CN107473239B - A kind of synthetic method of ZSM-51 molecular sieve and synthesized ZSM-51 molecular sieve - Google Patents
A kind of synthetic method of ZSM-51 molecular sieve and synthesized ZSM-51 molecular sieve Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The invention discloses a kind of synthetic method of ZSM-51 molecular sieve and synthesized ZSM-51 molecular sieve, which includes: a, by the mixing of tetraethyl ammonium hydroxide, silicon source, trimethylethyl ammonium bromide, water and silicon source, is obtained to crystallization mixture；B, gained in step a is subjected to the processing of first segment hydrothermal crystallizing to crystallization mixture and second segment hydrothermal crystallizing is handled, by obtained solid washing, drying after crystallization.Using the hydrogen storage large amount of adsorption of ZSM-51 molecular sieve synthesized by synthetic method of the invention.
Description
Technical field
The present invention relates to a kind of synthetic method of ZSM-51 molecular sieve and synthesized ZSM-51 molecular sieves.
Background technique
The initial stage eighties, Mobil company, the U.S. have synthesized new-type high silicon aluminium than molecular sieve ZSM-51, structure type for the first time
For NON type, belong to orthorhombic structure, there is hexatomic ring cellular structure.ZSM-51 molecular sieve is widely used as inhaling since aperture is small
Attached dose.In addition, it has unique advantage as carrier on hydrogenation catalyst, the valuable gold such as vanadium, molybdenum, nickel, platinum can be loaded
Belong to, is ideal hydrogenation activity carrier, hydrogen storage adsorbance is also an important performance of the ZSM-51 as catalyst carrier for hydrgenating
Index.
United States Patent (USP) US4568654 disclose Ernest W.Valyocsik et al. using containing cobalt metal complex, two
Methyl piperidine salt, bis- (trimethylene) leptodactylines, tetramethyl piperidine etc. are used as template, have synthesized ZSM-51 molecule for the first time
Sieve.
United States Patent (USP) US5194410 discloses David C.Calabro et al. and uses hard metylethylbenzyl [3- (front three
Base silicon substrate propane)] chlorination ammonium salt synthesized pure phase ZSM-51 molecular sieve at 180 DEG C.But template used in the patent
Structure is more complicated.
United States Patent (USP) US20020085976 discloses Saleh Elomari et al. using N, N, N- trimethyl (2- methyl-
The m- tolyl butyl of 2-) ammonium salt, N, N, N- trimethyl (the o- tolyl butyl of 2- methyl -2-) ammonium salt, N, N, N- trimethyl (2-
The p- tolyl butyl of methyl -2-) the complicated template such as ammonium salt synthesized ZSM-51 molecular sieve under certain condition.
Document " Moini A, Schmitt K D, Polomski R F.Pentamethyl diethylene triamine
and its quaternary cations as directing agents in zeolite synthesis:
Monitoring the stability of directing agents under hydrothermal conditions
[J] .Zeolites, 1997,18 (1): 2-6 ", which is reported using Ah 'ss ammonium salt, reacts 10 under conditions of 160 DEG C as template
It, is prepared the ZSM-51 molecular sieve of pure phase.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of ZSM-51 molecular sieve and synthesized ZSM-51 molecular sieves, adopt
The hydrogen storage large amount of adsorption of the ZSM-51 molecular sieve synthesized by synthetic method of the invention.
The synthetic method of ZSM-51 molecular sieve provided by the invention includes: a, by tetraethyl ammonium hydroxide, silicon source, trimethyl
Ethyl phosphonium bromide ammonium, water and silicon source mixing, obtain to crystallization mixture；Wherein, described in crystallization mixture, SiO2/Al2O3=
(10-100): 1, BA/SiO2=(0.01-2): 1, H2O/SiO2=(5-50): 1, R/SiO2=(0.05-0.5): 1, M2O/SiO2
=(0.05-0.3): 1, the BA are tetraethyl ammonium hydroxide, and the R is trimethylethyl ammonium bromide, the M2O is alkali metal
Oxide；
B, gained in step a is successively subjected to the processing of first segment hydrothermal crystallizing and second segment hydrothermal crystallizing to crystallization mixture
Processing, by obtained solid washing, drying after crystallization；Wherein, the condition of the first segment hydrothermal crystallizing processing includes: crystallization temperature
It is 80-140 DEG C, crystallization time is 1-7 days, and crystallization pressure is self-generated pressure；The condition packet of the second segment hydrothermal crystallizing processing
Include: crystallization temperature is 150-200 DEG C, and crystallization time is 5-14 days, and crystallization pressure is self-generated pressure.
The present invention also provides ZSM-51 molecular sieves synthesized by synthetic method provided by the present invention.
Compared with prior art, structure directing agent structure used by synthetic method of the present invention is simple, is easy to get, is closed
At ZSM-51 molecular sieve hydrogen storage large amount of adsorption.
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
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the XRD spectra of molecular sieve synthesized by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of molecular sieve synthesized by the embodiment of the present invention 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of molecular sieve synthesized by the embodiment of the present invention 2.
Fig. 4 is the XRD spectra of molecular sieve synthesized by comparative example 1 of the present invention.
Fig. 5 is the XRD spectra of molecular sieve synthesized by comparative example 4 of the present invention.
Fig. 6 is relative pressure-hydrogen storage absorption of the embodiment of the present invention 1, molecular sieve synthesized by embodiment 2 and comparative example 4
The figure of amount.
Specific embodiment
The present invention is in the presence of tetraethyl ammonium hydroxide, using trimethylethyl ammonium bromide as structure directing agent, passes through two sections
Hydrothermal crystallization method synthesizes ZSM-51 molecular sieve, and synthesis directed agents used and organic base structure are simple and easy to get, molecular sieve obtained
There is preferable absorption property.
Silicon source, trimethylethyl ammonium bromide and silicon source are well-known to those skilled in the art, the trimethylethyl bromines
Change the structural formula of ammonium are as follows:
Source of aluminium can be aluminium chloride, aluminum sulfate, aluminium hydroxide, sodium metaaluminate or Aluminum sol, preferably sodium metaaluminate
Or Aluminum sol.
The silicon source can be silica solution, silica white, ethyl orthosilicate, waterglass or white carbon black, preferably be easy depolymerization
Silicon source, such as silica solution or white carbon black.
The M2O can be sodium oxide molybdena.
Preferably, described in crystallization mixture, SiO2/Al2O3=(20-50): 1, BA/SiO2=(0.5-1.8): 1,
H2O/SiO2=(20-45): 1, R/SiO2=(0.05-0.35): 1, M2O/SiO2=(0.05-0.2): 1.
The present invention to the order by merging of tetraethyl ammonium hydroxide, silicon source, trimethylethyl ammonium bromide, water and silicon source not
It limits, as long as being uniformly mixed, it is preferable that at least stirred 30 minutes after the raw material being mixed.
Hydrothermal crystallizing processing be it is well-known to those skilled in the art, the present invention will be to crystallization mixture in different crystallization items
Two sections of crystallization are successively carried out under part, a temperature-rise period are generally comprised between two sections of crystallization, such as first segment hydrothermal crystallizing is produced
Object is warming up to the temperature of second segment hydrothermal crystallizing using the temperature of first segment hydrothermal crystallizing as starting point with 1-10 DEG C/min of heating rate
Degree.
Currently preferred to be: it is 110-140 that the condition of the first segment hydrothermal crystallizing processing, which may include: crystallization temperature,
DEG C, crystallization time is 2-6 days；It is 150-180 DEG C that the condition of the second segment hydrothermal crystallizing processing, which may include: crystallization temperature,
Crystallization time is 5-12 days.
Two sections of crystallization products therefroms are solidliquid mixture, therefore the present invention can also include consolidating the solidliquid mixture
Liquid separation, washing, drying and roasting and etc., abovementioned steps are well known to the skilled person, for example, the drying can
To be dried under atmospheric pressure or vacuum condition, roasting can be under steam, air or inert gas existence condition in 300-
It is roasted 2-6 hours at 700 DEG C.
The present invention is further illustrated below by embodiment, but is not thereby limited the invention.
The XRD of the embodiment of the present invention and comparative example is measured on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44
Kilovolt, 40 milliamperes, scanning speed is 2 °/minute.
The nuclear magnetic resonance spectroscopy that the present invention prepares embodiment is used using the production of U.S. Varian companyUNITYINOVA
500MHz nuclear magnetic resonance chemical analyser is measured.
The scanning electron microscope (SEM) photograph of the embodiment of the present invention and comparative example uses Japan's Hitachi S-4800 type scanning electron microscope
Device is measured.
The hydrogen storage adsorbance of ZSM-51 molecular sieve prepared by the embodiment of the present invention and comparative example is complete certainly using 3H-2000PH
Dynamic high pressure gas adsorption instrument is measured.Determination condition are as follows: using volumetric method at liquid nitrogen temperature (77K), in 1.51MPa pressure
Under tested.
Prepare embodiment 1
This preparation embodiment provides the preparation method of structure directing agent trimethylethyl ammonium bromide and prepared structure is led
To agent.
25g (0.4mol) triethylamine is added in 500ml there-necked flask, 200ml isopropanol is added, 46g is added dropwise under ice bath
(0.4mol) bromoethane, 15min are added dropwise, and stir 3h at room temperature, and solution becomes white from colourless, and removing solvent obtains colorless oil
Shape object 33.2g, as trimethylethyl ammonium bromide.
Nuclear magnetic resonance spectroscopy (1H-NMR) (300MHz, internal standard TMS, solvent C DCl3) δ (ppm) result is as follows: 1.48 (3H,
M), 3.22 (9H, s), 3.52 (2H, dd).
Embodiment 1-5 illustrates the synthetic method of ZSM-51 molecular sieve of the invention.
Embodiment 1
It takes 0.134g sodium metaaluminate to be added in 45ml polytetrafluoroethylene (PTFE) (Teflon) container, is separately added into 14.38g deionization
Water, (AlfaAesar (Tianjin) chemistry is limited for tetraethyl ammonium hydroxide (referred to as BA) solution that 13.69g mass fraction is 35%
Company, similarly hereinafter), structure directing agent trimethylethyl ammonium bromide (hereinafter referred to as R, similarly hereinafter) prepared by preparation embodiment 1
1.08g is stirred until homogeneous, and 2g white carbon black is added, gained mixture is uniformly mixed, is obtained to crystallization mixture.Wherein each group
The molar ratio divided are as follows: SiO2/Al2O3=40, Na2O/SiO2=0.12, BA/SiO2=1.0, H2O/SiO2=40, R/SiO2=
0.15。
It will be sealed in the steel autoclave of Teflon liner to crystallization mixture, which be placed in 120 DEG C
Rotation convection oven in, revolving speed is set as 20rpm, carry out first segment hydrothermal crystallizing and handle 4 days, temperature is raised to 160 DEG C, it
Second segment hydrothermal crystallizing is carried out afterwards to handle 10 days.It then takes out autoclave and it is made to be rapidly cooled to room temperature, then by crystallization institute
Solidliquid mixture is obtained by isolating solid and liquid on the supercentrifuge of 5000rpm, by the solid deionization of recycling
Water washing, 100 DEG C drying 3 hours, obtain molecular sieve.Gained sieve sample is passed through into XRD analysis and scanning electron microscope analysis.Fig. 1
It shows the XRD spectra for the sieve sample that embodiment 1 synthesizes, is ZSM-51 molecular sieve.Fig. 2 is sweeping for synthesis of molecular sieve sample
Electron microscope is retouched, finds out that ZSM-51 molecular sieve has shuttle shape pattern from Electronic Speculum, the dimensional structure of single shuttle shape is 10 μm of 5 μ m.
Embodiment 2
It takes 0.134g sodium metaaluminate to be added in 45mlTeflon container, is separately added into 17.16g deionized water, 9.52g mass
Score be 35% tetraethyl ammonium hydroxide solution, preparation embodiment 1 prepared by structure directing agent trimethylethyl ammonium bromide
1.08g is stirred until homogeneous, and 2g white carbon black is added, gained mixture is uniformly mixed, is obtained to crystallization mixture.Wherein each group
The molar ratio divided are as follows: SiO2/Al2O3=40, Na2O/SiO2=0.12, BA/SiO2=0.7, H2O/SiO2=40, R/SiO2=
0.15。
It will be sealed in the steel autoclave of Teflon liner to crystallization mixture, which be placed into 120 DEG C
Rotation convection oven in, revolving speed is set as 20rpm, carry out first segment hydrothermal crystallizing and handle 4 days, temperature is raised to 170 DEG C, it
Second segment hydrothermal crystallizing is carried out afterwards to handle 7 days.It then takes out autoclave and it is made to be rapidly cooled to room temperature, it then will be obtained by crystallization
Solidliquid mixture on the supercentrifuge of 5000rpm by isolating solid and liquid, by the solid deionized water of recycling
Washing, 100 DEG C drying 3 hours, obtain molecular sieve.By gained sieve sample, by XRD analysis, (spectrogram is similar to Fig. 1, does not show
Out) and scanning electron microscope analysis, XRD analysis show that the sieve sample that embodiment 2 synthesizes is ZSM-51 molecular sieve.Fig. 3 is synthesis
The scanning electron microscope (SEM) photograph of sample finds out that ZSM-51 molecular sieve has shuttle shape pattern from Electronic Speculum, and the dimensional structure of single shuttle shape is 5 μm
×10μm。
Embodiment 3
It takes 0.134g sodium metaaluminate to be added in 45mlTeflon container, is separately added into 18.90g deionized water, 6.845g matter
Measure structure directing agent trimethylethyl bromination prepared by the tetraethyl ammonium hydroxide solution that score is 35%, preparation embodiment 1
Ammonium 1.08g, is stirred until homogeneous, and 2g white carbon black is added, gained mixture is uniformly mixed, is obtained to crystallization mixture.It is wherein each
The molar ratio of component are as follows: SiO2/Al2O3=40, Na2O/SiO2=0.12, BA/SiO2=0.5, H2O/SiO2=40, R/SiO2=
0.15。
It will be put into crystallization mixture in the closed steel autoclave for having Teflon liner of 45ml, which placed
Into 120 DEG C of rotation convection oven, revolving speed is set as 20rpm, carries out first segment hydrothermal crystallizing and handles 2 days, temperature is raised to
170 DEG C, second segment hydrothermal crystallizing is carried out later and is handled 7 days.It takes out autoclave and it is made to be rapidly cooled to room temperature, it will be obtained by crystallization
Solidliquid mixture on the supercentrifuge of 5000rpm by isolating solid and liquid, by the solid deionized water of recycling
Washing, 100 DEG C drying 3 hours, by gained sieve sample pass through XRD analysis (spectrogram is similar to Fig. 1, is not shown), it is shown that
The sample that embodiment 3 synthesizes is ZSM-51 molecular sieve.Gained sample by scanning electron microscope analysis (scanning electron microscope (SEM) photograph is similar to Fig. 3,
It is not shown), find out that ZSM-51 molecular sieve has shuttle shape pattern from Electronic Speculum.
Embodiment 4
It takes 0.134g sodium metaaluminate to be added in 45mlTeflon container, is separately added into 18.90g deionized water, 6.845g matter
Measure structure directing agent trimethylethyl bromination prepared by the tetraethyl ammonium hydroxide solution that score is 35%, preparation embodiment 1
Ammonium 1.08g, is stirred until homogeneous, and 3g white carbon black is added, gained mixture is uniformly mixed, is obtained to crystallization mixture.It is wherein each
The molar ratio of component are as follows: SiO2/Al2O3=80, Na2O/SiO2=0.1, BA/SiO2=0.34, H2O/SiO2=27, R/SiO2=
0.13。
It will be sealed in steel autoclave to crystallization mixture, which is placed into 120 DEG C of rotation convection oven
In, revolving speed is set as 20rpm, after carrying out the processing of first segment hydrothermal crystallizing 1 day, temperature is raised to 170 DEG C, carries out second segment later
Hydrothermal crystallizing is handled 8 days.It takes out autoclave and it is made to be rapidly cooled to room temperature, solidliquid mixture is passed through into the height in 5000rpm
Isolate solid and liquid on fast centrifuge, the solid of recycling is washed with deionized, 100 DEG C drying 3 hours, obtain molecule
Sieve.Gained sieve sample pass through XRD analysis (spectrogram is similar to Fig. 1, is not shown), it is shown that embodiment 4 synthesis sample be
ZSM-51 molecular sieve.Gained sieve sample is scanned electron microscope analysis (scanning electron microscope (SEM) photograph is similar to Fig. 3, is not shown), from
Find out that ZSM-51 molecular sieve has shuttle shape pattern in Electronic Speculum.
Embodiment 5
Embodiment 5 and the preparation method of embodiment 1 are essentially identical, the difference is that charge ratio and crystallization condition, i.e.,
Charge ratio are as follows: SiO2/Al2O3=20, Na2O/SiO2=0.25, BA/SiO2=1.6, H2O/SiO2=10, R/SiO2=0.4,
The condition of first segment hydrothermal crystallizing processing includes: that crystallization temperature is 90 DEG C, and crystallization time is 2 days；The processing of second segment hydrothermal crystallizing
Condition include: crystallization temperature be 160 DEG C, crystallization time be 8 days, the XRD diagram and scanning electron microscope (SEM) photograph of gained sieve sample with
Embodiment 1 is similar, is not shown, i.e., gained sample is shuttle shape pattern ZSM-51 molecular sieve.
Comparative example 1
This comparative example illustrates that the molecular sieve that trimethylethyl ammonium bromide is added without using tetraethyl ammonium hydroxide as template closes
At method.
It takes 0.134g sodium metaaluminate to be added in 45mlTeflon container, is separately added into 14.45g deionized water, 13.69g matter
The tetraethyl ammonium hydroxide solution that score is 35% is measured, 2g white carbon black is added, is uniformly mixed, obtains to crystallization mixture.
The wherein molar ratio of each component are as follows: SiO2/Al2O3=40, Na2O/SiO2=0.12, BA/SiO2=1.0, H2O/SiO2=40.
It will be sealed in steel autoclave to crystallization mixture, which is placed into 120 DEG C of rotation convection oven
In, revolving speed is set as 20rpm, after carrying out the processing of first segment hydrothermal crystallizing 4 days, temperature is raised to 160 DEG C, carries out second segment later
Hydrothermal crystallizing is handled 10 days.Then take out autoclave and it made to be rapidly cooled to room temperature, then by solidliquid mixture by
Isolate solid and liquid on the supercentrifuge of 5000rpm, the solid of recycling is washed with deionized, 100 DEG C of dryings 3 it is small
When, molecular sieve is obtained, gained sieve sample is subjected to XRD analysis.Fig. 4 shows the XRD spectra of 1 synthetic sample of comparative example, is
ZSM-5 molecular sieve.
Comparative example 2
This comparative example illustrates using tetramethylammonium hydroxide as the method for template synthesis of molecular sieve.
It takes 0.134g sodium metaaluminate to be added in 45mlTeflon container, is separately added into 14.44g deionized water, 11.79g matter
Measure structure directing agent trimethyl second prepared by tetramethylammonium hydroxide (TMAOH) solution that score is 25%, preparation embodiment 1
Base ammonium bromide 1.08g, is stirred until homogeneous, and 2g white carbon black is added, gained mixture is uniformly mixed, is obtained to crystallization mixture.
The wherein molar ratio of each component are as follows: SiO2/Al2O3=40, Na2O/SiO2=0.12, TMAOH/SiO2=1.0, H2O/SiO2=
40, R/SiO2=0.15.
It will be sealed in steel autoclave to crystallization mixture, which is placed into 120 DEG C of rotation convection oven
In, revolving speed is set as 20rpm, carries out first segment hydrothermal crystallizing and handles 4 days, temperature is raised to 160 DEG C, carries out second segment water later
Thermal crystallisation is handled 10 days.Taking out autoclave simultaneously makes it be rapidly cooled to room temperature, then by solidliquid mixture obtained by crystallization by
Isolate solid and liquid on the supercentrifuge of 5000rpm, the solid of recycling is washed with deionized, 100 DEG C of dryings 3 it is small
When, molecular sieve is obtained, gained sieve sample is subjected to XRD analysis.XRD spectra (not shown) shows that sample is LTA and ZSM-51
The co-crystalline zeolite of molecular sieve.
Comparative example 3
This comparative example illustrates using tetrapropylammonium hydroxide as the method for template synthesis of molecular sieve.
It takes 0.134g sodium metaaluminate to be added in 45mlTeflon container, is separately added into 3.55g deionized water, 26.30g mass
Score be 25% tetrapropylammonium hydroxide (TPAOH) solution, preparation embodiment 1 prepared by structure directing agent trimethylethyl
Ammonium bromide 1.08g, is stirred until homogeneous, and 2g white carbon black is added, gained mixture is uniformly mixed, is obtained to crystallization mixture.Its
The molar ratio of middle each component are as follows: SiO2/Al2O3=40, Na2O/SiO2=0.12, TPAOH/SiO2=1.0, H2O/SiO2=40,
R/SiO2=0.15.
It will be sealed in steel autoclave to crystallization mixture, which is placed into 120 DEG C of rotation convection oven
In, revolving speed is set as 20rpm, carries out first segment hydrothermal crystallizing and handles 4 days, temperature is raised to 160 DEG C, carries out second segment water later
Thermal crystallisation is handled 10 days.Then take out autoclave and it made to be rapidly cooled to room temperature, then by solidliquid mixture by
Isolate solid and liquid on the supercentrifuge of 5000rpm, the solid of recycling is washed with deionized, 100 DEG C of dryings 3 it is small
When, molecular sieve is obtained, gained sieve sample is subjected to XRD analysis.XRD spectra (not shown) shows that sample is ZSM-5 and ZSM-
The co-crystalline zeolite of 51 molecular sieves.
Comparative example 4
With bis- (trimethylene) leptodactyline ((CH in United States Patent (USP) US 45686543)3N+-CH2-CH2-CH2-N+
(CH3)3) as template, be silicon source as silicon source, using aluminum sulfate using waterglass and be alkali source (with OH using NaOH-Indicate) synthesis
ZSM-51 molecular sieve.It is formulated as follows: SiO2/Al2O3=60, H2O/SiO2=40, OH-/SiO2=0.20, Na/SiO2=0.29,
R/SiO2=0.1, wherein R is bis- (trimethylene) leptodactylines, and 160 DEG C of hydrothermal crystallizings are handled 3 days, obtains ZSM-51 molecule
Sieve, specific XRD spectra are as shown in Figure 5.
Embodiment 6
ZSM-51 molecular sieve prepared by embodiment 1 is heated under the flowing of air to 550 DEG C in Muffle furnace and is protected
6 hours are held to be roasted, hydrogen is adsorbed in 3H-2000PH full-automatic high-pressure gas absorption instrument later, is measured
Relative pressure-hydrogen storage adsorbance figure is shown in Fig. 6, and saturation hydrogen storage adsorbance is shown in Table 1.
Embodiment 7-10
The hydrogen storage adsorbance of ZSM-51 molecular sieve prepared by test method measurement embodiment 2-5 using embodiment 6,
In, relative pressure-hydrogen storage adsorbance figure of molecular sieve prepared by the embodiment 2 that embodiment 7 measures is shown in Fig. 6, embodiment 7-10
The saturation hydrogen storage adsorbance for surveying each molecular sieve is shown in Table 1.
Comparative example 5
The hydrogen storage adsorbance of ZSM-51 molecular sieve prepared by test method measurement comparative example 4 using embodiment 6, gained
Relative pressure-hydrogen storage adsorbance figure is shown in Fig. 6, and saturation hydrogen storage adsorbance is shown in Table 1.
Table 1
Can be seen that from the data of table 1 has high unsaturation using the ZSM-51 molecular sieve that method of the invention synthesizes
Hydrogen storage adsorbance and saturation hydrogen storage adsorbance.
Claims (7)
1. a kind of synthetic method of ZSM-51 molecular sieve, the synthetic method include:
A, tetraethyl ammonium hydroxide, silicon source, trimethylethyl ammonium bromide, water and silicon source are mixed, is obtained to crystallization mixture；Its
In, described in crystallization mixture, SiO2/Al2O3=(10-100): 1, BA/SiO2=(0.01-2): 1, H2O/SiO2=(5-
50): 1, R/SiO2=(0.05-0.5): 1, M2O/SiO2=(0.05-0.3): 1, the BA are tetraethyl ammonium hydroxide, the R
For trimethylethyl ammonium bromide, the M2O is alkali metal oxide；
B, gained in step a is successively carried out at the processing of first segment hydrothermal crystallizing and second segment hydrothermal crystallizing to crystallization mixture
Reason, by obtained solid washing, drying after crystallization；Wherein, the condition of the first segment hydrothermal crystallizing processing includes: that crystallization temperature is
80-140 DEG C, crystallization time is 1-7 days, and crystallization pressure is self-generated pressure；The condition of second segment hydrothermal crystallizing processing includes:
Crystallization temperature is 150-200 DEG C, and crystallization time is 5-14 days, and crystallization pressure is self-generated pressure.
2. synthetic method according to claim 1, wherein described in crystallization mixture, SiO2/Al2O3=(20-50):
1, BA/SiO2=(0.5-1.8): 1, H2O/SiO2=(20-45): 1, R/SiO2=(0.05-0.35): 1, M2O/SiO2=
(0.05-0.2): 1.
3. synthetic method according to claim 1, wherein source of aluminium is aluminium chloride, aluminum sulfate, aluminium hydroxide, inclined aluminium
Sour sodium or Aluminum sol.
4. synthetic method according to claim 1, wherein the silicon source is silica solution, silica white, ethyl orthosilicate, water
Glass or white carbon black.
5. synthetic method according to claim 1, wherein the M2O is sodium oxide molybdena.
6. synthetic method according to claim 1, wherein the condition of the first segment hydrothermal crystallizing processing includes: crystallization
Temperature is 110-140 DEG C, and crystallization time is 2-6 days；The condition of the second segment hydrothermal crystallizing processing includes: that crystallization temperature is
150-180 DEG C, crystallization time is 5-12 days.
7. ZSM-51 molecular sieve synthesized by synthetic method described in any one of claim 1-6 has shuttle shape pattern.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4568654A (en) * | 1982-11-03 | 1986-02-04 | Mobil Oil Corporation | Zeolite ZSM-51 composition |
| US4840780A (en) * | 1983-03-28 | 1989-06-20 | Mobil Oil Corporation | ZSM-51, method of preparing same and catalytic conversion therewith |
| US5194410A (en) * | 1991-11-15 | 1993-03-16 | Mobil Oil Corporation | Crystalline molecular sieve synthesis using quaternary ammonium-functionalized organosiliconate |
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| US6632417B2 (en) * | 2000-03-07 | 2003-10-14 | Chevron U.S.A. Inc. | Process for preparing zeolites |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4568654A (en) * | 1982-11-03 | 1986-02-04 | Mobil Oil Corporation | Zeolite ZSM-51 composition |
| US4840780A (en) * | 1983-03-28 | 1989-06-20 | Mobil Oil Corporation | ZSM-51, method of preparing same and catalytic conversion therewith |
| US5194410A (en) * | 1991-11-15 | 1993-03-16 | Mobil Oil Corporation | Crystalline molecular sieve synthesis using quaternary ammonium-functionalized organosiliconate |
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