CN114832645A - Preparation method and application of SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel - Google Patents
Preparation method and application of SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 89
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 66
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- -1 silicon ester Chemical class 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 19
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 239000003345 natural gas Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 230000035515 penetration Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000012920 MOF membrane Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004941 mixed matrix membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- 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
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- 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
-
- 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
- C10L3/105—Removal of contaminants of nitrogen
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention relates to the technical field of preparation and application of molecular sieve membrane materials, and provides a preparation method of an SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel, wherein the fluorine-free and aluminum-free gel is adopted, sodium salt is used for replacing sodium hydroxide, and a high-flux and pure-phase high-silicon SSZ-13 molecular sieve membrane is synthesized on a macroporous support body. The method is simple to operate, low in energy consumption and harmless to the environment; the synthesized SSZ-13 molecular sieve membrane has good gas separation performance in CO 2 /CH 4 And N 2 /CH 4 Has good application prospect in separation.
Description
Technical Field
The invention relates to the technical field of preparation and application of molecular sieve membrane materials, in particular to a preparation method and application of an SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel.
Background
As a clean energy source, methane can be used not only as a fuel, but also as a raw material for other chemicals, and the treated methane can be used in commerce and households. Natural gas is the most important source of methane, including conventional natural gas and unconventional natural gas, such as biogas, coal bed gas, shale gas, and the like. CO 2 2 And N 2 Is the main impurity gas in natural gas, CO 2 And N 2 Not only will the combustion heat value of natural gas be reduced, but also CO will be generated in the presence of steam 2 The impurity gases can also corrode the transport pipeline, and therefore, to make efficient use of the natural gas, CO is separated from methane 2 ，N 2 Such as impurity gases, are highly desirable. The traditional gas separation method mainly comprises organic amine solution adsorption and low-temperature distillation, has a phase change process and high energy consumption, and is generally only suitable for large-scale industrial separation.
The membrane separation technology has the advantages of high efficiency, energy conservation, continuous operation, convenient scale adjustment and the like, and is considered to be a gas separation technology with great application prospect. In recent years, researchers have developed a variety of membranes, such as organic membranes, inorganic membranes, MOF membranes, mixed matrix membranes, and the like, that can be used for gas separation. Inorganic membranes have received continuous attention from researchers in recent years because of their high porosity and superior thermal and chemical stability. The SSZ-13 molecular sieve has CHA topology and three-dimensional pore channels, and the window size is about 0.38nm multiplied by 0.38nm, so that the molecular sieve can better remove CO 2 (kinetic diameter 0.33nm) and N 2 (kinetic diameter 0.36nm) from CH 4 (kinetic diameter 0.38 nm).
All-silicon or high-silicon SSZ-13 molecular sieve membranes are well suited for industrial applications because of their excellent hydrophobic properties. High silica molecular sieve membranes have higher stability in gas separation, but the synthesis of a large number of all-silica or high-silica SSZ-13 molecular sieve membranes reported to date generally requires the addition of a fluorine source, for example, in the literature [ K.Kida, Y.Maeta, K.Yogo, Pure silica CH ]A-type zeolite membranes for dry and humidified CO 2 /CH 4 mixtures separation,Sep.Purif.Technol.197(2018)116-121.]The addition of HF to the gel allows the synthesis of all-silicon CHA molecular sieve membranes, which can have a detrimental effect on the environment. Documents [ J.J.Zhou, F.Gao, K.Sun, X.Y.jin, Y.Zhang, B.Liu, R.F.Zhou, Green Synthesis of high hly CO 2 -Selective CHA Zeolite Membranes in All-Silica and Fluoride-Free Solution for CO 2 /CH 4 Separations,Energy&Fuels.34(2020)11307-11314.]The high-flux CHA zeolite membrane is synthesized in a small-pore support with the pore diameter of 200nm by adopting the all-silicon fluorine-free gel, but the high-silicon SSZ-13 molecular sieve membrane suitable for gas separation prepared by utilizing the fluorine-free aluminum-free gel on a large-pore support is not available at present.
Disclosure of Invention
The invention aims to overcome at least one of the defects of the prior art and provides a preparation method of an SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel, and the obtained SSZ-13 molecular sieve membrane has good gas separation performance. The purpose of the invention is realized based on the following technical scheme:
in one aspect, the invention provides a preparation method of an SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel, which comprises the following steps:
s1, preparing a synthetic gel: adding sodium salt and a silicon source into water for dissolving, adding a template agent, and aging for a certain time to obtain synthetic gel; wherein the sodium source is sodium chloride;
s2, coating SSZ-13 molecular sieve seed crystals on the surface of the micron-sized porous support to form a seed crystal layer;
s3, synthesis of SSZ-13 molecular sieve membrane: and (4) adding the synthetic gel obtained in the step S1 into a reaction kettle, placing the support body coated with the seed crystal layer in the step S2 into the reaction kettle, crystallizing for a certain time at 140-180 ℃, taking out the obtained membrane, washing, drying, calcining, and removing the template agent to obtain the high-silicon SSZ-13 molecular sieve membrane.
Preferably, the silicon source in step S1 includes silica sol, silicon powder, or organic silicone ester.
Preferably, the moles of components in the synthetic gel in step S1The molar ratio is as follows: n (SiO) 2 )：n(Na 2 O): n (templating agent): n (H) 2 O) ═ 1: (0.025-0.5): 0.05-0.5: (20 to 200), more preferably n (SiO) 2 )：n(Na 2 O): n (template): n (H) 2 O)＝1：(0.025～0.2)：0.1：(70～100)。
Preferably, the aging time in the step S1 is 3-12 h.
Preferably, the porous support in step S2 is porous mullite, stainless steel or alumina, and the shape of the porous support is tubular or flat. More preferably, the porous support is porous tubular alumina or mullite.
Preferably, the pore diameter of the porous support in step S2 is 1-5 μm.
Preferably, the method of coating the seed crystal in step S2 is a rubbing method.
Preferably, the silicon-aluminum ratio of the seed crystal in step S2 is equal to or more than 5, more preferably equal to or more than 26.
Preferably, the crystallization time in step S3 is 30-60 h.
Preferably, the calcining temperature in the step S3 is 450-600 ℃, and the time is 6-15 h.
In another aspect of the invention, there is provided an SSZ-13 molecular sieve membrane prepared according to any one of the above methods.
In another aspect, the invention provides an application of SSZ-13 molecular sieve membrane: the SSZ-13 molecular sieve membrane prepared by the method can be used for purifying natural gas in CO 2 /CH 4 Mixture and N 2 /CH 4 The separation of the mixture has good application prospect.
The invention can obtain at least one of the following beneficial effects:
according to the preparation method provided by the invention, a fluorine source and an aluminum source are not added in the synthetic sol, sodium salt is used for replacing sodium hydroxide, and the high-silicon pure-phase SSZ-13 molecular sieve membrane with good gas separation performance is prepared by a simple secondary growth method; and a fluorine source is not used, so that the harm to the environment caused by using fluorine is avoided. The high-silicon SSZ-13 molecular sieve membrane synthesized by the invention has high hydrophobicity,avoid the damage of water vapor and the like to the molecular sieve membrane, and have better hydrothermal stability. Can be used for purifying natural gas, and the SSZ-13 molecular sieve membrane can be used for purifying CO when the pressure difference is 0.2MPa 2 /CH 4 And N 2 /CH 4 The ideal selectivity of the catalyst is respectively 115 and 8.2, and CO 2 、N 2 The penetration amounts of (C) were about (6.73 and 0.48). times.10, respectively -7 mol/(m 2 ·s·Pa)。
Drawings
FIG. 1 is an XRD spectrum of the high silicon SSZ-13 molecular sieve membranes prepared in examples 1-5: (a) example 1, (b) example 2, (c) example 3, (d) example 4, (e) example 5;
FIG. 2 is an SEM image of the high-silicon SSZ-13 molecular sieve membranes prepared in examples 1-5: (a) example 1 surface SEM image, (a') example 1 cross-sectional SEM image; (b) example 2 surface SEM images, (b') example 2 cross-sectional SEM images; (c) example 3 surface SEM picture, (c') example 3 cross-sectional SEM picture; (d) example 4 surface SEM picture, (d') example 4 cross-sectional SEM picture; (e) SEM image of surface of example 5, (e') SEM image of cross-section of example 5;
FIG. 3 is an XRD spectrum of the high silicon SSZ-13 molecular sieve membrane prepared in comparative example 1;
FIG. 4 is an SEM image of a high-silicon SSZ-13 molecular sieve membrane prepared in comparative example 1: (a) surface SEM image, (b) cross-sectional SEM image.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following preferred embodiments: the crystal seed is purchased from Shanghai Songhu chemical industry Co., Ltd, and the silicon-aluminum ratio is 26; the pore diameter of the porous support is about 2 to 3 μm.
Example 1
Dissolving sodium chloride and silica sol in water, adding template TMADAOH, and aging for 6 hr to obtain the final productAnd (4) gelling. The molar ratio of each component is n (SiO) 2 )：n(Na 2 O)：n(TMAdaOH)：n(H 2 O) ═ 1: 0.025: 0.1: 80. SSZ-13 molecular sieve seed crystals are uniformly coated on the surface of the alumina support to form a seed crystal layer. The resulting synthetic gel was placed in a reaction vessel together with a support coated with a seed layer and crystallized at 165 ℃ for 48 h. And washing and drying the obtained membrane, and calcining the membrane at 500 ℃ for 10 hours to remove the template agent to obtain the high-silicon SSZ-13 molecular sieve membrane.
And (3) characterization results: FIG. 1(a) is an XRD representation of the product, from which it can be seen that the membrane synthesized under this example is a pure phase SSZ-13 molecular sieve membrane. FIG. 2(a, a') is an electron micrograph of an SSZ-13 molecular sieve film, from which it can be seen that the surface of the film is covered with a large number of amorphous and unformed crystalline particles and has a significant intergranular spacing, with a film thickness of approximately 1 μm.
The membrane is used for separating CO at 25 ℃ and 0.2MPa 2 /CH 4 And N 2 /CH 4 Performance testing of gases, CO 2 、N 2 The penetration amounts of (3.08 and 0.41) x 10, respectively -7 mol/(m 2 ·s·Pa)，CO 2 /CH 4 The selectivity is 15.1, N 2 /CH 4 The selectivity was 2.0.
Example 2
The procedure for preparing a high-silicon SSZ-13 molecular sieve membrane was the same as in example 1, except that the molar ratio of the gel was changed to n (SiO) 2 )：n(Na 2 O)：n(TMAdaOH)：n(H 2 O)＝1：0.05：0.1：80。
And (3) characterization results: FIG. 1(b) is an XRD representation of the product, from which it can be seen that the synthesized membrane is a phase-pure SSZ-13 molecular sieve membrane. FIG. 2(b, b') is an electron microscope image of SSZ-13 molecular sieve membrane, from which it can be seen that the crystal particles are shaped, the morphology is ellipsoidal, the particle size is about 400nm, the intergranular space disappears, but many amorphous particles still exist on the membrane surface, and the membrane layer becomes thicker by about 2-3 μm.
The membrane is used for separating CO at 25 ℃ and 0.2MPa 2 /CH 4 And N 2 /CH 4 Performance testing of gases, CO 2 、N 2 The penetration amounts of (c) were about (3.25 and 0, respectively.44)×10 -7 mol/(m 2 ·s·Pa)，CO 2 /CH 4 The selectivity is 22.6, N 2 /CH 4 The selectivity was 3.0.
Example 3
The procedure for preparing a high-silicon SSZ-13 molecular sieve membrane was the same as in example 1, except that the molar ratio of the gel was changed to n (SiO) 2 )：n(Na 2 O)：n(TMAdaOH)：n(H 2 O)＝1：0.1：0.1：80。
And (3) characterization results: FIG. 1(c) is an XRD representation of the product, from which it can be seen that the synthesized membrane is a phase-pure SSZ-13 molecular sieve membrane. FIG. 2(c, c') is an electron microscope image of SSZ-13 molecular sieve membrane, from which it can be seen that the amorphous particles on the surface are reduced, and the crystal morphology, size and thickness of the membrane layer are not changed significantly.
The membrane is used for separating CO at 25 ℃ and 0.2MPa 2 /CH 4 And N 2 /CH 4 Performance testing of gases, CO 2 、N 2 The penetration amounts of (C) were about (6.73 and 0.48). times.10, respectively -7 mol/(m 2 ·s·Pa)，CO 2 /CH 4 The ideal selectivity can reach 115, N 2 /CH 4 The ideal selectivity can reach 8.2. The results showed that n (Na) 2 O)：n(SiO 2 ) 0.1: the combination property is the most excellent when 1.
Example 4
The procedure for preparing a high-silicon SSZ-13 molecular sieve membrane was the same as in example 1, except that the molar ratio of the gel was changed to n (SiO) 2 )：n(Na 2 O)：n(TMAdaOH)：n(H 2 O)＝1：0.15：0.1：80。
And (3) characterization results: FIG. 1(d) is an XRD representation of the product, from which it can be seen that the synthesized membrane is a phase-pure SSZ-13 molecular sieve membrane. FIG. 2(d, d') is an electron microscope image of SSZ-13 molecular sieve membrane, from which it can be seen that the amorphous particles on the membrane surface have disappeared, the crystal size has slightly increased, and there is no significant change in the crystal morphology and the thickness of the membrane layer.
The membrane is used for separating CO at 25 ℃ and 0.2MPa 2 /CH 4 And N 2 /CH 4 Performance testing of gases, CO 2 、N 2 The infiltration capacity of (5.65 and 0.5) is prepared10 -7 mol/(m 2 ·s·Pa)，CO 2 /CH 4 The selectivity is 28.2, N 2 /CH 4 The selectivity was 2.5.
Example 5
The procedure for preparing a high-silicon SSZ-13 molecular sieve membrane was the same as in example 1, except that the molar ratio of the gel was changed to n (SiO) 2 )：n(Na 2 O)：n(TMAdaOH)：n(H 2 O)＝1：0.2：0.1：80。
And (3) characterization results: FIG. 1(e) is an XRD representation of the product, from which it can be seen that the synthesized membrane is a phase-pure SSZ-13 molecular sieve membrane. FIG. 2(e, e') is an electron micrograph of an SSZ-13 molecular sieve membrane, from which it can be seen that the crystal size growth is about 500nm and the surface is denser.
The membrane is used for separating CO at 25 ℃ and 0.2MPa 2 /CH 4 And N 2 /CH 4 Performance testing of gases, CO 2 、N 2 The penetration amount of (C) is about (10.01 and 1.3). times.10 -7 mol/(m 2 ·s·Pa)，CO 2 /CH 4 The selectivity was 45.4, N 2 /CH 4 The selectivity was 5.9.
Example 6
The procedure for the preparation of the high silicon SSZ-13 molecular sieve membrane was the same as in example 3, except that sodium chloride was changed to sodium sulfate. The membrane synthesized under these conditions was a phase-pure SSZ-13 molecular sieve membrane and was used for CO separation at 25 ℃ under 0.2MPa 2 /CH 4 And N 2 /CH 4 Performance testing of gases, CO 2 、N 2 The penetration amount of (C) was about (4.36 and 0.52). times.10 -7 mol/(m 2 ·s·Pa)，CO 2 /CH 4 The selectivity is 23.6, N 2 /CH 4 The selectivity was 2.8.
Example 7
The procedure for the preparation of high silicon SSZ-13 molecular sieve membrane was the same as in example 3, except that sodium chloride was changed to sodium bicarbonate. The membrane synthesized under these conditions was a phase-pure SSZ-13 molecular sieve membrane and was used for CO separation at 25 ℃ under 0.2MPa 2 /CH 4 And N 2 /CH 4 Performance testing of gases, CO 2 、N 2 The penetration amount of (9.41 and 1.08). times.10 -7 mol/(m 2 ·s·Pa)，CO 2 /CH 4 The selectivity is 28.5, N 2 /CH 4 The selectivity was 3.3.
Comparative example 1
The procedure for the preparation of the high silicon SSZ-13 molecular sieve membrane was the same as in example 3, except that sodium chloride was changed to sodium hydroxide. As can be seen from the XRD pattern of FIG. 4, there was the appearance of heterocrystals in the product and the synthesized membrane was not a phase pure SSZ-13 molecular sieve membrane. The presence of the hetero-crystalline particles can also be seen in the electron micrograph of FIG. 5.
In conclusion, the invention synthesizes the high-flux pure-phase high-silicon SSZ-13 molecular sieve membrane in the aluminum-free and fluorine-free gel by replacing sodium hydroxide with sodium salt. The method has the advantages of simple operation, low energy consumption, good hydrothermal stability of the synthesized membrane, no harm to the environment and good separation performance.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of an SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel is characterized by comprising the following steps:
s1, preparing a synthetic gel: adding sodium salt and a silicon source into water for dissolving, adding a template agent, and aging for a certain time to obtain synthetic gel;
s2, coating SSZ-13 molecular sieve seed crystals on the surface of the micron-sized porous support to form a seed crystal layer;
s3, synthesis of SSZ-13 molecular sieve membrane: and (4) adding the synthetic gel obtained in the step S1 into a reaction kettle, placing the support body coated with the seed crystal layer in the step S2 into the reaction kettle, crystallizing for a certain time at 140-180 ℃, taking out the obtained film, washing, drying, calcining, and removing the template agent to obtain the high-silicon SSZ-13 molecular sieve film.
2. The method of claim 1, wherein the sodium salt in step S1 comprises sodium chloride, sodium sulfate or sodium bicarbonate, and the silicon source in step S1 comprises silica sol, silica powder or organic silicon ester.
3. The method for preparing the SSZ-13 molecular sieve membrane in the fluoride-free and aluminum-free gel according to claim 1, wherein the molar ratio of each component in the synthetic gel in the step S1 is as follows: n (SiO) 2 )：n(Na 2 O): n (templating agent): n (H) 2 O)＝1：(0.025～0.5)：0.05～0.5：(20～200)。
4. The method for preparing SSZ-13 molecular sieve membrane in the fluoride-free and aluminum-free gel according to claim 1, wherein the aging time in step S1 is 3-12 h.
5. The method of claim 1, wherein the porous support in step S2 is porous mullite, stainless steel or alumina, and the shape of the porous support is tubular or flat.
6. The method for preparing SSZ-13 molecular sieve membrane in the fluoride-free and aluminum-free gel according to claim 1, wherein the silica-alumina ratio of the seed crystal in step S2 is not less than 5.
7. The method for preparing SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel according to claim 1, wherein the crystallization time in step S3 is 30-60 h.
8. The method for preparing SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel according to claim 1, wherein the calcination temperature in step S3 is 450-600 ℃ for 6-15 h.
9. An SSZ-13 molecular sieve membrane, characterized in that it is prepared by the method according to any one of claims 1 to 8.
10. Use of an SSZ-13 molecular sieve membrane according to claim 9 for the separation of CO 2 /CH 4 Mixtures, or separation of N 2 /CH 4 And (3) mixing.
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