CN108579449B - Method for rapidly synthesizing high-silicon SSZ-13 molecular sieve membrane - Google Patents

Method for rapidly synthesizing high-silicon SSZ-13 molecular sieve membrane Download PDF

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CN108579449B
CN108579449B CN201810455775.6A CN201810455775A CN108579449B CN 108579449 B CN108579449 B CN 108579449B CN 201810455775 A CN201810455775 A CN 201810455775A CN 108579449 B CN108579449 B CN 108579449B
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CN108579449A (en
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周荣飞
宋世超
高峰
李新平
王斌
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Nanjing Tech University
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • 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
    • 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
    • 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
    • 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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    • 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
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • 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]
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Abstract

the invention relates to a preparation method of a high-silicon SSZ-13 molecular sieve membrane. The molecular sieve membrane comprises a crystal membrane layer and a support body which are selectively separated, and the crystal membrane layer is coated on the surface of the support body; the selectively separated crystal film layer is composed of SSZ-13 molecular sieve; the support is Al2O3Mullite or stainless steel. The SSZ-13 molecular sieve membrane is rapidly prepared by adding crystal nuclei and heating in an oil bath. The membrane prepared by the method is compact, and compared with the traditional heating mode, the membrane synthesis time is greatly shortened while the separation performance of the membrane is ensured. Meanwhile, the structure directing agent is removed in the ozone atmosphere, so that the generation of crystal defects in the demolding process is effectively avoided. The SSZ-13 molecular sieve membrane prepared by the method is used for CO2/CH4And N2/CH4The mixed gas has good separation performance and can be used for purifying natural gas.

Description

Method for rapidly synthesizing high-silicon SSZ-13 molecular sieve membrane
Technical Field
The invention provides a preparation method of a high-silicon SSZ-13 molecular sieve membrane, belonging to the field of preparation and separation application of molecular sieve membrane materials.
Background
With the increasing scarcity of petroleum resources, natural gas is one of the important pillars of energy in the world, and people pay more and more attention to the development and utilization of the natural gas. In the natural gas which has been ascertained, in addition to the main component methane gas, it contains carbon dioxide and nitrogen as the main impurity gases, which lower the combustion calorific value of the fuel gas and therefore require separation before utilization. The separation method commonly used at present mainly comprises solvent absorption, membrane separation, pressure swing adsorption, cryogenic rectification and the like. Among them, membrane separation techniques are receiving increasing attention due to advantages such as low energy consumption and simple operation.
In recent years, the application of molecular sieve membrane in this aspect has been gaining attention because it has high chemical and thermal stability, and molecular sieve membrane can still be used in some complicated working environmentThe better separation performance is kept. To date, a number of large pore molecular sieve membranes have been prepared that can be used for gas separation, such as FAU, MFI, and the like. However, it is difficult to realize small molecule gas systems (e.g., N) because the size of the crystal pore channels of these molecular sieve membranes are too large2/CH4And CO2/CH4) The separation is efficient.
Microporous molecular sieve membranes have great advantages in this respect over these macroporous molecular sieve membranes, because they have a smaller pore structure and can therefore be used to separate some small gas molecules. Wherein SSZ-13 is a molecular sieve of CHA structure having an effective pore size of 0.38 nm x 0.38 nm between the kinetic diameters of carbon dioxide (0.33 nm), nitrogen (0.372 nm) and methane (0.38 nm), and the SSZ-13 molecular sieve itself has preferential adsorption of carbon dioxide, thereby rendering the SSZ-13 molecular sieve CO-selective2/CH4The separation of (A) is superior to other macroporous molecular sieve membranes.
In the existing preparation method of the SSZ-13 molecular sieve membrane, the conventional hydrothermal synthesis is mainly adopted. SSZ-13 molecular sieve membranes (Si/Al = 20) prepared by hydrothermal synthesis of 5d by Halil Kalipcilar et Al (Chem. Mater.,14(2012), 3458-2/CH4，H2/CH4Separation factors of (a) were 12 and 8.2, respectively. In 2014, Nikolay Kosinov et Al (J. mater. chem. A, 2 (2014)), 13083-2O3Hollow fiber is used as a carrier, an SSZ-13 molecular sieve membrane (Si/Al = 100) is prepared by hydrothermal synthesis for 144h at 433K, and CO is subjected to CO treatment under 0.6 MPa2/CH4Up to a separation factor of 42. Zhengshuhong et Al (Journal of Membrane Science 475 (2015); 303-) -310) prepared high performance SSZ-13 molecular sieve Membrane (Si/Al = 20) on the external surface of mullite carrier by using TMADAOH and TEAOH as mixed structure directing agent2/CH4Has a separation selectivity of 300 and is selective to C2H4/C2H6Also has better separation performance, but the permeation rate of the membrane is lower, such as CO2The permeation rate was 2.0X 10-7 mol/(m2 s Pa)。
In the past years, researchers have made certain progress on the synthesis of the SSZ-13 molecular sieve membrane, but at present, the synthesis time of the SSZ-13 molecular sieve membrane is generally too long (more than or equal to 4 d), which causes the synthesized membrane layer to be thicker and not uniform enough, and in the worse, a large number of crystals grow in the support, and the permeation rate of the membrane is seriously affected. The crystallization rate of the film layer is improved, the growth of crystals in the support body can be effectively reduced, the surface growth obtains obvious competitive advantage, and the SSZ-13 molecular sieve film with high flux and uniform growth on the high surface is obtained. At present, the SSZ-13 molecular sieve membrane is prepared by heating in a common oven, the efficiency of air as a heat transfer medium is low, and if the crystallization time is shortened excessively, the membrane layer is not compact enough, so that the separation performance is influenced.
Disclosure of Invention
the invention aims to improve the existing preparation method of high-silicon SSZ-13, and particularly, the method of adding effective crystal nucleus and combining oil bath heating greatly shortens the synthesis time and reduces the energy consumption in the synthesis process; and the structure directing agent in the molecular sieve pore channel is removed by ozone at low temperature, thereby effectively avoiding the generation of defects in the demoulding process. The SSZ-13 molecular sieve membrane prepared by the method is used for CO2/CH4And N2/CH4Has excellent separation performance. The invention is beneficial to the industrial scale-up production of the SSZ-13 molecular sieve membrane.
In order to achieve the purpose, the invention adopts the following technical scheme:
A method for rapidly synthesizing a high-silicon SSZ-13 molecular sieve membrane comprises the following steps:
(1) Preparation of SSZ-13 molecular sieves:
SSZ-13 molecular sieve seed preparation: mixing an alkali source, a Structure Directing Agent (SDA) and an aluminum source to form sol A, mixing a silicon source and water to form sol B, mixing the sol A and the sol B to form seed crystal to prepare sol, wherein the sol comprises the following components in a molar ratio: SiO 22/Al2O3=20~60、Na2O/SiO2=0.05~0.2、H2O/SiO2=30~60、SDA/SiO2=0.05 ~ 0.5.5, sol is in 65-120oAging for 24-72h under C to form crystal nucleus sol M;Then the sol prepared by the same proportion and steps is 20-40oStirring for 0.5-3h to form sol S, mixing crystal nucleus sol M and sol S at mass ratio of M: S =0.05 ~ 0.5.5, loading the above sol into a reaction kettle, and stirring at 110 ~ 200oC, reacting for 5-24h, taking out, cooling, centrifuging, washing, drying to obtain SSZ-13 molecular sieve crystal seeds, calcining the dried molecular sieve crystal seeds, and carrying out ball milling treatment for 5 ~ 15h for later use.
(2) Pretreatment of the porous support: weighing a proper amount of the molecular sieve seed crystal obtained in the step 1) and adding the molecular sieve seed crystal into an ethanol solution, and uniformly dispersing the seed crystal into a dispersion phase solution after ultrasonic treatment and oscillation treatment to form a uniform suspension, wherein the mass fraction of the suspension is 0.01-2%; coating the molecular sieve crystal seed suspension on a support body in a vacuumizing mode, keeping the vacuum degree at 0.01-0.08MPa, sucking for 5-90s, then extracting from the suspension at a constant speed, and forming a continuous and compact molecular sieve crystal layer on the surface of the support body after drying treatment of an oven.
(3) Preparation of SSZ-13 molecular sieve membrane
Preparation of SSZ-13 molecular sieve membrane: mixing an alkali source, a structure directing agent and an aluminum source to form sol A, mixing a silicon source and water to form sol B, mixing the sol A and the sol B to form seed crystal to prepare sol, wherein the sol comprises the following components in a molar ratio: SiO 22/Al2O3=80~250、Na2O/SiO2=0.05~0.5、H2O/SiO2=30~200、SDA/SiO2=0.05 ~ 0.5.5, sol is in 65-120oAging for 24-72h under C to form crystal nucleus sol M; the sol prepared by the same proportion and steps is 20-40oC stirring for 0.5-3h to form sol S, mixing crystal nucleus sol M and sol S according to the mass ratio of M: S =0.05-0.5, putting the sol into a reaction kettle, putting the support body coated with the seed crystal in the step (2) into the sol, and stirring at 110 ~ 200oC, reacting for 6-36h to form a film layer; and washing, drying and calcining under an ozone atmosphere to obtain the SSZ-13 molecular sieve membrane.
The support body material selected in the step (2) of the invention is alumina, mullite and stainless steel; the support body is tubular, sheet-like and hollow fiber in shape.
Preferably, the heating mode in step (3) of the present invention is an oil bath.
The density of the seed crystal obtained by the vacuum coating method in the step (2) of the invention is 0.5 ~ 2.5.5 mg/cm2。
The aluminum source is aluminum hydroxide, sodium metaaluminate, aluminum boehmite, aluminum isopropoxide, aluminum n-butoxide, aluminum foil, aluminum powder or aluminum oxide.
The silicon source is silica sol, tetraethyl orthosilicate, tetramethyl orthosilicate, sodium silicate, water glass or silicon powder.
The structure directing agent is one or a plurality of combinations of N, N, N-trimethyl adamantyl ammonium hydroxide, N, N, N-trimethyl adamantyl ammonium bromide, N, N, N-trimethyl adamantyl ammonium iodide, N, N, N-trimethyl benzyl ammonium hydroxide, N, N, N-trimethyl benzyl ammonium bromide, N, N, N-trimethyl benzyl ammonium iodide or tetraethyl ammonium hydroxide.
The structure directing agent removing mode is preferably carried out in an ozone atmosphere, the volume fraction (ozone/oxygen) of the ozone is preferably 1 ~ 50%, and the calcining temperature is preferably 150 ~ 300oC, the calcination time is preferably 5 ~ 48h, and the temperature rising and reducing rate is 0.5 ~ 10oC/min。
The SSZ-13 molecular sieve membrane prepared by the method is mainly used for gas separation, and the specific application system is CO2/CH4And N2/CH4。
The invention has the beneficial effects that:
(1) The invention effectively shortens the synthesis time of the high-silicon SSZ-13 molecular sieve membrane, saves the preparation cost of the molecular sieve membrane and is beneficial to industrial production by adding the solution with effective crystal nucleus into the membrane synthesis sol and replacing the traditional heating mode by an oil bath heating method.
(2) The method for removing the structure directing agent is carried out in ozone in a certain concentration atmosphere, the temperature of the traditional structure directing agent is reduced, the problem that the SSZ-13 molecular sieve crystal is not matched with the expansion coefficient of a support body at high temperature is effectively avoided, the intercrystalline defect formed during the structure directing agent removal is avoided, and the separation performance of the membrane is reduced.
drawings
FIG. 1 is the XRD patterns before and after ball milling of SSZ-13 molecular sieve seed crystals of example 1.
FIG. 2 is SEM images of SSZ-13 molecular sieve seeds of example 1 before and after ball milling: wherein (a) is SSZ-13 molecular sieve crystal seeds before ball milling, and (b) is SSZ-13 molecular sieve crystal seeds after ball milling.
FIG. 3 is an XRD pattern of the SSZ-13 molecular sieve membrane prepared in example 1 ~ 4, with the support diffraction peaks.
FIG. 4 is an SEM image of the SSZ-13 molecular sieve membrane prepared in example 1.
FIG. 5 is an XRD pattern of seeds of SSZ-13 molecular sieve prepared in example 13.
Detailed Description
In order to further describe the present invention, specific examples for carrying out the present invention are given below, but the scope of the present invention claimed is not limited to the examples.
Example 1
The preparation method of the SSZ-13 molecular sieve comprises the following specific steps:
The method comprises the following steps: SSZ-13 molecular sieve seed preparation. Adding sodium hydroxide, N, N, N-trimethyl adamantyl ammonium hydroxide (TMADAOH) and aluminum hydroxide into deionized water, stirring at room temperature for 30 min to form sol A, uniformly mixing the silica sol and the deionized water, and stirring for 10 min to form sol B. And uniformly stirring the sol A and the sol B to form a seed crystal to prepare the sol. The mol ratio of the final sol is SiO2/Al2O3=20、Na2O/SiO2=0.05、H2O/SiO2=30、SDA/SiO2= 0.05. The prepared sol is added in 65oC, aging for 72h to form a crystal seed crystal nucleus sol M; the sol prepared by the same preparation steps is 20oStirring for 3h under C to form sol S. And (2) mixing the crystal nucleus sol M and the sol S in a mass ratio of M: s =0.05 mixing, and the molar ratio of the synthetic sol was unchanged. After being stirred uniformly, the sol is put into a reaction kettle at 110 DEGoC, reacting for 24 hours, taking out, cooling, centrifuging, washing and drying to obtain the SSZ-13 seed crystal. The dried molecular sieve seed crystals 550oAnd C, calcining to remove the structure directing agent in the pore channel of the molecular sieve, taking out the calcined molecular sieve, and performing ball milling treatment for 15 hours for later use. By usingThe SSZ-13 molecular sieve seed crystal prepared by the method is marked as S1.
Step two: and (4) pretreating the porous support. Weighing a proper amount of the seed crystal of the embodiment 1, adding the seed crystal into an ethanol solution, and uniformly dispersing the crystal into a dispersion phase solution to form a uniform molecular sieve suspension after ultrasonic treatment and oscillation treatment, wherein the mass fraction of the suspension is 0.2%. Coating the molecular sieve crystal on an alumina sheet-shaped support body under 0.08MPa and vacuumizing for 5s, and drying by an oven to form a continuous and compact molecular sieve crystal layer on the surface of the support body, wherein the density of the seed crystal is 1.5 mg/cm2。
Step three: SSZ-13 molecular sieve membrane preparation. Fully stirring sodium hydroxide, TMADAOH as a structure directing agent and aluminum hydroxide for 30 min at room temperature to form sol A, adding the silica sol into deionized water, stirring for 20 min to form sol B, adding the sol A into the sol B, and finally obtaining the sol with the molar ratio: SiO 22/Al2O3=80、Na2O/SiO2=0.05、H2O/SiO2=30、SDA/SiO2=0.05, sol at 65oAging for 72h under C to form crystal nucleus sol M; the sol prepared by the same proportion and steps is 20oC, stirring for 3 hours to form sol S, and mixing the crystal nucleus sol M and the sol S in a mass ratio of M: s =0.05, and the molar ratio of the sol is unchanged after mixing; putting the sol into a reaction kettle, putting a support body coated with the seed crystal into the sol, and carrying out oil bath 180oC, reacting for 6h to form a film layer; and (5) cleaning and drying.
Step four: and (4) removing the structure directing agent. Removing the structure directing agent in an ozone atmosphere, wherein the volume fraction of ozone (ozone/oxygen) is 50 percent, and the calcining temperature is 200 percentoC, the calcining time is 2d, and the heating and cooling rate is preferably 0.5oAnd C/min. The calcined SSZ-13 zeolite membrane was designated M1.
XRD patterns and SEM patterns of the SSZ-13 molecular sieve seed crystal before and after ball milling are shown in figures 1 and 2. The XRD pattern shows that the diffraction peaks before and after ball milling are completely consistent with the peak patterns on the standard cards, the crystallinity is higher, and the crystals are pure-phase CHA structures. As can be seen from the electron micrograph (fig. 2), the ball-milled crystals were significantly crushed, which is beneficial for the coating seeds to be bonded more firmly on the support. The average grain size of the crystal grains before ball milling is 200nm, and the average grain size after ball milling is 80 nm.
The XRD pattern of film M1 (as in fig. 3) indicated that the synthesized film had an intact CHA structure. FIG. 4 is an SEM image of M1, and it can be seen that the surface of the composite membrane is continuously dense. Membrane M1 in CO2/CH4And N2/CH4the separation performance of the system is shown in table 1 and table 2, respectively. Under the test condition of 0.2 MPa, 25oC, membrane M1 vs CO2/CH4Has a separation selectivity of 95.6 to N2/CH4Separation selectivity of (2) is 8.0, corresponding to CO2the permeation rate was 6.6X 10-7 mol/(m2 s Pa)，N2Has a permeation rate of 5.2X 10-8 mol/(m2s Pa)。
Example 2
The procedure was as in example 1, except that in step three, the structure directing agent used in the membrane synthesis was N, N, N-trimethyladamantyl ammonium bromide and the aluminum source used was sodium metaaluminate. The SSZ-13 molecular sieve membrane prepared by this method was designated as M2.
The XRD pattern of film M2 (as in fig. 3) indicated that the synthesized film had an intact CHA structure. Membrane M2 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Example 3
The procedure is as in example 1, except that in step three the ageing temperature of the crystalline core sol M is 120 oCthe aging time is 24h, the aluminum source used in the film synthesis is aluminum oxide, and the silicon source is tetramethyl orthosilicate. The prepared SSZ-13 molecular sieve membrane is marked as M3.
The XRD pattern of film M3 (as in fig. 3) indicated that the synthesized film had an intact CHA structure. Membrane M3 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Example 4
The procedure was as in example 1, except that the aluminum source used in the film synthesis in step three was aluminum foil and the structure directing agent used was N, N, N-trimethyladamantyl ammonium iodide. The SSZ-13 molecular sieve membrane prepared by this method was designated as M4.
The XRD pattern of film M4 (as in fig. 3) indicated that the synthesized film had an intact CHA structure. Membrane M4 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Example 5
The procedure used is as in example 1, except that the aluminum source used in step three is aluminum powder, the structure directing agent used is N, N, N-trimethylbenzylammonium iodide, and the silicon source used is tetraethyl orthosilicate. And the mass fraction of the molecular sieve suspension used in the second step is 2%, the molecular sieve crystal seeds are coated on a stainless steel support body in a vacuumizing mode, a continuous and compact molecular sieve crystal layer is formed on the surface of the support body after drying treatment of an oven, and the density of the crystal seeds is 2.5mg/cm2. The SSZ-13 molecular sieve membrane prepared by this method was designated as M5.
Membrane M5 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Example 6
the procedure used was as in example 1, except that the molecular sieve suspension used in step two had a mass fraction of 0.01%, the support was also coated with molecular sieve seeds in a vacuum, and after oven drying, a continuous dense crystalline layer of molecular sieve was formed on the support surface, with a seed density of 0.5mg/cm2. Step three, when preparing the SSZ-13 molecular sieve membrane synthetic sol, the aluminum source is aluminum isopropoxide, the silicon source is water glass, and the molar ratio of the components in the synthetic solution is as follows: SiO 22/Al2O3=250、Na2O/SiO2=0.1、H2O/SiO2=50、SDA/SiO2And = 0.3. The SSZ-13 molecular sieve membrane prepared by this method was designated as M6.
Membrane M6 in CO2/CH4And N2/CH4Separation Performance of the SystemAs shown in tables 1 and 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Example 7
The procedure used was as in example 1, except that in step two, the surface of the hollow fibrous alumina support was coated with seed crystals using a vacuum method, the suction time was 90 seconds at 0.01MPa, then the seed crystals were extracted from the suspension at a constant speed, and after oven drying, a continuous dense layer of molecular sieve crystals was formed on the surface of the support. The SSZ-13 molecular sieve membrane prepared by this method was designated as M7.
Membrane M7 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Example 8
The procedure used is as in example 1, except that in step three the structure directing agent is tetraethylammonium hydroxide, the silicon source is sodium silicate, and the crystal nucleus sol M and sol S are mixed in the mass ratio M: s =0.5 blend. When the SSZ-13 molecular sieve membrane synthetic sol is prepared, the molar ratio of each component in the synthetic solution is as follows: SiO 22/Al2O3=100、Na2O/SiO2=0.5、H2O/SiO2=200、SDA/SiO2= 0.5. The SSZ-13 molecular sieve membrane prepared by this method was designated as M8.
Membrane M8 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Example 9
The procedure used is as in example 1, except that the calcination temperature in the case of the removal of the structure-directing agent in step four is changed to 300oC, the time is 15 h. The SSZ-13 molecular sieve membrane prepared by this method was designated as M9.
Membrane M9 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Example 10
The procedure used was as in example 1,Except that in the case of removing the structure directing agent in step four, the ozone volume fraction (ozone/oxygen) was 1% and the temperature was 150%oC, the time is 48 hours, and the heating rate and the cooling rate are both 10oAnd C/min. The SSZ-13 molecular sieve membrane prepared by this method was designated as M10.
Membrane M10 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Example 11
The procedure is as in example 1, except that the synthesis temperature in step three is 110oAnd C, the synthesis time is 36 h. The SSZ-13 molecular sieve membrane prepared by this method was designated as M11.
Membrane M11 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
example 12
The procedure was as in example 1, except that the synthesis temperature in step three was 200oAnd C, the synthesis time is 6h, and the adopted support body is a porous mullite tube. The SSZ-13 molecular sieve membrane prepared by this method was designated as M12.
Membrane M12 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Example 13
The procedure used is as in example 1, except that in step one the sol is composed in a molar ratio of SiO2/Al2O3=60、Na2O/SiO2=0.2、H2O/SiO2=60、SDA/SiO2= 0.5; the crystal nucleus sol M treatment condition is 120oC, aging for 24 hours; the sol prepared by the same preparation steps is 40oStirring for 0.5h under C to form sol S. Mass ratio M of added crystal nucleus sol M to sol S: s =0.5, after stirring uniformly, putting the sol into a reaction kettle, and 200 oCAnd reacting for 5 hours. Taking out, cooling, centrifuging, washing and drying to obtainTo SSZ-13 seed. The dried molecular sieve seed crystals 550oAnd C, calcining to remove the structure directing agent in the molecular sieve pore channel, and taking out the calcined molecular sieve crystal seed for ball milling treatment for 5 hours. The SSZ-13 molecular sieve seeds prepared by this method are designated S2. The average grain diameter of crystal grains before ball milling is 400 nm, and the average grain diameter after ball milling is 200 nm.
Figure 5 shows that the molecular sieve prepared by this process also has the CHA structure.
Comparative example 1
The procedure used is as in example 1, except that in step three the film is not added with the nucleation solution M during the synthesis. And the crystal clock coated on the surface of the support body in the first step is not subjected to ball milling treatment. The membrane is synthesized in an oven at a synthesis temperature of 180 DEGoAnd C, the synthesis time is 4 d. The removal of the molecular sieve membrane structure directing agent synthesized in the fourth step is carried out in the air, the calcining temperature is 450 ℃, and the heating and cooling rates are both 1oAnd C/min. . The SSZ-13 molecular sieve membrane prepared by this method was designated as M13.
Membrane M13 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Comparative example 2
The procedure used is as in example 1, except that in step three the film is synthesized without addition of a solution M with crystal nuclei for a synthesis time of 2 d. The SSZ-13 molecular sieve membrane prepared by this method was designated as M14.
Membrane M14 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
Comparative example 3
The procedure used is as in example 1, except that in step three the film is not added with the nucleation solution M during the synthesis. And the seed crystal coated on the surface of the support body in the first step is not subjected to ball milling treatment. The membrane is synthesized in an oven at a synthesis temperature of 180 DEGoAnd C, the synthesis time is 2 d. The removal of the molecular sieve membrane structure directing agent synthesized in the fourth step is carried out in oxygen atmosphere, and then calcination is carried outThe firing temperature is 400 DEGoC, the heating rate and the cooling rate are both 1oAnd C/min. The SSZ-13 molecular sieve membrane prepared by this method was designated as M15.
Membrane M15 in CO2/CH4And N2/CH4The separation performance of the system is shown in table 1 and table 2, respectively. And (3) testing conditions are as follows: 0.2 MPa and 25oC。
TABLE 1 SSZ-13 molecular sieve membrane vs. CO2/CH4Separation performance of mixed gas
TABLE 2 SSZ-13 molecular sieve membrane pair N2/CH4Separation performance of mixed gas

Claims (7)

  1. A preparation method of an SSZ-13 molecular sieve membrane is characterized by comprising the following steps:
    (1) SSZ-13 molecular sieve seed preparation: mixing an alkali source, a structure directing agent SDA and an aluminum source to form sol A, mixing a silicon source and water to form sol B, mixing the sol A and the sol B to form seed crystal to prepare sol, wherein the sol comprises the following components in a molar ratio: SiO 22/Al2O3＝20～60、Na2O/SiO2＝0.05～0.2、H2O/SiO2＝30～60、SDA/SiO2Aging the sol for 24-72h at 65-120 ℃ to form crystal nucleus sol M, wherein the temperature is 0.05-0.5%; then stirring the sol prepared by the same proportion and steps for 0.5-3h at 20-40 ℃ to form sol S, and mixing the crystal nucleus sol M and the sol S according to the mass ratio of M: mixing 0.05-0.5% of S; putting the sol into a reaction kettle, reacting for 5-24h at 110-200 ℃, taking out, cooling, centrifuging, washing and drying to obtain SSZ-13 molecular sieve seed crystals; calcining the dried molecular sieve crystal seeds, and performing ball milling treatment for 5-15 hours for later use; the prepared seed crystal is nano-scale, the seed crystal prepared in the step 1 is 400-600nm, and the particle size of the seed crystal obtained after ball milling is 80-200 nm;
    (2) Pretreatment of the porous support: weighing a proper amount of the molecular sieve seed crystal obtained in the step 1) and adding the molecular sieve seed crystal into an ethanol solution, and uniformly dispersing the seed crystal into a dispersion phase solution after ultrasonic treatment and oscillation treatment to form a uniform suspension, wherein the mass fraction of the suspension is 0.01-2%; coating the molecular sieve crystal seed suspension on a support body in a vacuumizing mode, keeping the vacuum degree at 0.01-0.08MPa, sucking for 5-90s, then extracting from the suspension at a constant speed, and forming a continuous and compact molecular sieve crystal layer on the surface of the support body after drying treatment of an oven;
    (3) Preparation of SSZ-13 molecular sieve membrane: mixing an alkali source, a structure directing agent and an aluminum source to form sol A, mixing a silicon source and water to form sol B, mixing the sol A and the sol B to form seed crystal to prepare sol, wherein the sol comprises the following components in a molar ratio: SiO 22/Al2O3＝80～250、Na2O/SiO2＝0.05～0.5、H2O/SiO2＝30～200、SDA/SiO2Aging the sol for 24-72h at 65-120 ℃ to form crystal nucleus sol M, wherein the temperature is 0.05-0.5%; stirring the sol prepared in the same proportion and steps at 20-40 ℃ for 0.5-3h to form sol S, and mixing the crystal nucleus sol M and the sol S according to the mass ratio of M: 0.05-0.5 percent of S; putting the sol into a reaction kettle, putting the support body coated with the seed crystal in the step (2) into the sol, and reacting at 180-200 ℃ for 6 hours to form a film layer; cleaning, drying, calcining in an ozone atmosphere to remove the structure-directing agent SDA, wherein the volume fraction of the introduced ozone in oxygen is 1-50%, the calcining temperature is 150-300 ℃, the calcining time is 5-48 h, and the heating and cooling rates are 0.5-10 ℃/min.
  2. 2. The method for preparing SSZ-13 zeolite membranes according to claim 1, wherein step 1 or 3 is heated by oil bath.
  3. 3. The method of claim 1, wherein the density of the seeds obtained by the vacuum coating method is 0.5-2.5 mg/cm2。
  4. 4. The method for preparing SSZ-13 molecular sieve membrane according to claim 1, wherein the aluminum source used in step 1 or 3 is aluminum hydroxide, sodium metaaluminate, aluminum boehmite, aluminum isopropoxide, aluminum n-butoxide, aluminum foil, aluminum powder or alumina.
  5. 5. The method of claim 1, wherein the SDA used in step 1 or 3 is one or more of N, N, N-trimethyladamantyl ammonium hydroxide, N, N, N-trimethyladamantyl ammonium bromide, N, N, N-trimethyladamantyl ammonium iodide, N, N, N-trimethylbenzylammonium hydroxide, N, N, N-trimethylbenzylammonium bromide, N, N, N-trimethylbenzylammonium iodide, or tetraethylammonium hydroxide.
  6. 6. The method of claim 1, wherein the silicon source used in step 1 or 3 is silica sol, tetraethyl orthosilicate, tetramethyl orthosilicate, sodium silicate, water glass, or silicon powder.
  7. 7. The method for preparing the SSZ-13 molecular sieve membrane according to claim 1, wherein the support material in step 2 or 3 is alumina, mullite or stainless steel, the effective pore diameter of the support is 0.05-3 μm, and the support is tubular, sheet-like or hollow fiber-like.
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CN109569320B (en) * 2018-12-26 2020-11-17 福州宇卓科技有限公司 Method for preparing pure-phase SSZ-13 molecular sieve membrane by mixed crystal seed method
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
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
CN111547735B (en) * 2020-04-30 2022-08-09 上海工程技术大学 Controllable synthesis method of pure silicon and high-silicon CHA molecular sieve
CN114437844B (en) * 2020-11-03 2022-12-09 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
CN112499642B (en) * 2020-12-02 2023-11-21 南京工业大学 Preparation method of multichannel SSZ-13 molecular sieve membrane
CN114634162A (en) * 2020-12-15 2022-06-17 南京工业大学 Hydrogen purification process adopting CHA type molecular sieve membrane
CN114669201A (en) * 2022-03-09 2022-06-28 南京工业大学 Preparation method of composite SSZ-13/MFI molecular sieve membrane
CN114560475A (en) * 2022-03-09 2022-05-31 南京工业大学 Preparation method of metal modified M-SSZ-13 molecular sieve membrane

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