CN107008157B - A kind of SAPO-56 molecular screen membrane and preparation method thereof - Google Patents

A kind of SAPO-56 molecular screen membrane and preparation method thereof Download PDF

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CN107008157B
CN107008157B CN201710252885.8A CN201710252885A CN107008157B CN 107008157 B CN107008157 B CN 107008157B CN 201710252885 A CN201710252885 A CN 201710252885A CN 107008157 B CN107008157 B CN 107008157B
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sapo
supporter
crystal seed
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screen membrane
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CN107008157A (en
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顾学红
彭莉
薛有泉
邱豪
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Nanjing Tech University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

Present invention relates particularly to a kind of SAPO-56 molecular screen membranes and preparation method thereof.Method of the invention is with N, N, N ', N '-tetramethyl -1,6- hexamethylene diamine is template machine, and aluminium isopropoxide is silicon source, and phosphoric acid is phosphorus source, silica solution is silicon source, SAPO-56 molecular screen membrane is prepared in alumina support through hydrothermal synthesis method, and remove template machine in ozone system.The SAPO-56 molecular screen membrane and preparation method being prepared are to report for the first time, and film surface is activated in ozone environment and all to be main improvement of the invention with the methods of removed template method at low temperature.

Description

A kind of SAPO-56 molecular screen membrane and preparation method thereof
Technical field
The present invention provides a kind of SAPO-56 molecular screen membrane and preparation method thereof, succeeds supported in porous aluminas for the first time SAPO-56 molecular screen membrane is prepared on body, belongs to field of inorganic materials.
Background technique
Natural gas is the important energy source and chemical raw material arranged side by side with petroleum, coal.Carbon dioxide be natural gas (effectively at Be divided into methane) major impurity gas, not only reduce the combustion heat value of natural gas, but also gas pipeline made under moisture conditions At corrosion.Separation CO at present2Method mainly include organic amine absorbing and removing and organic UF membrane.There are equipment investments for amine absorption High, bulky, the problems such as absorbent regeneration energy consumption is high.UF membrane is with low energy consumption, continuity operates, equipment investment is low, body The advantages that product is small, easy to maintain, but in the presence of high carbon dioxide concentration and high-carbon hydrocarbon phenomena such as carbon is crisp, shadow easily occur for organic film Ring the separating property and stability of film.In recent years, inoranic membrane, especially molecular screen membrane, by feat of good mechanical stability, Corrosion resistance and higher thermal stability, to CO in natural gas2Processing have broad application prospects.Molecular screen membrane has equal Even molecular scale duct and unique absorption property, it can use the difference and absorption property of gas molecule diffusion coefficient Difference separates to realize.Pass through the molecular sieve for selecting that there is suitable aperture, diffusion of the gas with various molecule in molecular sieve pore passage Coefficient can have the difference of several orders of magnitude, therefore can obtain high diffusion selectivity.Meanwhile gas molecule is in molecular sieve Selective absorption in crystal duct can also obtain higher selectivity.CO2Molecular dynamics diameter be 0.33 nm, CH4's Molecular dynamics diameter is 0.38 nm, therefore the molecular screen membrane of aperture, such as DDR type (0.36 × 0.44 nm), T-type (aperture 0.36 × 0.51 nm) and SAPO-34 (0.38 nm) etc., aperture and CH4Gas Molecules Kinetics diameter is similar, and bigger In CO2Gas Molecules Kinetics diameter, under molecule screening and competitive Adsorption synergistic effect, these molecular screen membranes are with higher CO2/ CH4Separating property.
SAPO-56 molecular sieve has AFX type topological structure and three-dimensional 8 membered ring channels communicated, pore size 0.34 × 0.36 nm, between CO2(0.33 nm) and CH4Between (0.38 nm).Absorption test display SAPO-56 molecular sieve is to CO2It inhales It is attached to can achieve 5.46 mmol/g (273 K, 101 kPa), it is apparently higher than other small pore moleculars such as SAP0-34 molecular sieve Sieve.SAPO-56 molecular sieve pore passage size is less than above-mentioned molecular sieve simultaneously, and therefore, SAP0-56 molecular sieve is in separation CO24 body of/CH Significantly higher preferred absorption and molecule sieving actoion [Cheung O, Liu Q, Bacsik Z, Hedin can be shown when being N, Microporous and Mesoporous Materials, 2012,156,90-96；Bacsik Z, Cheung O, Vasiliev P, Hedin N, Applied Energy, 2016,162,613-621], still, there has been no successfully synthesize at present The report of SAPO-56 molecular screen membrane.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the SAPO-56 molecular screen membrane of porous aluminas support, we It is owned by France that fine and close aluminium silicophosphate type SAPO-56 molecular screen membrane is prepared on porous alumina carrier in being put forward for the first time.
The first aspect of the invention:
A kind of SAPO-56 molecular screen membrane includes selection separating layer and supporter, separating layer is selected to be overlying on the table of supporter Face；The selection separating layer is made of fine and close SAPO-56 molecular sieve；The supporting layer is by porous ceramics institute structure At.
The configuration of the supporter is selected from chip, tubular type or hollow fiber form.
Number of channels inside the supporter of the hollow fiber form is 1~6, and external diametrical extent is 2~6mm, internal Channel diameter range is 0.3~1.5mm.
The thickness of the supporter of the chip is 1~10mm.
Outer diameter preferably 4~20mm of the tubular type supporter, internal diameter preferably 1~12mm.
One in the preferred silicon carbide of the material of porous ceramics, diatomite, mullite, aluminium oxide, zirconium oxide or titanium oxide Kind or several mixing.
The second aspect of the invention:
A kind of preparation method of SAPO-56 molecular screen membrane, includes the following steps:
Step 1 carries out ball-milling treatment to SAPO-56 molecular sieve using high energy ball mill, stand-by as crystal seed；
Crystal seed plus water are configured to suspension by step 2, add thickener, after mixing, as crystal seed liquid；Again will Dry porous ceramic support immerses in crystal seed liquid, carries out Best-Effort request, after taking-up, drying；Using calcining, loaded There is the supporter of crystal seed；
The supporter that load has crystal seed is placed in film Synthesis liquid by step 3, carries out hydrothermal synthesis, after taking-up, drying, then It is calcined under ozone environment, obtains SAPO-56 molecular screen membrane.
In the step 1, ball milling refers to the fine powder that SAPO-56 molecular sieve is broken for 50nm~2 μm, more preferably 0.3μm。
In the step 2, concentration of the crystal seed in suspension is 0.5~1wt%, concentration of the thickener in crystal seed liquid It is 0.02~0.1wt%.
In the step 2, thickener is hydroxypropyl cellulose (HPC).
In the step 2, the preferred silicon carbide of the material of porous ceramic support, diatomite, mullite, aluminium oxide, oxygen Change one of zirconium or titanium oxide or several mixing；The configuration of the supporter is selected from chip, tubular type or hollow Fiber type.
In the step 2, dry porous ceramic support is first passed through in distilled water plus was ultrasonically treated.
In the step 2, the parameter of calcination process is: 440~460 DEG C of 6~10h of calcining.
It is Al that silicon source, phosphorus source, silicon source, template, which are according to molar ratio, in the step 3, in film Synthesis liquid2O3: P2O5: SiO2: template: H2O=0.8:(0.8~1.2): (0.5~0.7): (1.8~2.2): the proportional arrangement of (45~55)；More preferably Ratio be 0.8:1.0:0.6:2:50.
The template is N, N, N ', N '-tetramethyl -1,6- hexamethylene diamine (TMHD).
In the step 3, the parameter of hydrothermal synthesis is: being warming up to 180~220 with the rate of 0.8~1.2 DEG C/min DEG C, 40~50h is kept the temperature, then be cooled to 20~30 DEG C with the rate of 0.8~1.2 DEG C/min.
In the step 3, calcining refers in ozone environment with 180~220 DEG C of 25~30h of calcining.
The third aspect of the invention:
SAPO-56 molecular screen membrane is in CO2/CH4Application in gas separation.
The application refers to and improves CO2/CH4CO in gas separation2Permeability and CO2/CH4Separation selectivity.
Beneficial effect
Treated that nanoscale SAPO-56 molecular sieve is induced as crystal seed using high-energy ball milling by the present invention, in hydro-thermal Fine and close flawless SAPO-56 molecular screen membrane is prepared in synthesis, and using special atmosphere or outfield ancillary technique in low temperature Lower activation SAPO-56 molecular screen membrane, so that the removing of template machine TMHD can solve template machine without carrying out at high temperature in this way Removing is not thorough film layer and support body layer the case where falling off when even calcination temperature is excessively high, can to avoid film layer cracking with And the formation of intergranular defect, the quality of film is improved, fine and close SAPO-56 molecular screen membrane is prepared.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) for the SAPO-56 molecular sieve that the partial size without high-energy ball milling processing is 20 μm Figure.
Fig. 2 is the scanning electron microscope for the SAPO-56 molecular sieve that the partial size handled through high energy ball mill is 0.3 μm (SEM) figure.
Fig. 3 is the XRD diffraction curve phenogram for the SAPO-56 molecular screen membrane prepared in embodiment 1.
Fig. 4 is the SAPO-56 for the crystal seed induction synthesis handled through high energy ball mill for being 0.3 μm with partial size in embodiment 1 Surface Scanning Electron microscope (SEM) macrostructure figure of molecular screen membrane.
Fig. 5 is the SAPO-56 for the crystal seed induction synthesis handled through high energy ball mill for being 0.3 μm with partial size in embodiment 1 Surface Scanning Electron microscope (SEM) micro-structure diagram of molecular screen membrane.
Fig. 6 is the SAPO-56 for the crystal seed induction synthesis handled through high energy ball mill for being 0.3 μm with partial size in embodiment 1 Section scanning electron microscope (SEM) micro-structure diagram of molecular screen membrane.
Fig. 7 is section scanning electron microscope (SEM) microstructure for the SAPO-56 molecular screen membrane that reference examples 1 synthesize Figure.
Fig. 8 is section scanning electron microscope (SEM) microstructure for the SAPO-56 molecular screen membrane that reference examples 2 synthesize Figure.
Fig. 9 is section scanning electron microscope (SEM) microstructure for the SAPO-56 molecular screen membrane that reference examples 3 synthesize Figure.
Figure 10 is section scanning electron microscope (SEM) microstructure for the SAPO-56 molecular screen membrane that reference examples 4 synthesize Figure.
Figure 11 is section scanning electron microscope (SEM) microstructure for the SAPO-56 molecular screen membrane that reference examples 5 synthesize Figure.
Specific embodiment
SAPO-56 molecular screen membrane is successfully prepared in the present invention on porous supporting body for the first time, and supporter here is It is made of porous ceramics, the selection separating layer being made of SAPO-56 molecular screen membrane is covered on its surface.Here supporter Configuration be not particularly limited, chip, tubular type or hollow fiber form can be selected from.
For the configuration of supporter, there is no particular limitation, in some embodiments, in the supporter of hollow fiber form The number of channels in portion can be 1~6, and external diametrical extent is preferably 2~6mm, inner passage diameter range is preferably 0.3~ 1.5mm；The thickness of the supporter of the chip is preferably 1~10mm；The outer diameter preferably 4 of the tubular type supporter~ 20mm, internal diameter preferably 1~12mm.
It for the material of porous ceramic support, is not particularly limited, the material that material can choose includes: oxidation Aluminium, zirconium oxide, magnesia, silica, titanium oxide, cerium oxide, yttrium oxide, the oxide materials such as barium titanate；Cordierite, more aluminium The combined oxidations species material such as andalusite, forsterite, steatite, sialon, zircon, ferrite；Silicon nitride, nitridation The nitride-based materials such as aluminium；The carbon compounds material such as silicon carbide；The hydroxides composition material such as hydroxyapatite；The elements such as carbon, silicon Class material；Or the two or more inorganic composite materials etc. containing them.Natural minerals (clay, clay pit can also be used Object, grog, silica sand, pottery stone, feldspar, white sand) or blast-furnace slag, flying dust etc., preferably silicon carbide, diatomite, mullite, oxidation One of aluminium, zirconium oxide or titanium oxide or several mixing.
Embodiment 1
Selecting four-way aluminium oxide doughnut supporter, (diameter 3.8mm, four-way are evenly distributed in section, and channel is straight Diameter about 1mm), supporter is placed in ultrasound 20 minutes, cleaning, drying in distilled water.It is 1wt%SAPO- that supporter, which is put into concentration, 56(+0.125wt%HPC) in crystal seed liquid, the SAPO-56 crystal seed size handled through high energy ball mill is about 0.3 μm, using dipping Aluminium oxide four-way doughnut supporter is placed on after impregnating 10s in crystal seed liquid and takes out, is put into 60 DEG C of baking ovens by the mode of lifting Middle drying 4h is then placed in Muffle furnace after 450 DEG C of 8 h of calcining removing HPC, obtains the supporter that load has crystal seed；
It with molar ratio is Al by boehmite, phosphoric acid, silica solution, TMHD2O3: P2O5: SiO2: TMHD:H2O=0.8: The proportional arrangement film synthesis mother liquid of 1.0:0.6:2:50 is put into the supporter of load crystal seed, in an oven with the rate of 1 DEG C/min 200 DEG C are warming up to, 48h is kept the temperature, then be cooled to 25 DEG C with the rate of 1 DEG C/min, takes out supporter, and keep in ozone environment 200 DEG C of calcining 28h, obtain product doughnut SAPO-56 molecular screen membrane.
Reference examples 1
Four-way aluminium oxide doughnut supporter is selected, supporter is placed in ultrasound 20 minutes in distilled water, and cleaning is dried It is dry.Supporter is put into concentration to be handled in 1wt%SAPO-56(+0.125wt%HPC) crystal seed liquid through high energy ball mill SAPO-56 crystal seed size is about 0.3 μm, and by the way of Best-Effort request, aluminium oxide four-way doughnut supporter is placed on It is taken out after impregnating 10s in crystal seed liquid, is put into 60 DEG C of baking ovens and dries 4h, be then placed in 450 DEG C of calcining 8h removing HPC in Muffle furnace Afterwards, the supporter that load has crystal seed is obtained；
It with molar ratio is Al by boehmite, phosphoric acid, silica solution, TMHD2O3: P2O5: SiO2: TMHD:H2O=0.8: The proportional arrangement film synthesis mother liquid of 1.0:0.6:2:40 is put into the supporter of load crystal seed, in an oven with the rate of 1 DEG C/min 200 DEG C are warming up to, 48h is kept the temperature, then be cooled to 25 DEG C with the rate of 1 DEG C/min, takes out supporter, and keep in ozone environment 200 DEG C of calcining 28h, obtain product doughnut SAPO-56 molecular screen membrane.
Reference examples 2
Four-way aluminium oxide doughnut supporter is selected, supporter, which is placed in 0.1mol/L NaOH weak caustic solution, to be impregnated 10h, cleaning, drying.It is 1wt%SAPO-56(+0.125wt%HPC that supporter, which is put into concentration) in crystal seed liquid, through high energy ball mill The SAPO-56 crystal seed size of processing is about 0.3 μm, and by the way of Best-Effort request, aluminium oxide four-way doughnut is supported Body is placed in crystal seed liquid and takes out after dipping 10s, is put into 60 DEG C of baking ovens and dries 4h, is then placed in 450 DEG C of calcining 8h in Muffle furnace After removing HPC, the supporter that load has crystal seed is obtained；
It with molar ratio is Al by boehmite, phosphoric acid, silica solution, TMHD2O3: P2O5: SiO2: TMHD:H2O=0.8: The proportional arrangement film synthesis mother liquid of 1.0:0.6:2:50 is put into the supporter of load crystal seed, in an oven with the speed of 1 DEG C/min Rate is warming up to 200 DEG C, keeps the temperature 48h, then be cooled to 25 DEG C with the rate of 1 DEG C/min, takes out supporter, and protect in ozone environment 200 DEG C of calcining 28h are held, product doughnut SAPO-56 molecular screen membrane is obtained.
Reference examples 3
Four-way aluminium oxide doughnut supporter is selected, supporter is placed in ultrasound 20 minutes in distilled water, and cleaning is dried It is dry.Supporter is put into concentration to be handled in 1wt%SAPO-56(+0.125wt%HPC) crystal seed liquid through high energy ball mill SAPO-56 crystal seed size is about 0.3 μm, and by the way of Best-Effort request, aluminium oxide four-way doughnut supporter is placed on It is taken out after impregnating 10s in crystal seed liquid, is put into 60 DEG C of baking ovens and dries 4h, be then placed in 450 DEG C of calcining 8h removing HPC in Muffle furnace Afterwards, the supporter that load has crystal seed is obtained；
It with molar ratio is Al by boehmite, phosphoric acid, silica solution, TMHD2O3: P2O5: SiO2: TMHD:H2O=0.8: The proportional arrangement film synthesis mother liquid of 1.0:0.6:2:50 is put into the supporter of load crystal seed, in an oven with the speed of 1 DEG C/min Rate is warming up to 200 DEG C, and heat preservation for 24 hours, then with the rate of 1 DEG C/min is cooled to 25 DEG C, takes out supporter, and protect in ozone environment 200 DEG C of calcining 28h are held, product doughnut SAPO-56 molecular screen membrane is obtained.
Reference examples 4
Four-way aluminium oxide doughnut supporter is selected, supporter is placed in ultrasound 20 minutes in distilled water, and cleaning is dried It is dry.Supporter is put into concentration to be handled in 1wt%SAPO-56(+0.125wt%HPC) crystal seed liquid without high energy ball mill SAPO-56 crystal seed size is about 15 μm, and by the way of Best-Effort request, aluminium oxide four-way doughnut supporter is placed on crystalline substance It is taken out after impregnating 10s in kind liquid, is put into 60 DEG C of baking ovens and dries 4h, be then placed in 450 DEG C of calcining 8h removing HPC in Muffle furnace Afterwards, the supporter that load has crystal seed is obtained；
It with molar ratio is Al by boehmite, phosphoric acid, silica solution, TMHD2O3: P2O5: SiO2: TMHD:H2O=0.8: The proportional arrangement film synthesis mother liquid of 1.0:0.6:2:50 is put into the supporter of load crystal seed, in an oven with the speed of 1 DEG C/min Rate is warming up to 200 DEG C, keeps the temperature 48h, then be cooled to 25 DEG C with the rate of 1 DEG C/min, takes out supporter, and protect in ozone environment 200 DEG C of calcining 28h are held, product doughnut SAPO-56 molecular screen membrane is obtained.
Reference examples 5
Four-way aluminium oxide doughnut supporter is selected, supporter is placed in ultrasound 20 minutes in distilled water, and cleaning is dried It is dry.Supporter is put into concentration to be handled in 1wt%SAPO-56(+0.125wt%HPC) crystal seed liquid through high energy ball mill SAPO-56 crystal seed size is about 0.3 μm, and by the way of Best-Effort request, aluminium oxide four-way doughnut supporter is placed on It is taken out after impregnating 10s in crystal seed liquid, is put into 60 DEG C of baking ovens and dries 4h, be then placed in 450 DEG C of calcining 8h removing HPC in Muffle furnace Afterwards, the supporter that load has crystal seed is obtained；
It with molar ratio is Al by boehmite, phosphoric acid, silica solution, TMHD2O3: P2O5: SiO2: TMHD:H2O=0.8: The proportional arrangement film synthesis mother liquid of 1.0:0.6:2:50 is put into the supporter of load crystal seed, in an oven with the rate of 1 DEG C/min 200 DEG C are warming up to, 48h is kept the temperature, then be cooled to 25 DEG C with the rate of 1 DEG C/min, takes out supporter, and keep in Muffle furnace 550 DEG C of calcining 3h, obtain product doughnut SAPO-56 molecular screen membrane.
It is as follows that gas separation test is carried out to film prepared by the various embodiments described above: at 25 DEG C, four-way doughnut The charging of SAPO-56 molecular screen membrane component is CO2/CH4Molar ratio is the mixed gas of 1:1, feed side pressure 0.1MPa, infiltration Side is atmospheric pressure.Per-meate side flow is measured with soap bubble flowmeter, and per-meate side gas composition is surveyed by Shimadzu gas-chromatography (GC-2014) ?.
The preparation condition and gas separating resulting of SAPO-56 molecular screen membrane synthesized by embodiment 1 and reference examples 1~5 are such as Shown in table 1.
Table 1
Table 1 is shown, according to SAPO-56 molecular screen membrane prepared by embodiment 1, separation selectivity highest, CO2Flux is also most It is high；The content of water is reduced in 1 synthesis mother liquid of reference examples, and Synthesis liquid concentration becomes larger, so that the molecular screen membrane that supporting body surface generates Not uniform compact, CO2Permeability and CO2/CH4Selection separation property it is also poor, surface Electronic Speculum SEM photograph such as Fig. 7 institute Show.Supporter is pre-processed with 0.1mol/L NaOH weak caustic solution in reference examples 2, the experimental results showed that the not useful distillation of effect Water treatment carrier is good, CO2Permeability and CO2/CH4Selection separation property be also inferior to embodiment 1, surface Electronic Speculum SEM photograph is such as Shown in Fig. 8.Reference examples 3 are compared to embodiment 1, and generated time is reduced to for 24 hours by 48h, and generated time shortening leads to supporter The film layer of Surface Creation cannot be fine and close, and separating effect is poor, caused by this is also in that film surface defect is more, surface Electronic Speculum SEM photograph is as shown in Figure 9.In reference examples 4, using the original crystal seed handled without high-energy ball milling, crystal seed size is about 15 μm, brilliant Kind is excessive to cause carrier that can not obtain the supporter that crystal seed is uniformly present in by the painting crystal type of Best-Effort request, so closing At that cannot prepare the good molecular screen membrane of air-tightness in mother liquor, surface Electronic Speculum SEM photograph is as shown in Figure 10, it is for CO2With CH4Without selection separation property.The SAPO-56 molecular screen membrane of preparation is placed in removing template machine TMHD in Muffle furnace in reference examples 5, In 550 DEG C of air atmosphere, there is carbonization phenomenon in film surface, film layer blackening, and without air-tightness, for CO2And CH4Without selection Separation property, surface Electronic Speculum SEM photograph are as shown in figure 11.
In addition, the CO in table 12Permeability is related with the thickness bring resistance to mass tranfer of supporter itself wall, and the present invention adopts With high-strength alumina four-way doughnut supporter, support body layer resistance to mass tranfer is reduced.

Claims (1)

  1. The preparation method of 1.SAPO-56 molecular screen membrane, which is characterized in that the SAPO-56 molecular screen membrane includes selection point Absciss layer and supporter select separating layer to be overlying on the surface of supporter；The selection separating layer is by fine and close SAPO-56 molecule Sieve is constituted；The supporter is made of porous ceramics, the material of the porous ceramics be silicon carbide, diatomite, One of mullite, aluminium oxide, zirconium oxide or titanium oxide or several mixing；The SAPO-56 molecular screen membrane Preparation method includes the following steps:
    Step 1 carries out ball-milling treatment to SAPO-56 molecular sieve using high energy ball mill, stand-by as crystal seed；
    Crystal seed plus water are configured to suspension by step 2, add thickener, after mixing, as crystal seed liquid；Supporter is set It is ultrasonic in distilled water, cleaning, drying；Dry porous ceramic support is immersed in crystal seed liquid again, Best-Effort request is carried out, takes After out, drying；Using calcining, the parameter of calcination process is: 440~460 DEG C of 6~10h of calcining, obtains the branch that load has crystal seed Support body；
    The supporter that load has crystal seed is placed in film Synthesis liquid by step 3, carries out hydrothermal synthesis, after taking-up, drying, then smelly With 180~220 DEG C of 25~30h of calcining under oxygen environment, SAPO-56 molecular screen membrane is obtained；In the step 1, ball milling refer to by SAPO-56 molecular sieve is broken for the fine powder of 50nm~2 μm；
    The configuration of the supporter is selected from chip, tubular type or hollow fiber form；
    In the step 2, concentration of the crystal seed in suspension is 0.5~1wt%, and concentration of the thickener in crystal seed liquid is 0.02~0.1wt%；Thickener is hydroxypropyl cellulose；
    It is Al that silicon source, phosphorus source, silicon source, template, water, which are according to molar ratio, in the step 3, in film Synthesis liquid2O3: P2O5: SiO2: template: H2O=0.8:(0.8~1.2): (0.5~0.7): (1.8~2.2): the ratio of (45~55) is prepared；Described Template is N, N, N ', N '-tetramethyl -1,6- hexamethylene diamine；
    In the step 3, the parameter of hydrothermal synthesis is: being warming up to 180~220 DEG C with the rate of 0.8~1.2 DEG C/min, protects 40~50h of temperature, then 20~30 DEG C are cooled to the rate of 0.8~1.2 DEG C/min.
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