CN108751217A - A kind of method that normal pressure prepares nanometer SAPO-34 molecular sieves - Google Patents
A kind of method that normal pressure prepares nanometer SAPO-34 molecular sieves Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention provides a kind of method that normal pressure prepares nanometer SAPO-34 molecular sieves, and the method includes at least：By phosphorus source, silicon source, silicon source and template, example is add to deionized water in molar ratio respectively first, is stirred evenly, and Primogel is obtained, and is continued to stir the Primogel to aging, is obtained ageing products；Then the ageing products are placed in crystallization in open-top receptacle, obtain crystallization product；Then the crystallization product is cooled to room temperature, a nanometer SAPO-34 original powders is obtained after washed, separation and drying；Nanometer SAPO-34 original powders roasting is finally removed into the template, obtains the nanometer SAPO-34 molecular sieves.The present invention, by controlling reaction ratio, reaction temperature and crystallization time, successfully synthesizes required nanometer SAPO-34 molecular sieves, and operating process is simple, reduces Zeolite synthesis cost under conditions of normal pressure.In addition, the SAPO-34 zeolite crystals size that the present invention obtains is between 10 nanometers~100 nanometers.
Description
Technical field
The invention belongs to domain of inorganic chemistry, be related to it is a kind of preparing a nanometer method for SAPO-34 molecular sieves, more particularly to
A kind of method that normal pressure prepares nanometer SAPO-34 molecular sieves.
Background technology
SAPO-34 molecular sieves are CHA configuration topological structures, belong to trigonal system, and there are three-dimensional 8 membered rings to intersect duct knot
Structure, aperture are about 0.38 × 0.38nm.SAPO-34 catalyst has excellent MTO catalytic performances, has high light olefin
(ethylene and propylene) selectivity, especially SAPO-34 molecular sieve catalysts are when methanol conversion is 100%, ethylene and propylene
The yield of diene can be more than 80%.
SAPO-34 molecular sieves usually synthesize under hydrothermal conditions, as Chinese invention patent CN 104556141A,
CN102557072A, CN 106167268A etc. are all made of hydrothermal synthesis method, are synthesized in autoclave using water as solvent, lead to
Primogel crystallization is formed SAPO-34 molecular sieves by the self-generated pressure crossed high temperature and generated in autoclave.The route needs
It synthesizes under high pressure, the crystallization in high to equipment requirement and high-pressure sealed reaction kettle does not have visuality, can not visually supervise
Control its building-up process.
In addition to hydrothermal synthesis method, solvent-thermal process method, xerogel synthetic method, ultrasonic wave added synthetic method and micro- also can be used
The methods of wave auxiliary synthesis prepares SAPO-34 molecular sieves.Solvent-thermal process method is to replace water to carry out molecular sieve using organic solvent
Crystallization synthesis.This method proposes (Nature, 1985,317 (6033), 157-158) by Bibby et al. earliest, then in Liu
The people and its partner carried out amine hot method synthesis SAPO-34 report (Journal of Materials Chemistry A,
2013,1 (45), 14206-14213), it the advantage is that the material that can be prepared to water sensitive；Xerogel synthetic method is by initial silicon
The dry colloidal solid of aluminium phosphorus is by Vapor-phase transport method or the further crystallization of steam auxiliary law at a kind of method of molecular sieve, and this method is most
It is early that (Chemical Communications, 1990 (10), 755-756) developed by Xu Wen Yang seminar, is answered later
Molecular sieve for synthesizing various structures.2003, Zhang et al. was synthesized using xerogel synthetic method system high efficiency
SAPO-34 molecular sieves (Chemical Communications, 2003,17,2232-2233), molecular sieve yield is high, waste liquid is few.
Ultrasonic wave added synthetic method is pre-processed to gel using ultrasonic wave during preparing Primogel, such as Halladj and its
Partner is prepared for SAPO-34 molecular sieve catalysts (Microporous And Mesoporous using ultrasonic wave added synthetic method
Materials, 2012,163,334-342), ultrasound can make gel mix evenly and contribute to the nucleation of Primogel.It is micro-
Wave auxiliary synthetic method is the synthesis that accessory molecule sieves under conditions of microwave heating, and with homogeneous heating, crystallization rate is fast, closes
The advantages that smaller and uniform at molecular sieve grain size.However above-mentioned synthetic method is both needed to carry out under high pressure, condition of high voltage pair
Synthesis device it is more demanding so that crystallizing kettle involves great expense.Therefore be badly in need of developing a kind of technology of atmospheric synthesis SAPO-34, from
And the generation of its production cost is reduced, while avoiding environmental pollution caused by acid-base waste fluid.
SAPO-34 molecular sieves have excellent preparing light olefins from methanol (MTO) performance, but conventional SAPO-34 molecular sieves
Crystallite dimension is micron order, leads to carbon distribution because the diffusion rate of product is slow, finally causes the rapid deactivation of catalyst.Nanometer
SAPO-34 has a clear superiority during MTO, and the SAPO-34 molecular sieves with small crystals size, which present, preferably urges
The agent service life.Therefore synthesis nanometer SAPO-34 can increase its external surface area and shorten diffusion path, inhibit coke formation, to
Improve MTO performances.
Present invention is disclosed it is a kind of can atmospheric synthesis SAPO-34 method, this method need not generate in the synthesis process
Self-generated pressure, it is low to crystallization containers demand, it round-bottomed flask, uncovered beaker or open reaction kettle and synthesis under normal pressure pipe can be used to carry out
Crystallization, be so far for the first time in open-top receptacle normal pressure prepare nanometer SAPO-34 molecular sieves report；Especially gained
SAPO-34 is nanometer product, has excellent MTO (methanol-to-olefins) performance.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of normal pressures to prepare nanometer SAPO-
The method of 34 molecular sieves prepares molecular sieve using autoclave in the prior art for solving, and synthetic operation is complicated and closes
At it is of high cost the problems such as.
In order to achieve the above objects and other related objects, the present invention provides a kind of normal pressure preparation nanometer SAPO-34 molecular sieves
Method, the method includes at least：
1) by phosphorus source, silicon source, silicon source and template, example is add to deionized water in molar ratio respectively, is stirred evenly,
Primogel is obtained, continues to stir the Primogel to aging, obtains ageing products；
2) ageing products are placed in crystallization in open-top receptacle, obtain crystallization product；
3) crystallization product is cooled to room temperature, a nanometer SAPO-34 original powders is obtained after washed, separation and drying；
4) nanometer SAPO-34 original powders roasting is removed into the template, obtains the nanometer SAPO-34 molecular sieves.
A kind of scheme of optimization of the method for nanometer SAPO-34 molecular sieves, phosphorus source packet are prepared as normal pressure of the present invention
Include the mixture of one or both of phosphoric acid, phosphorous acid.
A kind of scheme of optimization of the method for nanometer SAPO-34 molecular sieves, source of aluminium packet are prepared as normal pressure of the present invention
It includes one or more in aluminium isopropoxide, alchlor, aluminium hydroxide, kaolin, aluminum nitrate, aluminum sulfate and boehmite
Mixture.
A kind of scheme of optimization of the method for nanometer SAPO-34 molecular sieves, the silicon source packet are prepared as normal pressure of the present invention
Include one or more mixtures in Ludox, solid silicone, ethyl orthosilicate, white carbon, silicic acid, kaolin.
A kind of scheme of optimization of the method for nanometer SAPO-34 molecular sieves, the template are prepared as normal pressure of the present invention
Including one or more mixtures in diethylamine, triethylamine, morpholine, tetraethyl ammonium hydroxide.
The scheme that a kind of optimization of the method for nanometer SAPO-34 molecular sieves is prepared as normal pressure of the present invention, in step 1), institute
Silicon source, phosphorus source and silicon source are stated respectively with Al2O3、P2O5And SiO2Meter, wherein the molar ratio of phosphorus source and source of aluminium between
Between 0.5~2.0, the molar ratio of the silicon source and source of aluminium is between 0.05~2.0, the template and source of aluminium
Molar ratio between 0.5~5.0.
The scheme that a kind of optimization of the method for nanometer SAPO-34 molecular sieves is prepared as normal pressure of the present invention, in step 2), institute
The temperature for stating crystallization is 150~250 DEG C, and the time of the crystallization is 0.5~240 hour.Crystallization temperature is preferably 180~220
DEG C, crystallization time is preferably 5~20 hours.
The scheme that a kind of optimization of the method for nanometer SAPO-34 molecular sieves is prepared as normal pressure of the present invention, in step 2), institute
It includes for one kind in flask, beaker, open reaction tube and open reaction kettle to state open-top receptacle.
The scheme that a kind of optimization of the method for nanometer SAPO-34 molecular sieves is prepared as normal pressure of the present invention, in step 4), institute
It states roasting and removes the condition of the template and be：It is roasted 2~10 hours under 500~600 DEG C of air atmospheres.
The scheme that a kind of optimization of the method for nanometer SAPO-34 molecular sieves is prepared as normal pressure of the present invention in step 4), obtains
The crystallite dimension of the nanometer SAPO-34 molecular sieves obtained is between 10~100 nanometers.
As described above, the method that the normal pressure of the present invention prepares nanometer SAPO-34 molecular sieves, has the advantages that：
1, the present invention successfully synthesizes institute by controlling reaction ratio, reaction temperature and crystallization time under conditions of normal pressure
Nanometer SAPO-34 molecular sieves needed, and the preparation method of the present invention simplifies synthetic operation, reduce Zeolite synthesis at
This.
2, the present invention using atmospheric synthesis method in open-top receptacle as beaker, open flask or open reaction tube,
Reaction kettle carries out crystallization, and the SAPO-34 zeolite crystals size of production overcomes SAPO- between 10-100 nanometers
34 molecular sieves are conventionally synthesized required condition of high voltage and the larger problem of gained SAPO-34 crystal grain.
Description of the drawings
Fig. 1 is the XRD spectra of SAPO-34 synthesized by the embodiment of the present invention 1.
Fig. 2 is the SEM electromicroscopic photographs of SAPO-34 synthesized by the embodiment of the present invention 1.
Fig. 3 is the XRD spectra of SAPO-34 synthesized by the embodiment of the present invention 10.
Fig. 4 is the SEM electromicroscopic photographs of SAPO-34 synthesized by the embodiment of the present invention 10.
Fig. 5 is the XRD spectra of SAPO-34 synthesized by the embodiment of the present invention 25.
Fig. 6 is the SEM electromicroscopic photographs of SAPO-34 synthesized by the embodiment of the present invention 25.
Fig. 7 is the flow diagram for the method that normal pressure of the present invention prepares nanometer SAPO-34 molecular sieves.
Specific implementation mode
Illustrate that embodiments of the present invention, those skilled in the art can be by this specification below by way of specific specific example
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Please refer to attached drawing.It should be noted that the diagram provided in the present embodiment only illustrates the present invention in a schematic way
Basic conception, only display and related component in the present invention rather than component count, shape when according to actual implementation in schema then
Shape and size are drawn, when actual implementation kenel, quantity and the ratio of each component can be a kind of random change, and its component cloth
Office's kenel may also be increasingly complex.
As shown in fig. 7, the present invention provides a kind of method that normal pressure prepares nanometer SAPO-34 molecular sieves, the method is at least
Including：
Step S1 is first carried out, example is added to deionized water in molar ratio by phosphorus source, silicon source, silicon source and template respectively
In, it stirs evenly, obtains Primogel, continue to stir the Primogel to aging, obtain ageing products.
In this step, as preferred embodiment, first the template can be mixed with deionized water, then thereto
The silicon source is added, forms solution, stirring；Meanwhile silicon source being added after mixing phosphorus source with deionized water, gel is formed,
Stirring；The solution and gel of preparation are finally mixed and added into deionized water, to form Primogel；Continue stirring one
Make the abundant aging of the Primogel after fixing time.
Embodiment more preferably after abundant aging, before carrying out step S2, is first poured into the ageing products
It is being dried in culture dish, obtained solid is ground uniformly in mortar after drying.
As an example, phosphorus source includes the mixture of one or both of phosphoric acid, phosphorous acid.
As an example, source of aluminium includes aluminium isopropoxide, alchlor, aluminium hydroxide, kaolin, aluminum nitrate, aluminum sulfate
With one or more mixtures in boehmite.
As an example, the silicon source includes in Ludox, solid silicone, ethyl orthosilicate, white carbon, silicic acid, kaolin
One or more mixtures.
As an example, the template is in organic amine, including diethylamine, triethylamine, morpholine, tetraethyl ammonium hydroxide
One or more mixtures.
As an example, in step S1, source of aluminium, phosphorus source and silicon source are respectively with Al2O3、P2O5And SiO2Meter, wherein described
The molar ratio of phosphorus source and source of aluminium between 0.5~2.0, the molar ratio of the silicon source and source of aluminium between 0.05~
Between 2.0, the molar ratio of the template and source of aluminium is between 0.5~5.0.
Then step S2 is executed, the ageing products are placed in crystallization in open-top receptacle, obtain crystallization product.
As an example, in step S2, between 150 DEG C~250 DEG C, the time of the crystallization is situated between the temperature of the crystallization
Between 0.5 hour~240 hours.
As more optimized embodiment, the temperature of the crystallization between 180 DEG C~220 DEG C, the crystallization when
Between between 5 hours~20 hours.
As an example, in step S2, the open-top receptacle includes for flask, beaker, open reaction tube and open reaction kettle
In one kind.This step uses hardware device of the open-top receptacle as normal pressure crystallization synthetic reaction, simplifies synthetic operation, avoids height
Press strip part reduces Zeolite synthesis cost.
Then step S3 is executed, the crystallization product is cooled to room temperature, nanometer is obtained after washed, separation and drying
SAPO-34 original powders.
Step S4 is finally executed, nanometer SAPO-34 original powders roasting is removed into the template, obtains the nanometer
SAPO-34 molecular sieves.
As an example, in step S4, the condition that the roasting removes the template is：In 500 DEG C~600 DEG C air gas
It is roasted 2 hours~10 hours under atmosphere.
As more preferably embodiment, the condition that the roasting removes the template is：In 550 DEG C~600 DEG C air
It is roasted 2 hours~4 hours under atmosphere.
As an example, in step S4, the crystallite dimensions of the nanometer SAPO-34 molecular sieves of acquisition between 10 nanometers~
Between 100 nanometers.
As more preferably embodiment, the crystallite dimensions of the nanometer SAPO-34 molecular sieves of acquisition between 20 nanometers~
Between 70 nanometers.
The present invention is mixed phosphorus source, silicon source and silicon source, in a reservoir often according to a certain percentage using organic amine as template
Pressure carries out crystallization, synthesizes a nanometer SAPO-34 molecular sieves by controlling reaction temperature and crystallization time, avoids
SAPO-34 molecular sieves are conventionally synthesized required hyperbaric environment, and prepared SAPO-34 zeolite crystals be less than 100 nanometers,
Building-up process is discharged without acid-base waste fluid, environmental-friendly.
It is further carried out below by the method that specific embodiment prepares nanometer SAPO-34 molecular sieves to the normal pressure of the present invention
Explanation.
Embodiment 1
First, 10.0 grams of triethylamine solutions and 6.0 grams of deionized waters are mixed, and 5.0 grams of Ludox is added and are formed
After mixing 6.0 grams of concentrated phosphoric acids (85wt%) with 6.0 grams of deionized waters, 6.0 grams of boehmite shapes are added in solution A thereto
At sol B, A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.
Above-mentioned gel mixture is continued into stirring 2 hours so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
10 hours.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into open flask, the crystallization at 150 DEG C
12 hours.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C be dried overnight, 550
Obtain molecular sieve product after being roasted 4 hours under DEG C air atmosphere, the crystal grain of SAPO-34 is 50-70 nanometers obtained by the present embodiment.Such as
Fig. 1 show the XRD spectra of synthesis SAPO-34；Fig. 2 show the SEM electromicroscopic photographs of synthesis SAPO-34.
Embodiment 2
First, 10.0 grams of triethylamine solutions and 6.0 grams of deionized waters are mixed, and 5.0 grams of Ludox is added and are formed
After mixing 24.0 grams of concentrated phosphoric acids (85wt%) with 6.0 grams of deionized waters, 6.0 grams of boehmite shapes are added in solution A thereto
At sol B, A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.
Above-mentioned gel mixture is continued into stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
It is 10 hours dry.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into open flask, it is brilliant at 150 DEG C
Change 12 hours.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C be dried overnight,
Molecular sieve product is obtained after being roasted 2 hours under 500 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is received for 20-40
Rice.
Embodiment 3
First, 10.0 grams of triethylamine solutions and 6.0 grams of deionized waters are mixed, and 5.0 grams of Ludox is added and are formed
After mixing 12.0 grams of concentrated phosphoric acids (85wt%) with 6.0 grams of deionized waters, 6.0 grams of boehmite shapes are added in solution A thereto
At sol B, A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.
Above-mentioned gel mixture is continued into stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
It is 10 hours dry.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe,
Crystallization 12 hours at 150 DEG C.After crystallization, take out product after cooling, product centrifuged 3 times, and in baking oven 80 DEG C it is dry
It is dry overnight, molecular sieve product is obtained after being roasted 4 hours under 550 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is
20-50 nanometers.
Embodiment 4
First, 50.0 grams of tetraethyl ammonium hydroxide solution and 6.0 grams of deionized waters are mixed, and 5.0 grams of silicon is added
Acid forms solution A, after 24.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams is added thereto and intends thin water
Aluminium stone forms sol B, and A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, is formed just
Beginning gel.Above-mentioned gel mixture is continued into stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish
It is dried 10 hours at 80 DEG C.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is packed into opening stainless steel reaction
Guan Zhong, crystallization 12 hours at 150 DEG C.After crystallization, product is taken out after cooling, product is centrifuged 3 times, and in baking oven
80 DEG C are dried overnight, and molecular sieve product is obtained after being roasted 4 hours under 550 DEG C of air atmospheres, the present embodiment gained SAPO-34's
Crystal grain is 20-40 nanometers.
Embodiment 5
First, 15.0 grams of triethylamine solutions and 6.0 grams of deionized waters are mixed, and 5.0 grams of solid silicone shapes is added
At solution A, after 24.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of alchlor shapes are added thereto
At sol B, A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.
Above-mentioned gel mixture is continued into stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
It is 10 hours dry.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe,
Crystallization 12 hours at 150 DEG C.After crystallization, take out product after cooling, product centrifuged 3 times, and in baking oven 80 DEG C it is dry
It is dry overnight, molecular sieve product is obtained after being roasted 4 hours under 550 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is
20-40 nanometers.
Embodiment 6
First, 15.0 grams of triethylamine solutions and 6.0 grams of deionized waters are mixed, and 5.0 grams of Ludox is added and are formed
Solution A after mixing 24.0 grams of concentrated phosphoric acids (85wt%) with 6.0 grams of deionized waters, is added 6.0 grams of aluminium isopropoxides and is formed thereto
Sol B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will
Above-mentioned gel mixture continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
10 hours.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, 150
Crystallization 20 hours at DEG C.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 4 hours under 550 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 60-
80 nanometers.
Embodiment 7
First, 15.0 grams of tetraethyl ammonium hydroxide solution and 6.0 grams of deionized waters are mixed, and 5.0 grams of silicon is added
Colloidal sol forms solution A, and after 24.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of isopropyls are added thereto
Aluminium alcoholates forms sol B, and A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, is formed just
Beginning gel.Above-mentioned gel mixture is continued into stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish
It is dried 10 hours at 80 DEG C.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is packed into opening stainless steel reaction
Guan Zhong, crystallization 12 hours at 150 DEG C.After crystallization, product is taken out after cooling, product is centrifuged 3 times, and in baking oven
80 DEG C are dried overnight, and molecular sieve product is obtained after being roasted 4 hours under 550 DEG C of air atmospheres, the present embodiment gained SAPO-34's
Crystal grain is 20-40 nanometers.
Embodiment 8
First, 15.0 grams of tetraethyl ammonium hydroxide solution and 6.0 grams of deionized waters are mixed, and 5.0 grams of height is added
Ridge soil forms solution A, and after 24.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of isopropyls are added thereto
Aluminium alcoholates forms sol B, and A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, is formed just
Beginning gel.Above-mentioned gel mixture is continued into stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish
It is dried 10 hours at 80 DEG C.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is packed into opening stainless steel reaction
Guan Zhong, crystallization 12 hours at 150 DEG C.After crystallization, product is taken out after cooling, product is centrifuged 3 times, and in baking oven
80 DEG C are dried overnight, and molecular sieve product is obtained after being roasted 2 hours under 550 DEG C of air atmospheres, the present embodiment gained SAPO-34's
Crystal grain is 20-40 nanometers.
Embodiment 9
First, 15.0 grams of triethylamine solutions and 6.0 grams of deionized waters are mixed, and 5.0 grams of Ludox is added and are formed
Solution A after mixing 24.0 grams of concentrated phosphoric acids (85wt%) with 6.0 grams of deionized waters, is added 6.0 grams of aluminium isopropoxides and is formed thereto
Sol B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will
Above-mentioned gel mixture continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
10 hours.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, 150
Crystallization 12 hours at DEG C.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 2 hours under 600 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 20-
40 nanometers.
Embodiment 10
First, 10.0 morpholine solutions and 6.0 grams of deionized waters are mixed, and 5.0 grams of ethyl orthosilicates is added and are formed
Solution A after mixing 24.0 grams of concentrated phosphoric acids (85wt%) with 6.0 grams of deionized waters, is added 6.0 grams of aluminium isopropoxides and is formed thereto
Sol B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will
Above-mentioned gel mixture continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
10 hours.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, 150
Crystallization 12 hours at DEG C.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 4 hours under 600 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 20-
50 nanometers.It is illustrated in figure 3 the XRD spectra of synthesis SAPO-34；Fig. 4 show the SEM electromicroscopic photographs of synthesis SAPO-34.
Embodiment 11
First, 10.0 diethylamine solutions and 6.0 grams of deionized waters are mixed, and be added 5.0 grams of Ludox formed it is molten
Liquid A, after 6.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of aluminium isopropoxides of addition are formed molten thereto
Glue B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will be upper
It states gel mixture and continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and dries 10 at 80 DEG C
Hour.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, at 150 DEG C
Lower crystallization 12 hours.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 4 hours under 600 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 20-
50 nanometers.
Embodiment 12
First, 10.0 triethylamine solutions and 6.0 grams of deionized waters are mixed, and be added 5.0 grams of white carbons formed it is molten
Liquid A, after 12.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of aluminium isopropoxides of addition are formed molten thereto
Glue B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will be upper
It states gel mixture and continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and dries 10 at 80 DEG C
Hour.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, at 150 DEG C
Lower crystallization 12 hours.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 4 hours under 600 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 20-
50 nanometers.
Embodiment 13
First, 10.0 triethylamine solutions and 6.0 grams of deionized waters are mixed, and be added 5.0 grams of Ludox formed it is molten
Liquid A, after 12.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of aluminium isopropoxides of addition are formed molten thereto
Glue B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will be upper
It states gel mixture and continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and dries 10 at 80 DEG C
Hour.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, at 170 DEG C
Lower crystallization 12 hours.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 10 hours under 600 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 50-
70 nanometers.
Embodiment 14
First, 15.0 grams of triethylamine solutions and 6.0 grams of deionized waters are mixed, and 5.0 grams of Ludox is added and are formed
Solution A after mixing 24.0 grams of concentrated phosphoric acids (85wt%) with 6.0 grams of deionized waters, is added 6.0 grams of aluminium hydroxides and is formed thereto
Sol B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will
Above-mentioned gel mixture continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
10 hours.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, 190
Crystallization 12 hours at DEG C.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 10 hours under 550 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 70-
90 nanometers.
Embodiment 15
First, 15.0 grams of tetraethyl ammonium hydroxide solution and 6.0 grams of deionized waters are mixed, and 5.0 grams of silicon is added
Colloidal sol forms solution A, after 24.0 grams of phosphorous acid are mixed with 6.0 grams of deionized waters, 6.0 grams of aluminium isopropoxides is added thereto and are formed
Sol B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will
Above-mentioned gel mixture continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
10 hours.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, 210
Crystallization 6 hours at DEG C.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 4 hours under 550 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 80-
100 nanometers.
Embodiment 16
First, 15.0 grams of tetraethyl ammonium hydroxide solution and 6.0 grams of deionized waters are mixed, and 5.0 grams of height is added
Ridge soil forms solution A, and after 24.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of isopropyls are added thereto
Aluminium alcoholates forms sol B, and A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, is formed just
Beginning gel.Above-mentioned gel mixture is continued into stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish
It is dried 10 hours at 80 DEG C.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is packed into opening stainless steel reaction
Guan Zhong, crystallization 4 hours at 210 DEG C.After crystallization, product is taken out after cooling, product is centrifuged 3 times, and in baking oven
80 DEG C are dried overnight, and molecular sieve product, the present embodiment gained SAPO-34 are obtained after being roasted 10 hours under 500 DEG C of air atmospheres
Crystal grain be 20-100 nanometers.
Embodiment 17
First, 15.0 grams of triethylamine solutions and 6.0 grams of deionized waters are mixed, and 5.0 grams of Ludox is added and are formed
Solution A after mixing 24.0 grams of concentrated phosphoric acids (85wt%) with 6.0 grams of deionized waters, is added 6.0 grams of aluminium isopropoxides and is formed thereto
Sol B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will
Above-mentioned gel mixture continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
10 hours.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, 210
Crystallization 2 hours at DEG C.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 4 hours under 600 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 80-
100 nanometers.
Embodiment 18
First, 15.0 grams of tetraethyl ammonium hydroxide solution and 6.0 grams of deionized waters are mixed, and 5.0 grams of silicon is added
Colloidal sol forms solution A, and after 24.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of isopropyls are added thereto
Aluminium alcoholates forms sol B, and A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, is formed just
Beginning gel.Above-mentioned gel mixture is continued into stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish
It is dried 10 hours at 80 DEG C.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is packed into opening stainless steel reaction
Guan Zhong, crystallization 12 hours at 190 DEG C.After crystallization, product is taken out after cooling, product is centrifuged 3 times, and in baking oven
80 DEG C are dried overnight, and molecular sieve product is obtained after being roasted 4 hours under 550 DEG C of air atmospheres, the present embodiment gained SAPO-34's
Crystal grain is 60-90 nanometers.
Embodiment 19
First, 15.0 grams of tetraethyl ammonium hydroxide solution and 6.0 grams of deionized waters are mixed, and 5.0 grams of height is added
Ridge soil forms solution A, and after 24.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of isopropyls are added thereto
Aluminium alcoholates forms sol B, and A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, is formed just
Beginning gel.Above-mentioned gel mixture is continued into stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish
It is dried 10 hours at 80 DEG C.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is packed into opening stainless steel reaction
Guan Zhong, crystallization 12 hours at 190 DEG C.After crystallization, product is taken out after cooling, product is centrifuged 3 times, and in baking oven
80 DEG C are dried overnight, and molecular sieve product is obtained after being roasted 4 hours under 550 DEG C of air atmospheres, the present embodiment gained SAPO-34's
Crystal grain is 60-80 nanometers.
Embodiment 20
First, 15.0 grams of triethylamine solutions and 6.0 grams of deionized waters are mixed, and 5.0 grams of Ludox is added and are formed
Solution A after mixing 24.0 grams of concentrated phosphoric acids (85wt%) with 6.0 grams of deionized waters, is added 6.0 grams of aluminium isopropoxides and is formed thereto
Sol B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will
Above-mentioned gel mixture continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
10 hours.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, 190
Crystallization 12 hours at DEG C.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 4 hours under 600 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 60-
90 nanometers.
Embodiment 21
First, 10.0 triethylamine solutions and 6.0 grams of deionized waters are mixed, and be added 5.0 grams of Ludox formed it is molten
Liquid A, after 24.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of aluminium isopropoxides of addition are formed molten thereto
Glue B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will be upper
It states gel mixture and continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and dries 10 at 80 DEG C
Hour.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, at 190 DEG C
Lower crystallization 12 hours.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 4 hours under 600 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 70-
100 nanometers.
Embodiment 22
First, 15.0 grams of tetraethyl ammonium hydroxide solution and 6.0 grams of deionized waters are mixed, and 5.0 grams of silicon is added
Colloidal sol forms solution A, and after 24.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of isopropyls are added thereto
Aluminium alcoholates forms sol B, and A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, is formed just
Beginning gel.Above-mentioned gel mixture is continued into stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish
It is dried 10 hours at 80 DEG C.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is packed into opening stainless steel reaction
Guan Zhong, crystallization 0.5 hour at 190 DEG C.After crystallization, product is taken out after cooling, product is centrifuged 3 times, and in baking oven
In 80 DEG C be dried overnight, obtain molecular sieve product after being roasted 4 hours under 550 DEG C of air atmospheres, SAPO-34 obtained by the present embodiment
Crystal grain be 20-50 nanometers.
Embodiment 23
First, 15.0 grams of tetraethyl ammonium hydroxide solution and 6.0 grams of deionized waters are mixed, and 5.0 grams of height is added
Ridge soil forms solution A, and after 24.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of isopropyls are added thereto
Aluminium alcoholates forms sol B, and A and B is stirred 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, is formed just
Beginning gel.Above-mentioned gel mixture is continued into stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish
It is dried 10 hours at 80 DEG C.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is packed into opening stainless steel reaction
Guan Zhong, crystallization 240 hours at 150 DEG C.After crystallization, product is taken out after cooling, product is centrifuged 3 times, and in baking oven
In 80 DEG C be dried overnight, obtain molecular sieve product after being roasted 4 hours under 550 DEG C of air atmospheres, SAPO-34 obtained by the present embodiment
Crystal grain be 70-100 nanometers.
Embodiment 24
First, 15.0 grams of triethylamine solutions and 6.0 grams of deionized waters are mixed, and 5.0 grams of Ludox is added and are formed
Solution A after mixing 24.0 grams of concentrated phosphoric acids (85wt%) with 6.0 grams of deionized waters, is added 6.0 grams of aluminium isopropoxides and is formed thereto
Sol B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will
Above-mentioned gel mixture continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and is dried at 80 DEG C
10 hours.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, 250
Crystallization 5 hours at DEG C.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 4 hours under 600 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 80-
100 nanometers.
Embodiment 25
First, 10.0 triethylamine solutions and 6.0 grams of deionized waters are mixed, and be added 5.0 grams of Ludox formed it is molten
Liquid A, after 24.0 grams of concentrated phosphoric acids (85wt%) are mixed with 6.0 grams of deionized waters, 6.0 grams of aluminium isopropoxides of addition are formed molten thereto
Glue B stirs A and B 2 hours respectively.2.0 grams of deionized waters are poured into B and be added to solution A again, forms Primogel.It will be upper
It states gel mixture and continues stirring a period of time so that the abundant aging of mixture, is subsequently poured into culture dish and dries 10 at 80 DEG C
Hour.Obtained solid is ground uniformly in mortar after drying.Above-mentioned solid is fitted into opening stainless steel reaction pipe, at 250 DEG C
Lower crystallization 0.5 hour.After crystallization, take out product after cooling, by product centrifuge 3 times, and in baking oven 80 DEG C it is dried
Night obtains molecular sieve product after being roasted 4 hours under 600 DEG C of air atmospheres, the crystal grain of the present embodiment gained SAPO-34 is 50-
70 nanometers.It is illustrated in figure 5 the XRD spectra of synthesis SAPO-34；Fig. 6 show the SEM electromicroscopic photographs of synthesis SAPO-34.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (11)
1. a kind of method that normal pressure prepares nanometer SAPO-34 molecular sieves, which is characterized in that the method includes at least：
1) by phosphorus source, silicon source, silicon source and template, example is add to deionized water in molar ratio respectively, is stirred evenly, and is obtained
Primogel continues to stir the Primogel to aging, obtains ageing products；
2) ageing products are placed in crystallization in open-top receptacle, obtain crystallization product；
3) crystallization product is cooled to room temperature, a nanometer SAPO-34 original powders is obtained after washed, separation and drying；
4) nanometer SAPO-34 original powders roasting is removed into the template, obtains the nanometer SAPO-34 molecular sieves.
2. the method that normal pressure according to claim 1 prepares nanometer SAPO-34 molecular sieves, it is characterised in that：Phosphorus source
Include the mixture of one or both of phosphoric acid, phosphorous acid.
3. the method that normal pressure according to claim 1 prepares nanometer SAPO-34 molecular sieves, it is characterised in that：Source of aluminium
Including one or more in aluminium isopropoxide, alchlor, aluminium hydroxide, kaolin, aluminum nitrate, aluminum sulfate and boehmite
Mixture.
4. the method that normal pressure according to claim 1 prepares nanometer SAPO-34 molecular sieves, it is characterised in that：The silicon source
Including one or more mixtures in Ludox, solid silicone, ethyl orthosilicate, white carbon, silicic acid, kaolin.
5. the method that normal pressure according to claim 1 prepares nanometer SAPO-34 molecular sieves, it is characterised in that：The template
Agent includes one or more mixtures in diethylamine, triethylamine, morpholine, tetraethyl ammonium hydroxide.
6. the method that normal pressure according to claim 1 prepares nanometer SAPO-34 molecular sieves, it is characterised in that：In step 1),
Source of aluminium, phosphorus source and silicon source are respectively with Al2O3、P2O5And SiO2Meter, wherein the molar ratio of phosphorus source and source of aluminium between
Between 0.5~2.0, the molar ratio of the silicon source and source of aluminium is between 0.05~2.0, the template and source of aluminium
Molar ratio between 0.5~5.0.
7. the method that normal pressure according to claim 1 prepares nanometer SAPO-34 molecular sieves, it is characterised in that：In step 2),
The temperature of the crystallization is 150~250 DEG C, and the time of the crystallization is 0.5~240 hour.
8. the method that normal pressure according to claim 7 prepares nanometer SAPO-34 molecular sieves, it is characterised in that：In step 2),
The temperature of the crystallization is 180~220 DEG C, and the time of the crystallization is 5~20 hours.
9. the method that normal pressure according to claim 1 prepares nanometer SAPO-34 molecular sieves, it is characterised in that：In step 2),
The open-top receptacle includes for one kind in flask, beaker, open reaction tube and open reaction kettle.
10. the method that normal pressure according to claim 1 prepares nanometer SAPO-34 molecular sieves, it is characterised in that：Step 4)
In, the condition that the roasting removes the template is：It is roasted 2 hours~10 hours under 500 DEG C~600 DEG C air atmospheres.
11. the method that normal pressure according to claim 1 prepares nanometer SAPO-34 molecular sieves, it is characterised in that：Step 4)
In, the crystallite dimension of the nanometer SAPO-34 molecular sieves of acquisition is between 10 nanometers~100 nanometers.
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