CN108744997A - Electrostatic self-assembly seed crystal coating method for preparing molecular sieve membrane - Google Patents
Electrostatic self-assembly seed crystal coating method for preparing molecular sieve membrane Download PDFInfo
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- CN108744997A CN108744997A CN201810547361.6A CN201810547361A CN108744997A CN 108744997 A CN108744997 A CN 108744997A CN 201810547361 A CN201810547361 A CN 201810547361A CN 108744997 A CN108744997 A CN 108744997A
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- crystal seed
- carrier
- seed
- molecular sieve
- screen membrane
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- 239000013078 crystal Substances 0.000 title claims abstract description 167
- 239000012528 membrane Substances 0.000 title claims abstract description 64
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 32
- 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 32
- 238000000576 coating method Methods 0.000 title abstract description 14
- 238000000707 layer-by-layer assembly Methods 0.000 title abstract 2
- 125000002091 cationic group Chemical group 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 230000009881 electrostatic interaction Effects 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 238000001764 infiltration Methods 0.000 claims description 12
- 230000008595 infiltration Effects 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 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 7
- 229910052863 mullite Inorganic materials 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical group 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012466 permeate Substances 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 235000012489 doughnuts Nutrition 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- -1 acrylyl Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000002791 soaking Methods 0.000 abstract description 5
- 230000034655 secondary growth Effects 0.000 abstract description 2
- 238000003618 dip coating Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 241000256135 Chironomus thummi Species 0.000 description 8
- 238000010422 painting Methods 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 7
- 208000023445 Congenital pulmonary airway malformation Diseases 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 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
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- IOFGECNTUNGCMK-UHFFFAOYSA-N ethyl-dimethyl-(prop-2-enoyloxymethyl)azanium Chemical group CC[N+](C)(C)COC(=O)C=C IOFGECNTUNGCMK-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/002—Pretreatement
- B05D3/005—Pretreatment for allowing a non-conductive substrate to be electrostatically coated
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
An electrostatic self-assembly seed crystal coating method for preparing a molecular sieve membrane. The invention provides a high-efficiency seed coating method for preparing a molecular sieve membrane on a carrier. Modifying the surface of a carrier by adopting Cationic Polyacrylamide (CPAM), changing the Zeta potential of the surface of the carrier, soaking the treated carrier in mixed crystal liquid by using a dip-coating method, improving the coating effect of crystal seeds by virtue of electrostatic interaction between crystal seed particles and the modified carrier, and finally preparing the molecular sieve membrane by adopting a hydrothermal synthesis method. The method is suitable for the process of preparing the molecular sieve membrane by the secondary growth method, the coating process of the crystal seeds on the surface of the carrier with the aperture of 0.6-3.0 mu m is adopted, the problem of uneven adhesion of the crystal seeds on the surface of the carrier is solved, the cost is low, the operation is simple, and the method is suitable for large-scale application.
Description
Technical field
The present invention provides a kind of crystal seed painting methods being used to prepare molecular screen membrane.It is carried using the method for electrostatic self-assembled
Coating effect of the high crystal seed in carrier surface, it is intended to prepare fine and close zero defect molecular screen membrane, improve the separation selectivity of film, belong to
Zeolite membrane material preparing technical field.
Background technology
Infiltration evaporation membrane separation technique be using different by dissolving diffusion rate of the separation blending ingredients in membrane material and
Realize separation, separation process is not limited generally by vapor liquid equilibrium, and separating energy consumption is relatively low, especially suitable for azeotropic, nearly boiling
The separation of mixture.With the continuous consumption of fossil energy, global environment deteriorates brings serious threat, the world to human life
Various countries also increasingly pay attention to application of membrane separation technology, while efficiency to UF membrane and application range propose higher want
It asks.Molecular screen membrane more more advantageous than conventional separation techniques just gradually realizes industrialization in recent years.
Molecular screen membrane is a kind of micropore alumino-silicate materials with regular pore passage structure, in terms of gas and liquid separation
Show superior separating property.The preparation of overwhelming majority support type molecular screen membrane uses hydrothermal synthesis method at present, wherein comparing
Commonly secondary growth method, i.e., one layer crystal kind of first precoating induces coating growth on carrier.But crystal seed during applying brilliant
The continuity stand under load body surface surface properties of layer are affected, and abundant experimental results research is found：The seed layer of even compact is easier
Induction prepares zero defect, high duplication molecular screen membrane.But when carrier surface aperture is larger, hair of the one side carrier to crystal seed
Thin midge effect is reduced, and it is difficult attachment carrier surface to lead to crystal seed；Another aspect crystal seed may penetrate into carrier inside, influence to permeate
Flux.Domestic and foreign scholars have done numerous studies, adhesion effect of the promotion crystal seed in carrier surface thus.Mainly pass through chemical reagent
Modify carrier surface and improve binding force between crystal seed and carrier, for example, silane coupling agent, dopamine, polyvinylpyrrolidone,
Diisocyanate, thionyl chloride etc. are to enhance binding force by chemical bond, but the formation of chemical bond generally requires strictly
Experiment condition, cause it is complicated for operation, be difficult to realize industrial applications.For this purpose, finding a kind of efficient, easy, applied widely
Crystal seed painting method it is very urgent.
Invention content
The purpose of the present invention is：Solve the crystal seed coating during carrier surface of large aperture prepares molecular screen membrane it is difficult,
Uneven, capillary midge declines are coated, causing crystal seed to be difficult attachment carrier surface or even crystal seed may penetrate into carrier
The problem of portion causes crystal seed coating uneven, influences the separation selectivity for preparing molecular screen membrane.The present invention provides a kind of efficient
Electrostatic self-assembled crystal seed painting method.Technical concept is:It tests conventionally used to aluminium oxide, zirconium oxide, mullite carrier
It is in elecrtonegativity under the Zeta potential operating condition of surface, and molecular sieve surface is also in elecrtonegativity, is existed both during applying brilliant
Electrostatic repulsion.Crystal seed is the capillary midge ability by carrier surface duct in carrier surface attachment under normal conditions, but
It is the coating effect of strong influence crystal seed when this midge ability weakens due to carrier surface change of properties.The present invention
Using cationic polyacrylamide modify carrier surface, change carrier surface Zeta potential, using crystal seed electrostatic self-assembled and
Coating effect of the capillary midge energy force effect raising crystal seed of carrier itself in carrier surface.
The first aspect of the invention provides：
A kind of molecular screen membrane includes the crystal seed of carrier and carrier surface, and carrier is inorganic, and crystal seed passes through in carrier surface
The electrostatic interaction of cationic polyacrylamide is loaded.
In one embodiment, the pore diameter range of the carrier is 0.6 μm~3 μm, can also be 1 μm~3 μ
M can also be 2 μm~3 μm.
In one embodiment, the material of the carrier can be aluminium oxide, zirconium oxide or titanium oxide or not
Carry out stone；Carrier type is one kind in chip, tubular type, doughnut.
In one embodiment, crystal seed is selected from NaA, T-type, CHA, ZSM-5, MOR or NaY molecular sieve crystal seed.
In one embodiment, the molecular screen membrane is more than 4.0 for the flux that ethanol/water mixed system detaches
kg∙m-2∙h-1, separation factor is more than 1600.
The second aspect of the invention provides：
The preparation method of above-mentioned molecular screen membrane, includes the following steps：
1st step uses cationic polyacrylamide solution dipping carrier, drying；
The carrier that 1st step obtains is immersed in molecular sieve seed suspension by the 2nd step, takes out drying；
The load that 2nd step obtains is had the carrier of crystal seed to carry out hydrothermal synthesis in molecular screen membrane Synthesis liquid, is divided by the 3rd step
Sub- sieve membrane.
In one embodiment, the cationic polyacrylamide class average molecular weight 300~12,000,000, cation
Degree 2~20%.
In one embodiment, the cation group in the cationic polyacrylamide is selected from acrylyl oxy-ethyl
Trimethyl ammonium chloride（DAC）, acrylic acid N, N- dimethylamino ethyl ester（DA）, dimethyl diallyl ammonium chloride（DMDAAC）,
One or more of mixing.
In one embodiment, content is 0.1~0.7 wt.% to cationic polyacrylamide in the solution.
In one embodiment, the crystal seed used in crystal seed suspension is the mixing of original crystal seed and ball milling crystal seed.
In one embodiment, original crystal seed particle size range is 2~4 μm；The particle size range of ball milling crystal seed is 0.3~
0.5 μm。
In one embodiment, original crystal seed and ball milling crystal seed mass ratio are 2:3~7:3.
In one embodiment, the mass content of crystal seed is 0.8~2.0 wt.% in molecular sieve seed suspension.
In one embodiment, before the 1st step, carrier is handled using aqueous slkali.
In one embodiment, the aqueous slkali is inorganic base.
In one embodiment, the inorganic base is sodium hydroxide or potassium hydroxide.
In one embodiment, the inorganic alkali concentration is 0.05~0.5 mol/L, it is preferred to use is 0.1 mol/
L。
The third aspect of the invention provides：
Purposes of the above-mentioned molecular screen membrane in infiltration evaporation and/or Steam soak solvent dehydration.
In one embodiment, the solvent is organic solvent.
In one embodiment, the organic solvent is selected from alcohols solvent, esters solvent, ether solvent or benzene class
The mixing of one or more of solvent.
In one embodiment, 70~120 °C of feeding temperature in infiltration evaporation or Steam soak process, per-meate side
Absolute pressure be 10~3000 Pa.
The fourth aspect of the invention provides：
A kind of method of macropore carrier area load molecular sieve seed, includes the following steps：
1st step includes the mixing crystal seed of original crystal seed and ball milling crystal seed in the area load of carrier；
The carrier of 2nd step, the load crystal seed obtained to the 1st step carries out hydrothermal synthesis in molecular screen membrane Synthesis liquid, obtains molecule
Sieve membrane.
In one embodiment, original crystal seed particle size range is 2~4 μm；The particle size range of ball milling crystal seed is 0.3~
0.5 μm。
In one embodiment, original crystal seed and ball milling crystal seed mass ratio are 2:3~7:3.
In one embodiment, the mass content of crystal seed is 0.8~2.0 wt.% in molecular sieve seed suspension.
The fifth aspect of the invention provides：
Purposes of the cationic polyacrylamide in improving molecular screen membrane Zeta potential.
Advantageous effect
The present invention is improved using cationic polyacrylamide modification carrier surface using electrostatic self-assembled crystal seed painting method
Crystal seed successfully prepares the molecular screen membrane with high separation selectivity energy in carrier surface adhesion effect.
Description of the drawings
Fig. 1 is Zeta potential characterization result figure.
Fig. 2 is the surface electron microscope for the molecular screen membrane that embodiment 1 is prepared.
Fig. 3 is the surface electron microscope for the molecular screen membrane that reference examples 1 are prepared.
Specific implementation mode
Below by specific implementation mode combination attached drawing, invention is further described in detail.But those skilled in the art
It will be understood that the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment
Particular technique or condition person carry out according to technology or condition described in document in the art or according to product description.
Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.
The value expressed using range format should be interpreted as not only in a flexible way including clearly enumerating as range
The numerical value of limit value, but also include all single numbers or the subinterval covered in the range, like each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood as including not only clearly enumerating
4%) and subinterval (example the concentration of about 0.1% to about 5% further includes the single concentration in how (e.g., 1%, 2%, 3% and
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).Word "include", "comprise" used herein, " having " or its is any
What other variants were intended to cover non-exclusionism includes.E.g., including technique, method, article or the equipment for listing element need not be by
It is limited to those elements, but may include that other are not explicitly listed or belong to this technique, method, article or equipment inherently
Element.
The present invention provides a kind of preparation method of molecular screen membrane, this method main purpose is for solving to carry in large aperture
When body area load crystal seed, since still when carrier surface aperture is larger, one side carrier subtracts the capillary midge effect of crystal seed
Few, it is difficult attachment carrier surface to lead to crystal seed；Another aspect crystal seed may penetrate into carrier inside, the problem of influencing permeation flux.
The technical concept that the present invention uses is that cationic polyacrylamide is used to carry out at modification the surface of inorganic carrier first
Reason makes its surface carry positive charge, simultaneously as seed surface is typically to carry negative electrical charge, it therefore, can be with by electrostatic interaction
So that crystal seed is preferably carried on the surface of macropore carrier, solves that midge effect is low, load capacity is few, crystal seed load non-uniform is asked
Topic.
The carrier of the large aperture used in the present invention is primarily referred to as that its surface average pore size is larger, and the pore diameter range of carrier is
0.6 μm~3 μm, can also be 1 μm~3 μm, can also be 2 μm~3 μm.
In above process, molecular sieve carrier can select aluminium oxide, zirconium oxide or titanium oxide or mullite,
Carrier type is one kind in chip, tubular type, doughnut.The crystal seed of use be mainly NaA, T-type, CHA, ZSM-5, MOR or
Person's NaY molecular sieve crystal seed.
Cationic-type polyacrylamide used in the present invention, average molecular weight can be 300~12,000,000, cation
Degree 2~20%；In addition, the cationic gene in cationic polyacrylamide is selected from acrylyl oxy-ethyl-trimethyl salmiac
（DAC）, acrylic acid N, N- dimethylamino ethyl ester（DA）, dimethyl diallyl ammonium chloride（DMDAAC）One or more of
Mixing.Content is 0.1~0.7 wt.% to cationic polyacrylamide in the solution.
It is coated using cationic polyacrylamide to the surface modification of carrier and then by carrier by way of soaking paste
Crystal seed suspension can be carried on the surface of carrier since the surface of crystal seed carries negative electrical charge by electrostatic interaction, gram
The problem of midge power is insufficient, load is uneven, crystal seed blocks carrier duct is taken.Again by the method for hydrothermal synthesis, synthesizing
Molecular screen membrane is prepared in liquid.
For hydrothermal synthesis here, the Synthesis liquid used is not particularly limited, such as the film of NaA molecular sieve membrane
Liquid can be made by conventional method, such as：Silicon source and sodium hydroxide are added in deionized water and are sufficiently stirred, is clarified
Aluminum solutions when, be added silicon source solution, in homogeneous, obtained solution be the film of synthesis NaA molecular sieve membrane for stirring to solution
Liquid.The silicon source can be one kind in sodium aluminate, sodium metaaluminate, aluminium foil, aluminium powder or aluminium hydroxide；The silicon source can
Think one kind in sodium metasilicate, Ludox or sodium metasilicate.The consumption proportion of raw material is the silicon source and silicon by use in preparation liquid
The difference in source, according to A12O3、SiO2、Na2O、H2What the proportioning of O was converted into；Preferred proportioning is A12O3 : SiO2 :
Na2O : H2O=1:1~5:1~50:100~1000 (molar ratios).Hydrothermal synthesis temperature is preferably 40~150 °C；Crystallization is anti-
Preferably 0.5~5 h between seasonable；Crystallization number is preferably 1~3 time.
In the other embodiment of the present invention, the surface of carrier can be carried out using inorganic alkali solution in advance
On the one hand dipping pretreatment can be carried more hydroxyls, more conducively be loaded by the surface of the carrier after alkaline solution treatment
More cationic polyacrylamide improve the electrostatic efficiency between crystal seed, improve the separating property and flux of film；Another party
Face can remove the impurity of carrier inside, including carrier surface and internal unformed impurity particle.Aqueous slkali can be inorganic base
（Sodium hydroxide or potassium hydroxide）, inorganic alkali concentration is 0.05~0.5 mol/L, it is preferred to use is 0.1 mol/L.Hydroxide
The relatively low structure for not interfering with carrier of na concn.
In the other embodiment of the present invention, during the cement-dipping method coating crystal seed of use, crystal seed suspends
Using the mixing crystal seed of original crystal seed and ball milling crystal seed in liquid.Due to original crystal seed, grain size is larger, in the present invention,
It acts on the macropore that mainly can be used for blocking carrier surface, prevents short grained crystal seed from penetrating into inside the duct of carrier and occurs
Inside blocks；Meanwhile the ball milling crystal seed used, it is to have original crystal seed compared with Gao Bibiao by being obtained after ball-milling treatment
Area is big and active, is mutually cooperateed with original crystal seed, on the one hand ensure that and plug-hole does not occur, and on the other hand, it is equal to improve seed layer
Even property improves induced activity.Original crystal seed particle size range is 2~4 μm；The particle size range of ball milling crystal seed is 0.3~0.5 μm；
In one embodiment, original crystal seed and ball milling crystal seed mass ratio are 2:3~7:3；Crystal seed in molecular sieve seed suspension
Mass content is 0.8~2.0 wt.%.
The step of typical operating method of the present invention, is as follows：
The first step：Diluted sodium hydroxide solution impregnates carrier 12 h, distilled water flushing, drying；
Second step：The processed carrier of the first step is impregnated with cationic polyacrylamide solution, after immersion, Adsorption of Filter Paper carries
The polymer of body excess surface, is dried for standby；
Third walks：Molecular sieve crystal (the mixing crystal seed of original crystal seed and ball milling crystal seed), water, Ludox are made into crystal seed to suspend
Crystal seed is coated in carrier outer surface under room temperature by liquid using the method for Best-Effort request, drying obtain applying it is brilliant after carrier；
4th step：Third is walked the carrier after obtained painting crystalline substance and is put into film Synthesis liquid by weighing, stirring with film Synthesis liquid, into
Row hydrothermal synthesis.It takes out after reaction and is washed with distilled water, is dried, obtain fine and close zero defect molecular screen membrane.
Above-mentioned molecular screen membrane is suitable for the dehydration of solvent, and applicable organic solvent can be that amides are molten here
The mixing of one or more of agent, alcohols solvent, nitrile solvents, amine solvent, ether solvent or sulfone class solvent.Above-mentioned
Molecular screen membrane during solvent dehydration, can show promoted filtration flux, good operation stability, good separating effect it is excellent
Point.
Infiltration evaporation performance test methods are carried out to molecular screen membrane：The infiltration evaporation performance of film is usually by saturating in the unit interval
Cross the permeation flux of per membrane areaJ (kg/m2H) weighed with separation factor α two parameters, α andJIt is defined as follows：
In formulay i Withy j The mass fraction of per-meate side organic matter and water is indicated respectively,x i Withx j Respectively indicate raw material in organic matter and
The mass fraction of water.
In formulaΔMIndicate penetrating fluid quality (kg),SIndicate that film surface accumulates (m2),tIndicate time of penetration (h).
Embodiment 1
Step 1：70 mm of length, 3.6 mm carrier 12 h of outer diameter, the material of carrier are impregnated with the sodium hydroxide solution of 0.1 mol/L
Matter is mullite, and average pore size scope is 2 μm, after distilled water flushing, 60 °C of drying.By the carrier both ends raw material after drying
Band package, then with the cationic polyacrylamide of 0.7wt.%（Molecular weight 5,000,000,20 % of cationic degree）Aqueous solution soaking carrier
1.5 h, after immersion, filter paper absorbs the extra polymer of carrier surface, and 70 °C of baking 3h are spare.
Step 2:Weigh the original crystal seed of a certain amount of NaA molecular sieve (about 3.2 μm of average grain diameter) and ball milling crystal seed (average grain
About 0.36 μm of diameter) mass content ratio be 1:1 mixing crystal seed is add to deionized water, then is added into crystal seed suspension
Ludox uses cell disruptor 200 W, 0.5 h of ultrasound under room temperature, keeps crystal seed evenly dispersed.Wherein seed count is 1 wt.%；
Ludox content is 1 wt.%.By treated, carrier is immersed in crystal seed liquid, and it is 15 s to apply the brilliant time, then in 60 °C of baking ovens
Middle drying obtains applying the carrier after crystalline substance.
Step 3：It weighs, uniform films Synthesis liquid is prepared in stirring, carrier merging stainless steel reaction after the crystallization that step 2 is obtained
In kettle, Synthesis liquid is poured into, for a period of time, taking-up is dipped to weakly acidic pH, 60 °C of bakings to crystallization with deionized water at a certain temperature
It is dry, you can to obtain dense molecular sieve membrane, characterized for infiltration evaporation.
Embodiment 2
Step 1：70 mm of length, 3.6 mm carrier 12 h of outer diameter, the material of carrier are impregnated with the sodium hydroxide solution of 0.1 mol/L
Matter is mullite, and average pore size scope is 2 μm, after distilled water flushing, 60 °C of drying.By the carrier both ends raw material after drying
Band package, then with the cationic polyacrylamide of 0.3 wt.%（Molecular weight 5,000,000,20 % of cationic degree）Aqueous solution soaking carrier
1.5 h, after immersion, filter paper absorbs the extra polymer of carrier surface, and 70 °C of 3 h of baking are spare.
Step 2：Specific steps are identical as 1 step 2 of embodiment.
Step 3：Specific steps are identical as 1 step 3 of embodiment.
Embodiment 3
Step 1：Specific steps are identical as 1 step 1 of embodiment.
Step 2：Weigh the original crystal seed of a certain amount of NaA molecular sieve (about 3.2 μm of average grain diameter) and ball milling crystal seed (average grain
About 0.36 μm of diameter) mass content ratio be 2:3 mixing crystal seed is add to deionized water, then is added into crystal seed suspension
Ludox uses cell disruptor 200 W, 0.5 h of ultrasound under room temperature, keeps crystal seed evenly dispersed.Wherein seed count is 1 wt.%；
Ludox content is 1 wt.%.By treated, carrier is immersed in crystal seed liquid, and it is 15 s to apply the brilliant time, then in 60 °C of baking ovens
Middle drying obtains applying the carrier after crystalline substance.
Step 3：Specific steps are identical as 1 step 3 of embodiment.
Embodiment 4
Step 1：Specific steps are identical as 1 step 1 of embodiment.
Step 2：Weigh the original crystal seed of a certain amount of NaA molecular sieve (about 3.2 μm of average grain diameter) and ball milling crystal seed (average grain
About 0.36 μm of diameter) mass content ratio be 7:3 mixing crystal seed is add to deionized water, then is added into crystal seed suspension
Ludox uses cell disruptor 200 W, 0.5 h of ultrasound under room temperature, keeps crystal seed evenly dispersed.Wherein seed count is 1 wt.%；
Ludox content is 1 wt.%.By treated, carrier is immersed in crystal seed liquid, and it is 15 s to apply the brilliant time, then in 60 °C of baking ovens
Middle drying obtains applying the carrier after crystalline substance.
Step 3：Specific steps are identical as 1 step 3 of embodiment.
Embodiment 5
Step 1：Specific steps are identical as 1 step 1 of embodiment.
Step 2：Weigh the original crystal seed of a certain amount of NaA molecular sieve (about 3.2 μm of average grain diameter) and ball milling crystal seed (average grain
About 0.36 μm of diameter) mass content ratio be 1:1 mixing crystal seed is add to deionized water, then is added into crystal seed suspension
Ludox uses cell disruptor 200 W, 0.5 h of ultrasound under room temperature, keeps crystal seed evenly dispersed.Wherein seed count is 0.8
wt.%；Ludox content is 1 wt.%.By treated, carrier is immersed in crystal seed liquid, and it is 15 s to apply the brilliant time, then at 60 °C
It is dried in baking oven, obtains applying the carrier after crystalline substance.
Step 3：Specific steps are identical as 1 step 3 of embodiment.
Embodiment 6
Step 1：Specific steps are identical as 1 step 1 of embodiment.
Step 2：Weigh the original crystal seed of a certain amount of NaA molecular sieve (about 3.2 μm of average grain diameter) and ball milling crystal seed (average grain
About 0.36 μm of diameter) mass content ratio be 1:1 mixing crystal seed is add to deionized water, then is added into crystal seed suspension
Ludox uses cell disruptor 200 W, 0.5 h of ultrasound under room temperature, keeps crystal seed evenly dispersed.Wherein seed count is 2 wt.%；
Ludox content is 1 wt.%.By treated, carrier is immersed in crystal seed liquid, and it is 15 s to apply the brilliant time, then in 60 °C of baking ovens
Middle drying obtains applying the carrier after crystalline substance.
Step 3：Specific steps are identical as 1 step 3 of embodiment.
Reference examples 1
Difference with embodiment 1 is：Carrier is not pre-processed using cationic polyacrylamide.
Step 1：70 mm of length, 3.6 mm carrier 12 h of outer diameter, carrier are impregnated with the sodium hydroxide solution of 0.1 mol/L
Material be mullite, average pore size scope is 2 μm, after distilled water flushing, 60 °C drying.
Step 2:Weighing the original crystal seeds of a certain amount of NaA (about 3.2 μm of average grain diameter), (average grain diameter is about with NaA ball millings crystal seed
0.36 μm) mass content ratio be 1:1 mixing crystal seed is add to deionized water, then addition silicon is molten into crystal seed suspension
Glue uses cell disruptor 200 W, 0.5 h of ultrasound under room temperature, keeps crystal seed evenly dispersed.Wherein seed count is 1 wt.%；Silicon is molten
Glue content is 1 wt.%.By treated, carrier is immersed in crystal seed liquid, and it is 15s to apply the brilliant time, is then dried in 60 °C of baking ovens
It is dry, obtain the carrier of crystallization.
Step 3：It weighs, uniform films Synthesis liquid is prepared in stirring, carrier merging stainless steel reaction after the crystallization that step 2 is obtained
In kettle, Synthesis liquid is poured into, for a period of time, taking-up is dipped to weakly acidic pH, 60 °C of bakings to crystallization with deionized water at a certain temperature
It is dry, you can to obtain molecular screen membrane, characterized for infiltration evaporation.
Reference examples 2
Difference with embodiment 1 is：Carrier is not pre-processed using sodium hydroxide solution.
Step 1：Using 70 mm of length, 3.6 mm carrier 12 h of outer diameter, the material of carrier is mullite, average pore size model
It is 2 μm to enclose, after distilled water flushing, 60 °C of drying.Carrier both ends after drying are wrapped up with raw material band, then with 0.7 wt.%'s
Cationic polyacrylamide（Molecular weight 5,000,000,20 % of cationic degree）1.5 h of aqueous solution soaking carrier, after immersion, filter paper
The extra polymer of carrier surface is absorbed, 70 °C of 3 h of baking are spare.
Step 2:Weighing the original crystal seeds of a certain amount of NaA (about 3.2 μm of average grain diameter), (average grain diameter is about with NaA ball millings crystal seed
0.36 μm) mass content ratio be 1:1 mixing crystal seed is add to deionized water, then addition silicon is molten into crystal seed suspension
Glue uses cell disruptor 200 W, 0.5 h of ultrasound under room temperature, keeps crystal seed evenly dispersed.Wherein seed count is 1 wt.%；Silicon is molten
Glue content is 1 wt.%.By treated, carrier is immersed in crystal seed liquid, and it is 15 s to apply the brilliant time, is then dried in 60 °C of baking ovens
It is dry, obtain the carrier of crystallization.
Step 3：It weighs, uniform films Synthesis liquid is prepared in stirring, carrier merging stainless steel reaction after the crystallization that step 2 is obtained
In kettle, Synthesis liquid is poured into, for a period of time, taking-up is dipped to weakly acidic pH, 60 °C of bakings to crystallization with deionized water at a certain temperature
It is dry, you can to obtain molecular screen membrane, characterized for infiltration evaporation.
Reference examples 3
Difference with embodiment 1 is：Crystal seed is all using original crystal seed in crystal seed suspension.
Reference examples 4
Difference with embodiment 1 is：Crystal seed is all using ball milling crystal seed in crystal seed suspension.
Zeta potential characterizes
The stream of carrier used in embodiment 1, NaA molecular sieve crystal seed and the carrier after being modified by cationic polyacrylamide
Potentiodynamic technique measures Zeta potential as shown in Figure 1, from the figure, it can be seen that the current potential of carrier, NaA molecular sieve crystal seed is essentially negative
Electrically, and cationic polyacrylamide is electropositive under acid and weak basic condition.Pass through cation poly- third in neutrallty condition
It is electrical that acrylamide modification can change carrier surface.
Electronic Speculum characterizes
The surface Electronic Speculum of the molecular screen membrane being prepared in embodiment 1 is as shown in Fig. 2, it can be seen from the figure that be prepared
The surface compact of molecular screen membrane is uniform, and crystal grain is generally smaller.The molecular screen membrane Electronic Speculum being prepared in reference examples 1 is as schemed
Shown in 3, it can be seen from the figure that there are the crystal grains of a large amount of large-sizes for film surface, and surface even compact is poor.
Lot of experiments finds, the uniformity of seed layer the pattern of induced synthesis film layer is served it is huge, so being repaiied through CPAM
Carrier after decorations can significantly improve the coating effect of crystal seed.
Infiltration evaporation separation test
Molecular screen membrane characterizes experimental result for infiltration evaporation.Material liquid is 90 wt.% ethanol/water mixed systems, experimental temperature
It is 75 °C.
It can be seen that, the preparation method in the present invention can effectively be prepared on the surface of macropore carrier from upper table
The molecular screen membrane of high separation selectivity energy.Meanwhile by embodiment 1 and the comparison of reference examples 1 as can be seen that modifying without CPAM
Carrier, the brilliant effect of painting is undesirable, the separation factor 441 of the molecular screen membrane of preparation, permeation flux 4.25kg.m-2.h-1.And it passes through
After CPAM modifies carrier, the molecular screen membrane separation factor of preparation>10000,5.45 kg.m of permeation flux-2.h-1, this is mainly
After being modified by CPAM due to carrier, seed particles are improved in the Load Balanced of carrier surface, while original bulky grain is brilliant
Kind can prevent ball milling crystal seed from penetrating into carrier inside, prevent from blocking duct, the molecular screen membrane separating property and permeation flux of preparation
It is significantly improved.By reference examples 2 and the comparison of embodiment 1 it can also be seen that using sodium hydroxide to the surface of carrier
It is pre-processed, the surface hydroxyl amount of carrier can be effectively improved, while improving the load capacity of cationic polyacrylamide,
Crystal seed electrostatic assembly coating effect can be improved, the separation selectivity of film is improved.It can be seen that, passed through by reference examples 3 and control 4
After CPAM modifies carrier, original crystal seed and ball milling crystal seed coated carrier surface are individually used, does not all form continuous seed layer, with
There are a large amount of defects, no separation selectivities for the molecular sieve film layer prepared as induction.So after CPAM modifies carrier, original crystalline substance
The mixing crystal seed liquid coated carrier of kind and ball milling crystal seed, is the essential condition for preparing high-performance molecular screen membrane.
Claims (10)
1. a kind of molecular screen membrane, includes the crystal seed of carrier and carrier surface, carrier is inorganic, which is characterized in that crystal seed
It is loaded by the electrostatic interaction of cationic polyacrylamide in carrier surface.
2. molecular screen membrane according to claim 1, which is characterized in that the pore diameter range of the carrier is 0.6 μm~3
μm, it can also be 1 μm~3 μm, can also be 2 μm~3 μm；The material of the carrier can be aluminium oxide, zirconium oxide,
Titanium oxide or mullite；Carrier type is one kind in chip, tubular type, doughnut；Crystal seed be selected from NaA, T-type, CHA,
ZSM-5, MOR or NaY molecular sieve crystal seed；The molecular screen membrane is more than 4.0 for the flux that ethanol/water mixed system detaches
kg∙m-2∙h-1, separation factor is more than 1600.
3. the preparation method of molecular screen membrane described in claim 1, which is characterized in that include the following steps：
1st step uses cationic polyacrylamide solution dipping carrier, drying；
The carrier that 1st step obtains is immersed in molecular sieve seed suspension, takes out drying by the 2nd step；
The load that 2nd step obtains is had the carrier of crystal seed to carry out hydrothermal synthesis in molecular screen membrane Synthesis liquid, is divided by the 3rd step
Sub- sieve membrane.
4. the preparation method of molecular screen membrane according to claim 3, which is characterized in that the cationic polyacrylamide
Class average molecular weight 300~12,000,000, cationic degree 2~20%；Cation group choosing in the cationic polyacrylamide
From acrylyl oxy-ethyl-trimethyl salmiac（DAC）, acrylic acid N, N- dimethylamino ethyl ester（DA）, dimethyl diallyl chlorine
Change ammonium（DMDAAC）One or more of mixing；Content is 0.1~0.7 wt.% to cationic polyacrylamide in the solution
；The crystal seed used in crystal seed suspension is the mixing of original crystal seed and ball milling crystal seed；Original crystal seed particle size range is 2~4 μm；
The particle size range of ball milling crystal seed is 0.3~0.5 μm；Original crystal seed and ball milling crystal seed mass ratio are 2:3~7:3；Molecular sieve seed
The mass content of crystal seed is 0.8~2.0 wt.% in suspension.
5. the preparation method of molecular screen membrane according to claim 3, which is characterized in that before the 1st step, using aqueous slkali
Carrier is handled；The aqueous slkali is inorganic base；The inorganic base is sodium hydroxide or potassium hydroxide；Described
Inorganic alkali concentration is 0.05~0.5 mol/L, it is preferred to use is 0.1 mol/L.
6. use of claim 1~2 any one of them molecular screen membrane in infiltration evaporation and/or Steam soak solvent dehydration
On the way.
7. purposes according to claim 6, which is characterized in that the solvent is organic solvent；The organic solvent
Mixing selected from one or more of alcohols solvent, esters solvent, ether solvent or benzene kind solvent；Infiltration evaporation or steaming
The absolute pressure of 70~120 °C of feeding temperature in vapour process of osmosis, per-meate side is 10~3000 Pa.
8. a kind of method of macropore carrier area load molecular sieve seed, which is characterized in that include the following steps：
1st step includes the mixing crystal seed of original crystal seed and ball milling crystal seed in the area load of carrier；
The carrier of 2nd step, the load crystal seed obtained to the 1st step carries out hydrothermal synthesis in molecular screen membrane Synthesis liquid, obtains molecule
Sieve membrane.
9. the method for macropore carrier area load molecular sieve seed according to claim 8, which is characterized in that original crystal seed
Particle size range is 2~4 μm；The particle size range of ball milling crystal seed is 0.3~0.5 μm；Original crystal seed and ball milling crystal seed mass ratio are
2:3~7:3；The mass content of crystal seed is 0.8~2.0 wt.% in molecular sieve seed suspension.
10. purposes of the cationic polyacrylamide in improving molecular screen membrane Zeta potential.
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| CN109499273A (en) * | 2018-11-26 | 2019-03-22 | 上海绿强新材料有限公司 | A kind of EMT molecular screen membrane and its preparation method and application |
| CN109824010A (en) * | 2019-01-21 | 2019-05-31 | 北京师范大学 | A kind of micro-nano particle X-Y scheme absorbing process based on ion implantation technique |
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| CN112624141A (en) * | 2019-10-08 | 2021-04-09 | 中国石油化工股份有限公司 | Preparation method of MFI molecular sieve membrane |
| CN114405293A (en) * | 2021-08-06 | 2022-04-29 | 江苏九天高科技股份有限公司 | Preparation method and device of flat molecular sieve membrane |
| CN115121132A (en) * | 2022-07-25 | 2022-09-30 | 浙江汇甬新材料有限公司 | NaA/NaY type zeolite molecular sieve membrane and preparation method thereof |
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| CN112624141B (en) * | 2019-10-08 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of MFI molecular sieve membrane |
| CN111992050A (en) * | 2020-09-10 | 2020-11-27 | 南京惟新环保装备技术研究院有限公司 | Carrier surface modified hydrophilic molecular sieve membrane and preparation method thereof |
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| CN115121132A (en) * | 2022-07-25 | 2022-09-30 | 浙江汇甬新材料有限公司 | NaA/NaY type zeolite molecular sieve membrane and preparation method thereof |
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Application publication date: 20181106 |