/min, by white carbon black, etamon chloride, sodium hydroxide, sodium chloride and deionization
After mixing, the mol ratio for obtaining mixture is OH to water-: SiO2: R:F:H2O=1.5:1:0.3:2:30, then by gained
Mixture is transferred in closed pressure vessel.
Under the stirring condition of 300r/min, crystallization system is warming up to 135 DEG C, constant temperature 12 days, obtain at autogenous pressures
To the mixture of crystallization product；This mixture is filtered, after being washed with water several times；In 130 DEG C of at a temperature of drying 4h, will dry
Mixture grinding uniformly after the original powder of Silicalite-1 molecular sieve that is not roasted；Finally, 550 DEG C at a temperature of it is right
The original powder of Silicalite-1 molecular sieve carries out calcination process, and calcining time 6h obtains Silicalite-1 molecular sieve, X
The crystalline phase figure of x ray diffraction (XRD) is similar with Fig. 1 (proving it for Silicalite-1 molecular sieve), scanning electron microscope
(SEM) pattern result is similar with Fig. 2.
Embodiment 3
Under the mixing speed of 400r/min, silica solution, tetraethylammonium bromide, sodium hydroxide and deionized water are mixed equal
After even, the mol ratio for obtaining mixture is OH-: SiO2: R:F:H2O=3:1:0.35:3:50 then turns gained mixture
It moves in closed pressure vessel.
Under the stirring condition of 200r/min, crystallization system is warming up to 180 DEG C, constant temperature 5 days, obtain at autogenous pressures
The mixture of crystallization product；This mixture is filtered, after being washed with water several times；It, will be dry in 150 DEG C of at a temperature of drying 2h
The original powder for the Silicalite-1 molecular sieve not roasted after mixture grinding uniformly；Finally, 650 DEG C at a temperature of it is right
The original powder of Silicalite-1 molecular sieve carries out calcination process, and calcining time 8h obtains Silicalite-1 molecular sieve, X
The crystalline phase figure of x ray diffraction (XRD) is similar with Fig. 1 (proving it for Silicalite-1 molecular sieve), scanning electron microscope
(SEM) pattern result is as shown in Figure 3.
Embodiment 4
Under the mixing speed of 400r/min, after mixing by silica gel, triethylamine, sodium hydroxide and deionized water, obtain
Mol ratio to mixture is OH-: SiO2: R:F:H2Gained mixture is then transferred to close by O=5:1:0.39:5:100
In the pressure vessel closed.
Under the stirring condition of 600r/min, crystallization system is warming up to 200 DEG C, constant temperature 0.5 day, obtains at autogenous pressures
To the mixture of crystallization product；This mixture is filtered, after being washed with water several times；In 90 DEG C of at a temperature of drying 12h, will dry
Mixture grinding uniformly after the original powder of Silicalite-1 molecular sieve that is not roasted；Finally, 450 DEG C at a temperature of it is right
The original powder of Silicalite-1 molecular sieve carries out calcination process, and calcining time 12h obtains Silicalite-1 molecular sieve, X
The crystalline phase figure of x ray diffraction (XRD) is similar with Fig. 1 (proving it for Silicalite-1 molecular sieve), scanning electron microscope
(SEM) pattern result is similar with Fig. 3.
Embodiment 5
Under the mixing speed of 400r/min, by ethyl orthosilicate, tetraethyl ammonium fluoride, sodium hydroxide, sodium chloride and go
After mixing, the mol ratio for obtaining mixture is OH to ionized water-: SiO2: R:F:H2O=0.1:1:0.2:0.4:20, then
Gained mixture is transferred in closed pressure vessel.
Under the stirring condition of 800r/min, crystallization system is warming up to 140 DEG C, constant temperature 10 days, obtain at autogenous pressures
To the mixture of crystallization product；This mixture is filtered, after being washed with water several times；60 DEG C at a temperature of it is dry for 24 hours, will dry
Mixture grinding uniformly after the original powder of Silicalite-1 molecular sieve that is not roasted；Finally, 400 DEG C at a temperature of it is right
The original powder of Silicalite-1 molecular sieve carries out calcination process, and calcining time 16h obtains Silicalite-1 molecular sieve, X
The crystalline phase figure of x ray diffraction (XRD) is similar with Fig. 1 (proving it for Silicalite-1 molecular sieve), scanning electron microscope
(SEM) pattern result is as shown in Figure 4.
Embodiment 6
Under the mixing speed of 400r/min, silica gel, tetraethyl ammonium hydroxide, sodium fluoride and deionized water are uniformly mixed
Afterwards, the mol ratio for obtaining mixture is OH-: SiO2: R:F:H2O=0.15:1:0.15:0.05:10 then mixes gained
Object is transferred in closed pressure vessel.
Under the stirring condition of 500r/min, crystallization system is warming up to 120 DEG C, constant temperature 20 days, obtain at autogenous pressures
To the mixture of crystallization product；This mixture is filtered, after being washed with water several times；In 120 DEG C of at a temperature of drying 4h, will dry
Mixture grinding uniformly after the original powder of Silicalite-1 molecular sieve that is not roasted；Finally, 500 DEG C at a temperature of it is right
The original powder of Silicalite-1 molecular sieve carries out calcination process, and calcining time 5h obtains Silicalite-1 molecular sieve, X
The crystalline phase figure of x ray diffraction (XRD) is similar with Fig. 1 (proving it for Silicalite-1 molecular sieve), scanning electron microscope
(SEM) pattern result is as shown in Figure 5.
Embodiment 7
Under the mixing speed of 400r/min, white carbon black, tetraethyl ammonium hydroxide, sodium hydroxide and deionized water are mixed
After uniformly, the mol ratio for obtaining mixture is OH-: SiO2: R:F:H2O=0.2:1:0.1:0.1:5 then mixes gained
Object is transferred in closed pressure vessel.
Under the stirring condition of 700r/min, crystallization system is warming up to 100 DEG C, constant temperature 30 days, obtain at autogenous pressures
To the mixture of crystallization product；This mixture is filtered, after being washed with water several times；In 140 DEG C of at a temperature of drying 5h, will dry
Mixture grinding uniformly after the original powder of Silicalite-1 molecular sieve that is not roasted；Finally, 800 DEG C at a temperature of it is right
The original powder of Silicalite-1 molecular sieve carries out calcination process, and calcining time 3h obtains Silicalite-1 molecular sieve, X
The crystalline phase figure of x ray diffraction (XRD) is similar with Fig. 1 (proving it for Silicalite-1 molecular sieve), scanning electron microscope
(SEM) pattern result is as shown in Figure 6.
Embodiment 8
Under the mixing speed of 400r/min, silica solution, tetraethyl ammonium hydroxide, sodium chloride and deionized water are mixed equal
After even, the mol ratio for obtaining mixture is OH-: SiO2: R:F:H2O=0.05:1:0.05:0.1:2 then mixes gained
Object is transferred in closed pressure vessel.
Under the stirring condition of 100r/min, crystallization system is warming up to 80 DEG C, constant temperature 60 days, obtain at autogenous pressures
The mixture of crystallization product；This mixture is filtered, after being washed with water several times；In 180 DEG C of at a temperature of drying 0.5h, will dry
Mixture grinding uniformly after the original powder of Silicalite-1 molecular sieve that is not roasted；Finally, 1000 DEG C at a temperature of
Calcination process is carried out to the original powder of Silicalite-1 molecular sieve, calcining time 1h obtains Silicalite-1 molecular sieve,
The crystalline phase figure of X-ray diffraction (XRD) is similar with Fig. 1 (proving it for Silicalite-1 molecular sieve), scanning electron microscope
(SEM) pattern result is as shown in Figure 7.
Embodiment 9
Under the mixing speed of 400r/min, by silica solution, tetraethyl ammonium fluoride, sodium hydroxide, sodium chloride and deionization
After mixing, the mol ratio for obtaining mixture is OH to water-: SiO2: R:F:H2O=1:1:0.25:1.5:20, then by institute
Mixture is obtained to be transferred in closed pressure vessel.
Under the stirring condition of 400r/min, crystallization system is warming up to 150 DEG C, constant temperature 24 days, obtain at autogenous pressures
To the mixture of crystallization product；This mixture is filtered, after being washed with water several times；In 105 DEG C of at a temperature of drying 8h, will dry
Mixture grinding uniformly after the original powder of Silicalite-1 molecular sieve that is not roasted；Finally, 600 DEG C at a temperature of it is right
The original powder of Silicalite-1 molecular sieve carries out calcination process, and calcining time 7h obtains Silicalite-1 molecular sieve, X
The crystalline phase figure of x ray diffraction (XRD) is similar with Fig. 1 (proving it for Silicalite-1 molecular sieve), scanning electron microscope
(SEM) pattern result is as shown in Figure 8.
Comparative example 1
This comparative example illustrates technical solution not according to the invention, but use existing with tetrapropylammonium hydroxide is to tie
It is prepared by the synthetic method (Microporous Mesoporous Mater, 2012,155:56-64.) of structure directed agents
The effect of Silicalite-1.
Under the mixing speed of 400r/min, by SiO2: R:OH-: H2The mol ratio of O=1:0.2:0.2:50, by positive silicon
Acetoacetic ester, tetrapropylammonium hydroxide and deionized water are uniformly mixed, and the aging 10h at a temperature of 65 DEG C, by gained mixture
It is transferred in closed pressure vessel.
Under the stirring condition of 100r/min, crystallization system is warming up to 180 DEG C, constant temperature 6 days, obtain at autogenous pressures
The mixture of crystallization product；This mixture is filtered, being washed with water to PH is about 6~8；It, will in 110 DEG C of at a temperature of drying 6h
The original powder for the Silicalite-1 molecular sieve not roasted after dry mixture grinding uniformly；Finally, in 550 DEG C of temperature
Under calcination process is carried out to the original powder of Silicalite-1 molecular sieve, calcining time 4h obtains Silicalite-1 molecular sieve,
The crystalline phase figure of its X-ray diffraction (XRD) is similar with Fig. 1 (proving it for Silicalite-1 molecular sieve), scanning electron microscopy
The pattern result of mirror (SEM) is as shown in Figure 9.
Comparative example 2
This comparative example illustrates technical solution not according to the invention, but uses existing using 4-propyl bromide as structure
It is prepared by the synthetic method (Microporous Mesoporous Mater, 2000,39:117-123.) of directed agents
The effect of Silicalite-1.
Under the mixing speed of 400r/min, by SiO2: R:OH-: H2The mol ratio of O=1:0.2:0.2:50, by hard charcoal
Black, 4-propyl bromide, sodium hydroxide and deionized water are uniformly mixed, and the aging 10h at a temperature of 65 DEG C, and gained is mixed
Object is transferred in closed pressure vessel.
Under the stirring condition of 100r/min, crystallization system is warming up to 180 DEG C, constant temperature 6 days, obtain at autogenous pressures
The mixture of crystallization product；This mixture is filtered, being washed with water to PH is about 6~8；It, will in 110 DEG C of at a temperature of drying 6h
The original powder for the Silicalite-1 molecular sieve not roasted after dry mixture grinding uniformly；Finally, in 550 DEG C of temperature
Under calcination process is carried out to the original powder of Silicalite-1 molecular sieve, calcining time 4h obtains Silicalite-1 molecular sieve,
The crystalline phase figure of its X-ray diffraction (XRD) is similar with Fig. 1 (proving it for Silicalite-1 molecular sieve), scanning electron microscopy
The results are shown in Figure 10 for the pattern of mirror (SEM).
It can be seen that the method according to the invention by the result of embodiment and comparative example to be oriented to by using new structure
Agent simultaneously carries out hydrothermal crystallizing under alkaline condition and can synthesize that crystal grain is intact, uniform Silicalite-1 molecular sieve.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (8)
1. a kind of method for synthesizing Silicalite-1 molecular sieve, comprising the following steps:
(1) silicon source, structure directing agent, mineralizer and water are uniformly mixed, obtaining mol ratio is OH-: SiO2: R:F:H2O=
(0.15-1.5): 1:(0.15-0.30): (0.15-2): the reaction mixture of (10-30), wherein R is represented in reaction mixture
The molal quantity of structure directing agent, F represent the molal quantity of mineralizer；The structure directing agent is selected from tetraethylammonium bromide, four
At least one of ethyl ammonium chloride, tetraethyl ammonium fluoride and tetraethyl ammonium iodide；
(2) reaction mixture that step (1) obtains is gone in the closed container of pressure resistance, and in 80-200 DEG C of temperature and spontaneous
Crystallization 0.5-60 days under pressure, obtain crystallization product；
(3) crystallization product that recycling step (2) obtains.
2. synthetic method according to claim 1, wherein silicon source described in step (1) is selected from estersil, solid silicon
At least one of glue, white carbon black and silica solution.
3. synthetic method according to claim 1, wherein silicon source, structure directing agent, mineralizer described in step (1)
Be uniformly mixed with water is that silicon source, structure directing agent, mineralizer and water are heated to 0.1-48 within the temperature range of 20-100 DEG C is small
When.
4. synthetic method according to claim 1, wherein mineralizer described in step (1) be selected from containing lithium, sodium, potassium,
At least one of rubidium and the alkali metal compound of cesium ion.
5. synthetic method according to claim 1, wherein mineralizer described in step (1) be selected from NaCl, NaF and
At least one of NaOH.
6. synthetic method according to claim 1, wherein the condition of crystallization described in step (2) is: crystallization temperature is
100-180 DEG C, crystallization time is 3-30 days.
7. synthetic method according to claim 1, wherein this method further includes step (4): the crystalline substance that step (3) are recycled
Change product and carries out calcination process.
8. synthetic method according to claim 7, wherein roasting condition described in step (4) is: maturing temperature is
300-1000 DEG C, calcining time is 0.5-16 hours.
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| CN108002396B (en) * | 2017-12-21 | 2020-12-01 | 吉林大学 | Method for synthesizing Silicalite-1 molecular sieve by taking TPABr as template agent |
| CN114644347B (en) * | 2020-12-17 | 2023-07-04 | 中国石油化工股份有限公司 | SAPO-20 molecular sieve and preparation method thereof |
| CN112624146B (en) * | 2021-01-12 | 2022-11-18 | 国家能源集团宁夏煤业有限责任公司 | Molecular sieve and preparation method and application thereof |
| FR3145293A1 (en) | 2023-01-27 | 2024-08-02 | Arkema France | SILICALITE-1 CRYSTALS AND THEIR SYNTHESIS PROCESS |
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| CN102515193A (en) * | 2011-12-31 | 2012-06-27 | 中国天辰工程有限公司 | Synthetic method of siliceous molecular sieve |
| CN102774851A (en) * | 2012-08-06 | 2012-11-14 | 黑龙江省科学院高技术研究院 | Method for preparing nano sillicalite-1 type total-silicalite molecular sieve |
| CN102794117A (en) * | 2012-07-29 | 2012-11-28 | 北京工业大学 | Preparation method of silazane-modified silicalite-1 molecular sieve filling silicon rubber composite membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102515193A (en) * | 2011-12-31 | 2012-06-27 | 中国天辰工程有限公司 | Synthetic method of siliceous molecular sieve |
| CN102794117A (en) * | 2012-07-29 | 2012-11-28 | 北京工业大学 | Preparation method of silazane-modified silicalite-1 molecular sieve filling silicon rubber composite membrane |
| CN102774851A (en) * | 2012-08-06 | 2012-11-14 | 黑龙江省科学院高技术研究院 | Method for preparing nano sillicalite-1 type total-silicalite molecular sieve |
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