CN108579449A - A kind of method of the high silicon SSZ-13 molecular screen membranes of Fast back-projection algorithm - Google Patents
A kind of method of the high silicon SSZ-13 molecular screen membranes of Fast back-projection algorithm Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0044—Inorganic membrane manufacture by chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The present invention relates to a kind of preparation methods of high 13 molecular screen membranes of silicon SSZ.Molecular screen membrane includes the crystalline film and supporter for having Selective Separation, and crystalline film is overlying on supporting body surface；The crystalline film of Selective Separation is made of 13 molecular sieves of SSZ；The supporter is Al2O3, mullite or stainless steel.13 molecular screen membranes of SSZ are quickly prepared by way of adding nucleus and oil bath heating.Film layer prepared by the method is fine and close, and more traditional mode of heating is compared, and film generated time is greatly shortened while ensureing the separating property of film.Structure directing agent is removed in ozone atmosphere simultaneously, effectively prevents the generation of crystal defect in knockout course.13 molecular screen membranes of SSZ prepared by the method are to CO2/CH4And N2/CH4Mixed gas has good separating property, can be used for purification of natural gas.
Description
Technical field
The present invention provides a kind of preparation method of high silicon SSZ-13 molecular screen membranes, belong to zeolite membrane material preparation and
Detach application field.
Background technology
As current petroleum resources are increasingly deficient, natural gas is as one of world today's energy mainstay, and people are to it
Development and utilization also more and more paid attention to.In explored natural gas, in addition to main component methane gas, it includes
Major impurity gas also has carbon dioxide and nitrogen, they can reduce the combustion heat value of combustion gas, it is therefore desirable to preceding by it utilizing
Separation.Currently used separation method includes mainly solvent absorption, UF membrane, pressure-variable adsorption, cryogenic rectification etc..Wherein UF membrane
Technology since low energy consumption, the advantages such as easy to operate and it is of increasing concern.
In recent years, the application of molecular screen membrane in this respect is gradually paid attention to, because it has higher chemical stability
And thermal stability, even if in some complicated working environments, molecular screen membrane can still keep preferable separating property.It is so far
Only, the Large pore molecular sieve membrane that a batch can be used for gas separation, such as FAU, MFI etc. have been prepared.But due to these molecular screen membranes
Crystal pore size itself is too big, therefore micro-molecular gas system difficult to realize（Such as N2/CH4And CO2/CH4）Efficiently separate.
Compared to these Large pore molecular sieve membranes, microporous molecular sieve membrane has prodigious advantage in this respect, because it has
Smaller pore passage structure, therefore can be used for detaching some small gas molecules.Wherein SSZ-13 is a kind of molecule for CHA structure
Sieve, its effective pore size is the nm of 0.38 nm × 0.38, between carbon dioxide（0.33 nm）, nitrogen（0.372 nm）With
Methane（0.38 nm）Kinetic diameter between, along with SSZ-13 molecular sieves itself to carbon dioxide have Preferential adsorption,
So that SSZ-13 molecular sieves are to CO2/CH4Separation when be better than other Large pore molecular sieve membranes.
In the preparation method of existing SSZ-13 molecular screen membranes, what is mainly used is all conventional hydrothermal synthesis.Halil
Kalipcilar etc. (Chem .Mater., 14 (2012), 3458-3464) SSZ- that hydrothermal synthesis 5d is prepared at 433K
13 molecular screen membranes（Si/Al=20）To CO2/CH4, H2/CH4Separation factor be respectively 12 and 8.2.2014, Nikolay
Kosinov etc.（J. Mater. Chem. A, 2(2014), 13083-13092）With Al2O3Doughnut is carrier, in 433K
Lower hydrothermal synthesis 144h prepares SSZ-13 molecular screen membranes（Si/Al=100）, to CO at 0.6 MPa2/CH4Separation factor reach
To 42.Zheng Yihong etc.（Journal of Membrane Science 475(2015), 303–310）With TMAdaOH and TEAOH
For mixed structure directed agents high performance SSZ-13 molecular screen membranes are prepared in mullite carrier outer surface（Si/Al=20）, the conjunction
Film forming is not only to CO2/CH4Separation selectivity reach 300, and to C2H4/C2H6Also there is a preferable separating property, but film
Infiltration rate is relatively low, such as CO2Infiltration rate is 2.0 × 10-7 mol/(m2 s Pa)。
Within past several years, researchers achieved in terms of the synthesis of SSZ-13 molecular screen membranes it is certain into
Exhibition, but it is generally long to the generated time of SSZ-13 molecular screen membranes at present（≥4d）, this make the film layer synthesized partially thick and
Thickness low LCL is uniform, more seriously, and a large amount of crystal are also grown inside supporter, seriously affect the infiltration rate of film.It carries
High film layer crystallization velocity can effectively reduce crystal in supporter growth inside so that surface growth obtains apparent competitive advantage, obtains
Obtain the SSZ-13 molecular screen membranes of high-throughput and high uniform surface growth.The preparation of SSZ-13 molecular screen membranes is all made of common baking at present
Case heats, and the efficiency of air as a heat transfer medium is low, if excessive shortening crystallization time, and film layer can be caused not fine and close enough,
Influence its separating property.
Invention content
The purpose of the invention is to improve the preparation method of existing high silicon SSZ-13, especially by addition effective nucleation
And the method for combining oil bath heating, so that generated time is greatly shortened, reduces the consumption of the building-up process energy；And it uses at low temperature
Ozone removes the structure directing agent in molecular sieve pore passage, effectively prevents the generation of defect in knockout course.It is prepared with the method
SSZ-13 molecular screen membranes are to CO2/CH4And N2/CH4With excellent separating property.The present invention will be helpful to SSZ-13 molecular screen membranes
Industrial amplification production.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of method of the high silicon SSZ-13 molecular screen membranes of Fast back-projection algorithm, steps are as follows：
（1）The preparation of SSZ-13 molecular sieves：
It is prepared by SSZ-13 molecular sieve seeds：By alkali source, structure directing agent（SDA）It is mixed to form Sol A with silicon source, by silicon source and water
It is mixed to form sol B, forming crystal seed after Sol A and B mixing prepares colloidal sol, and colloidal sol constitutive molar ratio is：SiO2/Al2O3=20~
60、Na2O/SiO2=0.05~0.2、H2O/SiO2=30~60、SDA/SiO2=0.05 ~ 0.5, colloidal sol is in 65-120oAging 24- under C
72h forms nucleus colloidal sol M；The colloidal sol prepared again with identical proportioning and step is in 20-40o0.5-3h is stirred under C forms colloidal sol S,
By nucleus colloidal sol M and colloidal sol S with mass ratio M：S=0.05 ~ 0.5 mixes；Above-mentioned colloidal sol is fitted into reaction kettle, 110 ~ 200oC reacts 5-24h, takes out, cooling, centrifuges, and washing obtains SSZ-13 molecular sieve seeds after dry；Molecular sieve after drying is brilliant
Kind calcining, then after 5 ~ 15h of ball-milling treatment, it is spare.
（2）The pretreatment of porous supporting body：Weigh appropriate step 1）Molecular sieve seed is added in ethanol solution, through super
Crystal seed is evenly dispersed in dispersed phase solution after sound and concussion processing, forms uniform suspension, suspension quality score
For 0.01-2%；In a manner of vacuumizing by molecular sieve seed suspension on supporter, holding vacuum degree is 0.01-
0.08 MPa, suction time 5-90s, then at the uniform velocity proposes from suspension, after oven drying is handled, in supporting body surface
Form continuous fine and close molecular sieve crystal layer.
（3）The preparation of SSZ-13 molecular screen membranes
The preparation of SSZ-13 molecular screen membranes：Alkali source, structure directing agent and silicon source are mixed to form Sol A, silicon source is mixed with water
Sol B is formed, forming crystal seed after Sol A and B mixing prepares colloidal sol, and colloidal sol constitutive molar ratio is：SiO2/Al2O3=80~250、
Na2O/SiO2=0.05~0.5、H2O/SiO2=30~200、SDA/SiO2=0.05 ~ 0.5, colloidal sol is in 65-120oAging 24- under C
72h forms nucleus colloidal sol M；The colloidal sol that identical proportioning and step are prepared is in 20-40o0.5-3h is stirred under C forms colloidal sol S, it will be brilliant
Core colloidal sol M and colloidal sol S are with mass ratio M：S=0.05-0.5 is mixed；Above-mentioned colloidal sol is fitted into reaction kettle, by step（2）It is coated with crystalline substance
In the supporter merging colloidal sol of kind, 110 ~ 200oC reacts 6-36h and forms film layer；It is cleaned, it is dry, it is calcined under ozone atmosphere
Obtain SSZ-13 molecular screen membranes.
Step of the present invention（2）In selected support body material be aluminium oxide, mullite, stainless steel；Support shape be
Tubulose, sheet and doughnut.
Preferably, the present invention is in step（3）Middle mode of heating is oil bath.
Step of the present invention（2）The seed density that middle vacuum crystal method obtains is 0.5 ~ 2.5mg/cm2。
The silicon source is aluminium hydroxide, sodium metaaluminate, the thin stone of aluminium, aluminium isopropoxide, Tributyl aluminate, aluminium foil, aluminium powder or oxygen
Change aluminium.
The silicon source is Ludox, tetraethyl orthosilicate, positive quanmethyl silicate, sodium metasilicate, waterglass or silica flour.
The structure directing agent is N, N, N- front three adamantyls ammonium hydroxide, N, N, N- front three adamantyl bromines
Change ammonium, N, N, N- front three adamantyls ammonium iodide, N, N, N- trimethyl benzyls ammonium hydroxide, N, N, N- trimethyl benzyl brominations
One or more combinations of ammonium, N, N, N- trimethyl benzyls ammonium iodide or tetraethyl ammonium hydroxide.
It is carried out in the structure directing agent removing preferred ozone atmosphere of mode, ozone（Ozone/oxygen gas）It is excellent
1 ~ 50% is selected, calcination temperature preferably 150 ~ 300oC, calcination time preferably 5 ~ 48 h, heat up rate of temperature fall 0.5 ~ 10oC/min。
SSZ-13 molecular screen membranes prepared by aforesaid way are mainly used for gas separation, and concrete application system is CO2/CH4With
N2/CH4。
Beneficial effects of the present invention：
（1）By solution of the addition with effective nucleation in synthesizing colloidal sol in film, the method that oil bath heating is used in combination replaces the present invention
Traditional mode of heating effectively shortens the generated time of high silicon SSZ-13 molecular screen membranes, has saved being prepared into for molecular screen membrane
This, is conducive to industrial production.
（2）The method for the removing structure directing agent that the present invention is taken carries out in a certain concentration atmosphere in ozone,
This method reduce the temperature of tradition removing structure directing agent, effectively prevent SSZ-13 molecular sieve crystals and supporter under high temperature
The coefficient of expansion unmatched problem forms intergranular defect when avoiding de- structure directing agent, reduces the separating property of film.
Description of the drawings
Fig. 1 is XRD diagram before and after 1 SSZ-13 molecular sieve seed ball millings of embodiment.
Fig. 2 is SEM figures before and after 1 SSZ-13 molecular sieve seed ball millings of embodiment：Wherein（a）For SSZ-13 molecules before ball milling
Crystal seed is sieved,（b）For SSZ-13 molecular sieve seeds after ball milling.
Fig. 3 is the SSZ-13 molecular screen membrane XRD diagram prepared by embodiment 1 ~ 4, wherein with * being supporter diffraction maximum.
Fig. 4 is the SSZ-13 molecular screen membranes SEM figures prepared by embodiment 1.
Fig. 5 is the SSZ-13 molecular sieve seed XRD diagram prepared by embodiment 13.
Specific implementation mode
In order to further describe the present invention, implementation specific embodiments of the present invention are given below, but the present invention is claimed
Range be not limited to embodiment.
Embodiment 1
The mode that the present invention prepares SSZ-13 molecular sieves is specific as follows：
Step 1：It is prepared by SSZ-13 molecular sieve seeds.By sodium hydroxide, N, N, N- front three adamantyl ammonium hydroxide
（TMAdaOH）Be added in deionized water with aluminium hydroxide, be stirred at room temperature 30 min, form Sol A, by Ludox and go from
Sub- water is uniformly mixed, and 10 min of stirring form sol B.Sol A and sol B are mixing uniformly to form crystal seed and prepare colloidal sol.Most
The molar ratio of colloidal sol is SiO afterwards2/Al2O3=20、Na2O/SiO2=0.05、H2O/SiO2=30、SDA/SiO2=0.05.By preparation
Colloidal sol is 65o72 H-shaped of burin-in process is at crystal seed nucleus colloidal sol M under C；The colloidal sol that identical preparation process is prepared is 20oUnder C
It stirs 3h and forms colloidal sol S.By nucleus colloidal sol M and colloidal sol S with mass ratio M：S=0.05 is mixed, and synthesis colloidal sol molar ratio is constant.It waits for
After stirring evenly, above-mentioned colloidal sol is fitted into reaction kettle, 110oC reacts for 24 hours, takes out, cooling, centrifuges, washing, after dry
Obtain SSZ-13 crystal seeds.By the molecular sieve seed 550 after dryingoStructure directing agent in C calcining removal molecular sieve pore passages, will
It is spare after molecular sieve after calcining takes out 15 h of ball-milling treatment.The SSZ-13 molecular sieve seeds prepared with the method are denoted as S1.
Step 2：The pretreatment of porous supporting body.It weighs 1 crystal seed of suitable embodiment to be added in ethanol solution, through super
Crystal is evenly dispersed in dispersed phase solution after sound and concussion processing and forms uniform molecular sieve suspension, suspension quality
Score is 0.2%.0.08MPa vacuumizes 5s by molecular sieve crystal coated on aluminium oxide sheet supporter, is handled through oven drying
Afterwards, the molecular sieve crystal layer of continuous densification is formed in supporting body surface, seed density is 1.5 mg/cm2。
Step 3：It is prepared by SSZ-13 molecular screen membranes.By sodium hydroxide, structure directing agent TMAdaOH and aluminium hydroxide in room
It is sufficiently stirred 30 min under temperature and forms Sol A, Ludox is added in deionized water, sol B is formed after stirring 20 min, it will be molten
Glue A is added in sol B, and the colloidal sol molar ratio finally obtained is：SiO2/Al2O3=80、Na2O/SiO2=0.05、H2O/SiO2=30、
SDA/SiO2=0.05, colloidal sol is 65oAging 72h forms nucleus colloidal sol M under C；The colloidal sol that identical proportioning and step are prepared is 20oC
Lower stirring 3h forms colloidal sol S, by nucleus colloidal sol M and colloidal sol S with mass ratio M：S=0.05 is mixed, and colloidal sol molar ratio is not after mixing
Become；Above-mentioned colloidal sol is fitted into reaction kettle, will be coated in the supporter merging colloidal sol of crystal seed, in oil bath 180oC reactions 6h is formed
Film layer；Cleaning, it is dry.
Step 4：The removing of structure directing agent.The removing of structure directing agent, ozone are carried out in ozone atmosphere
（Ozone/oxygen gas）It is 50%, calcination temperature 200oC, calcination time are 2 d, and heat up rate of temperature fall preferably 0.5oC/min.It will
SSZ-13 molecular screen membranes after calcining are denoted as M1.
XRD diagram and SEM figures are as depicted in figs. 1 and 2 before and after SSZ-13 molecular sieve seed ball millings.XRD diagram is shown before and after ball milling
Diffraction maximum and standard card on peak type fit like a glove, crystallinity is higher, crystal be pure phase CHA structure.From electron microscope（Figure
2）In as can be seen that crystal after ball milling by apparent broken, be conducive to coat crystal seed combined on supporter it is more firm
Gu.Crystal grain average grain diameter is 200nm before ball milling, and average grain diameter is 80nm after ball milling.
The XRD diagram of film M1（Such as Fig. 3）Show that synthesizing film has complete CHA structure.Fig. 4 is the SEM figures of M1, it can be seen that is closed
Film formation surface is continuously fine and close.Film M1 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.It is testing
Condition be 0.2 MPa, 25oWhen C, film M1 is to CO2/CH4Separation selectivity be 95.6, to N2/CH4Separation selectivity be
8.0, corresponding CO2Infiltration rate is 6.6 × 10-7 mol/(m2S Pa), N2Infiltration rate be 5.2 × 10-8 mol/(m2
s Pa)。
Embodiment 2
The operating procedure of use such as embodiment 1, except that the structure directing agent in step 3 used in film synthesis is
N, N, N- front three adamantyl ammonium bromide, used silicon source are sodium metaaluminate.The SSZ-13 molecular screen membranes prepared with the method
It is denoted as M2.
The XRD diagram of film M2（Such as Fig. 3）Show that synthesizing film has complete CHA structure.Film M2 is in CO2/CH4And N2/CH4System
Separating property difference it is as shown in Table 1 and Table 2.Test condition：0.2 MPa and 25oC。
Embodiment 3
The operating procedure of use such as embodiment 1, except that the aging temperature of nucleus colloidal sol M is 120 in step 3 oC, aging
Time is that for 24 hours, the silicon source used in film synthesis is aluminium oxide, and silicon source is positive quanmethyl silicate.The SSZ-13 molecules of preparation
Sieve membrane is denoted as M3.
The XRD diagram of film M3（Such as Fig. 3）Show that synthesizing film has complete CHA structure.Film M3 is in CO2/CH4And N2/CH4System
Separating property difference it is as shown in Table 1 and Table 2.Test condition：0.2 MPa and 25oC。
Embodiment 4
The operating procedure of use such as embodiment 1, except that the silicon source in step 3 used in film synthesis is aluminium foil, institute
The structure directing agent used is N, N, N- front three adamantyl ammonium iodides.The SSZ-13 molecular screen membranes prepared with the method are denoted as
M4。
The XRD diagram of film M4（Such as Fig. 3）Show that synthesizing film has complete CHA structure.Film M4 is in CO2/CH4And N2/CH4System
Separating property difference it is as shown in Table 1 and Table 2.Test condition：0.2 MPa and 25oC。
Embodiment 5
The operating procedure of use such as embodiment 1, except that the silicon source used in step 3 is aluminium powder, used structure
Directed agents are N, and N, N- trimethyl benzyl ammonium iodides, silicon source used is tetraethyl orthosilicate.And point used in step 2
The mass fraction of son sieve suspension is 2%, and molecular sieve seed is coated on stainless steel supporter equally in a manner of vacuumizing,
After oven drying is handled, the molecular sieve crystal layer of continuous densification, seed density 2.5mg/cm are formed in supporting body surface2。
The SSZ-13 molecular screen membranes prepared with the method are denoted as M5.
Film M5 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.Test condition：0.2 MPa
With 25oC。
Embodiment 6
The operating procedure of use such as embodiment 1, except that the quality point of the molecular sieve suspension used in step 2
Number is 0.01%, and molecular sieve seed is coated on supporter equally in a manner of vacuumizing, after oven drying is handled, is being propped up
Support body surface forms the molecular sieve crystal layer of continuous densification, seed density 0.5mg/cm2.Step 3 is preparing SSZ-13 molecules
When sieve membrane synthesizes colloidal sol, silicon source is aluminium isopropoxide, and silicon source is waterglass, and the molar ratio of each component is in the Synthesis liquid：
SiO2/Al2O3=250、Na2O/SiO2=0.1、H2O/SiO2=50、SDA/SiO2=0.3.The SSZ-13 molecular screen membranes prepared with the method
It is denoted as M6.
Film M6 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.Test condition：0.2 MPa
With 25oC。
Embodiment 7
The operating procedure of use such as embodiment 1, except that using vacuum pumping method in hollow fiber oxygen in step 2
Change aluminium support body surface and coat crystal seed, the time of 0.01MPa suctions is 90 s, is then at the uniform velocity proposed from suspension, through baking oven
After drying process, the molecular sieve crystal layer of continuous densification is formed in supporting body surface.The SSZ-13 molecular screen membranes prepared with the method
It is denoted as M7.
Film M7 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.Test condition：0.2 MPa
With 25oC。
Embodiment 8
The operating procedure of use such as embodiment 1, except that structure directing agent is tetraethyl ammonium hydroxide, silicon in step 3
Source is sodium metasilicate, by nucleus colloidal sol M and colloidal sol S with mass ratio M：S=0.5 is mixed.Colloidal sol is synthesized preparing SSZ-13 molecular screen membranes
When, the molar ratio of each component is in the Synthesis liquid：SiO2/Al2O3=100、Na2O/SiO2=0.5、H2O/SiO2=200、
SDA/SiO2=0.5.The SSZ-13 molecular screen membranes prepared with the method are denoted as M8.
Film M8 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.Test condition：0.2 MPa
With 25oC。
Embodiment 9
The operating procedure of use such as embodiment 1, except that the temperature that will be calcined when removing structure directing agent in step 4
Become 300oC, time are 15 h.The SSZ-13 molecular screen membranes prepared with the method are denoted as M9.
Film M9 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.Test condition：0.2 MPa
With 25oC。
Embodiment 10
The operating procedure of use such as embodiment 1, except that when removing structure directing agent in step 4, ozone
（Ozone/oxygen gas）It is 1%, temperature 150oC, time 48h, heating and rate of temperature fall are 10oC/min.It is prepared with the method
SSZ-13 molecular screen membranes be denoted as M10.
Film M10 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.Test condition：0.2
MPa and 25oC。
Embodiment 11
The operating procedure of use such as embodiment 1, except that synthesis temperature is 110 in step 3oC, generated time 36
h.The SSZ-13 molecular screen membranes prepared with the method are denoted as M11.
Film M11 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.Test condition：0.2
MPa and 25oC。
Embodiment 12
The operating procedure of use such as embodiment 1, except that synthesis temperature is 200 in step 3oC, generated time 6
H, the supporter used is porous mullite pipe.The SSZ-13 molecular screen membranes prepared with the method are denoted as M12.
Film M12 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.Test condition：0.2
MPa and 25oC。
Embodiment 13
The operating procedure of use such as embodiment 1, except that the constitutive molar ratio of colloidal sol is SiO in step 12/Al2O3=
60、Na2O/SiO2=0.2、H2O/SiO2=60、SDA/SiO2=0.5；Nucleus colloidal sol M treatment conditions are 120oBurin-in process 24 under C
h；The colloidal sol that identical preparation process is prepared is 40o0.5h is stirred under C forms colloidal sol S.The matter of the nucleus colloidal sol M and colloidal sol S of addition
Amount compares M：S=0.5, it is to be mixed uniformly after, above-mentioned colloidal sol is fitted into reaction kettle, 200 oCReact 5h.It takes out, cooling, centrifugation is washed
It washs, SSZ-13 crystal seeds is obtained after dry.By the molecular sieve seed 550 after dryingoStructure in C calcining removal molecular sieve pore passages
Molecular sieve seed after calcining is taken out 5 h of ball-milling treatment by directed agents.The SSZ-13 molecular sieve seeds prepared with the method are denoted as
S2.Crystal grain average grain diameter is 400 nm before ball milling, and average grain diameter is 200 nm after ball milling.
Fig. 5 shows equally there is CHA structure with molecular sieve prepared by the method.
Comparative example 1
The operating procedure of use such as embodiment 1, except that film is not added during synthesis with crystalline substance in step 3
Core solution M.And the brilliant clock of supporting body surface is coated in step 1 without ball-milling treatment.Film synthesizes in an oven, synthesis temperature
Degree is 180oC, generated time 4d.The removing of the molecular screen membrane structure directing agent synthesized in step 4 carries out in air, forges
It is 450 DEG C to burn temperature, and heating and rate of temperature fall are 1oC/min..The SSZ-13 molecular screen membranes prepared with the method are denoted as M13.
Film M13 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.Test condition：0.2
MPa and 25oC。
Comparative example 2
The operating procedure of use such as embodiment 1, except that film is not added during synthesis with crystalline substance in step 3
Core solution M, generated time 2d.The SSZ-13 molecular screen membranes prepared with the method are denoted as M14.
Film M14 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.Test condition：0.2
MPa and 25oC。
Comparative example 3
The operating procedure of use such as embodiment 1, except that film is not added during synthesis with crystalline substance in step 3
Core solution M.And step 1 is coated in the crystal seed of supporting body surface without ball-milling treatment.Film synthesizes in an oven, synthesis temperature
It is 180oC, generated time 2d.The removing of the molecular screen membrane structure directing agent synthesized in step 4 carries out in oxygen atmosphere,
Calcination temperature is 400oC, heating and rate of temperature fall are 1oC/min.The SSZ-13 molecular screen membranes prepared with the method are denoted as M15.
Film M15 is in CO2/CH4And N2/CH4The separating property difference of system is as shown in Table 1 and Table 2.Test condition：0.2
MPa and 25oC。
1 SSZ-13 molecular screen membranes of table are to CO2/CH4Mixed gas separating property
2 SSZ-13 molecular screen membranes of table are to N2/CH4Mixed gas separating property
Claims (9)
1.SSZ-13 the preparation method of molecular screen membrane, which is characterized in that include the following steps：
（1）It is prepared by SSZ-13 molecular sieve seeds：Alkali source, structure directing agent and silicon source are mixed to form Sol A, silicon source and water are mixed
Conjunction forms sol B, and forming crystal seed after Sol A and B mixing prepares colloidal sol, and colloidal sol constitutive molar ratio is：SiO2/Al2O3=20~60、
Na2O/SiO2=0.05~0.2、H2O/SiO2=30~60、SDA/SiO2=0.05 ~ 0.5, colloidal sol is in 65-120oAging 24-72h under C
Form nucleus colloidal sol M；The colloidal sol prepared again with identical proportioning and step is in 20-40o0.5-3h is stirred under C forms colloidal sol S, it will
Nucleus colloidal sol M and colloidal sol S are with mass ratio M：S=0.05 ~ 0.5 mixes；Above-mentioned colloidal sol is fitted into reaction kettle, 110 ~ 200oC
5-24h is reacted, is taken out, it is cooling, it centrifuges, washing obtains SSZ-13 molecular sieve seeds after dry；By the molecular sieve seed after drying
Calcining, then after 5 ~ 15h of ball-milling treatment, it is spare；
（2）The pretreatment of porous supporting body：Weigh appropriate step 1）Molecular sieve seed is added in ethanol solution, through ultrasound and
Crystal seed is evenly dispersed in dispersed phase solution after concussion processing, forms uniform suspension, suspension quality score is
0.01-2%；In a manner of vacuumizing by molecular sieve seed suspension on supporter, holding vacuum degree is 0.01-0.08
MPa, suction time 5-90s, then at the uniform velocity proposes from suspension, after oven drying is handled, is formed in supporting body surface
Continuous fine and close molecular sieve crystal layer；
（3）The preparation of SSZ-13 molecular screen membranes：Alkali source, structure directing agent and silicon source are mixed to form Sol A, silicon source and water are mixed
Conjunction forms sol B, and forming crystal seed after Sol A and B mixing prepares colloidal sol, and colloidal sol constitutive molar ratio is：SiO2/Al2O3=80~250、
Na2O/SiO2=0.05~0.5、H2O/SiO2=30~200、SDA/SiO2=0.05 ~ 0.5, colloidal sol is in 65-120oAging 24- under C
72h forms nucleus colloidal sol M；The colloidal sol that identical proportioning and step are prepared is in 20-40o0.5-3h is stirred under C forms colloidal sol S, it will be brilliant
Core colloidal sol M and colloidal sol S are with mass ratio M：S=0.05-0.5 is mixed；Above-mentioned colloidal sol is fitted into reaction kettle, by step（2）It is coated with crystalline substance
In the supporter merging colloidal sol of kind, 110 ~ 200oC reacts 6-36h and forms film layer；It is cleaned, it is dry, it is calcined under ozone atmosphere
Obtain SSZ-13 molecular screen membranes.
2. the preparation method of SSZ-13 molecular screen membranes according to claim 1, which is characterized in that used in step 1 or 3
Oil bath heating.
3. the preparation method of SSZ-13 molecular screen membranes according to claim 1, which is characterized in that the crystal seed of step 1 is
Nanoscale, crystal seed prepared by step 1 are 400-600nm, and the crystal seed grain size obtained after ball milling is 80-200 nm.
4. the preparation method of SSZ-13 molecular screen membranes according to claim 1, which is characterized in that vacuum crystal method obtains
Seed density be 0.5 ~ 2.5mg/cm2。
5. the preparation method of SSZ-13 molecular screen membranes according to claim 1, which is characterized in that synthesized in step 3
The removing of the structure directing agent SDA of SSZ-13 molecular screen membranes is carried out in ozone atmosphere, and be passed through ozone accounts for the volume of oxygen
Score is 1% ~ 50%, and calcination temperature is 150 ~ 300oC, 5 ~ 48 h of calcination time, heating and rate of temperature fall are 0.5-10oC/
min。
6. the preparation method of SSZ-13 molecular screen membranes according to claim 1, which is characterized in that adopted in step 1 or 3
Silicon source is aluminium hydroxide, sodium metaaluminate, the thin stone of aluminium, aluminium isopropoxide, Tributyl aluminate, aluminium foil, aluminium powder or aluminium oxide.
7. the preparation method of SSZ-13 molecular screen membranes according to claim 1, which is characterized in that adopted in step 1 or 3
Structure directing agent SDA is N, N, N- front three adamantyls ammonium hydroxide, N, N, N- front three adamantyls ammonium bromide, N,
N, N- front three adamantyl ammonium iodide, N, N, N- trimethyl benzyls ammonium hydroxide, N, N, N- tri-methyl benzyl ammonium bromides, N, N,
One or more combinations of N- trimethyl benzyls ammonium iodide or tetraethyl ammonium hydroxide.
8. the preparation method of SSZ-13 molecular screen membranes according to claim 1, which is characterized in that step 13 is used
Silicon source be Ludox, tetraethyl orthosilicate, positive quanmethyl silicate, sodium metasilicate, waterglass or silica flour.
9. the preparation method of SSZ-13 molecular screen membranes according to claim 1, which is characterized in that step 2 or 3 support
Body material is aluminium oxide, mullite or stainless steel, and the supporter effective aperture is 0.05 ~ 3 μm, the support bodily form
Shape is tubulose, sheet or hollow fiber.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569320A (en) * | 2018-12-26 | 2019-04-05 | 韩小学 | A method of mixing crystal seed method prepares pure phase SSZ-13 molecular screen membrane |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289115A (en) * | 2014-08-25 | 2015-01-21 | 南京工业大学 | High silicon CHA type SSZ-13 zeolite membrane preparation method |
| WO2015081648A1 (en) * | 2013-12-04 | 2015-06-11 | 北京化工大学 | Method for synthesizing molecular sieve ssz-13 |
| CN107029561A (en) * | 2017-05-05 | 2017-08-11 | 南京工业大学 | A kind of preparation method of the MFI-type molecular screen membrane of h0h orientations |
| CN107570018A (en) * | 2017-10-25 | 2018-01-12 | 大连理工大学 | A kind of method of the zeolite molecular sieve films of Fast back-projection algorithm SSZ 13 |
-
2018
- 2018-05-14 CN CN201810455775.6A patent/CN108579449B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015081648A1 (en) * | 2013-12-04 | 2015-06-11 | 北京化工大学 | Method for synthesizing molecular sieve ssz-13 |
| CN104289115A (en) * | 2014-08-25 | 2015-01-21 | 南京工业大学 | High silicon CHA type SSZ-13 zeolite membrane preparation method |
| CN107029561A (en) * | 2017-05-05 | 2017-08-11 | 南京工业大学 | A kind of preparation method of the MFI-type molecular screen membrane of h0h orientations |
| CN107570018A (en) * | 2017-10-25 | 2018-01-12 | 大连理工大学 | A kind of method of the zeolite molecular sieve films of Fast back-projection algorithm SSZ 13 |
Cited By (14)
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|---|---|---|---|---|
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| US20220203307A1 (en) * | 2019-04-09 | 2022-06-30 | Georgia Tech Research Corporation | Zeolite membranes, molecular separation methods, and manufacturing processes for zeolite membranes |
| US11964242B2 (en) * | 2019-04-09 | 2024-04-23 | Georgia Tech Research Corporation | Zeolite membranes, molecular separation methods, and manufacturing processes for zeolite membranes |
| CN110182826A (en) * | 2019-05-17 | 2019-08-30 | 大连理工大学 | A method of synthesizing hollow SSZ-13 molecular sieve |
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| KR102316205B1 (en) * | 2020-01-15 | 2021-10-25 | 고려대학교 산학협력단 | Method of Controlling Structure of Defects in Chabazite Zeolite Membranes Through Low Temperature Heat Treatment |
| US11904282B2 (en) | 2020-01-15 | 2024-02-20 | Korea University Research And Business Foundation | Method of controlling structure of defects in chabazite zeolite membranes through low temperature heat treatment |
| CN111547735A (en) * | 2020-04-30 | 2020-08-18 | 上海工程技术大学 | Controllable synthesis method of pure silicon and high-silicon CHA molecular sieve |
| CN114437844A (en) * | 2020-11-03 | 2022-05-06 | 中国石油化工股份有限公司 | Automatic optimization method for parameters of selective denitrification process of natural gas by computer |
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