CN101874990A - Repair method of intergranular pore channel of molecular sieve membrane - Google Patents
Repair method of intergranular pore channel of molecular sieve membrane Download PDFInfo
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- CN101874990A CN101874990A CN2009102350206A CN200910235020A CN101874990A CN 101874990 A CN101874990 A CN 101874990A CN 2009102350206 A CN2009102350206 A CN 2009102350206A CN 200910235020 A CN200910235020 A CN 200910235020A CN 101874990 A CN101874990 A CN 101874990A
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- molecular sieve
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- 239000012528 membrane Substances 0.000 title claims abstract description 101
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 44
- 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 42
- 239000011148 porous material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000008439 repair process Effects 0.000 title abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 238000005086 pumping Methods 0.000 claims abstract description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229910000077 silane Inorganic materials 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 235000012489 doughnuts Nutrition 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 125000005375 organosiloxane group Chemical group 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000002045 lasting effect Effects 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 60
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 56
- 108091006146 Channels Proteins 0.000 description 25
- 239000007789 gas Substances 0.000 description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 8
- 238000000329 molecular dynamics simulation Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000002950 deficient Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910018503 SF6 Inorganic materials 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 108090000862 Ion Channels Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 238000005859 coupling reaction Methods 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a repair method of an intergranular pore channel of a molecular sieve membrane. The repair method comprises the following steps of: putting the molecular sieve membrane into a permeator so as to divide the interior of the permeator into two chambers of a membrane side and a support body side; pumping silane into the membrane side so as to flow through the membrane surface continuously; meanwhile, pumping deionized water into the support body side chamber so as to flow through the support body surface continuously; lasting for 0.5 to 3h, stopping pumping, taking the molecular sieve membrane out, drying and then heating to 450 to 500 DEG C at the speed of 1 to 2 DEG C/min, sintering for 4 to 5h, and cooling to the room temperature at the speed of 1 to 2 DEG C/min. In the invention, organic silane modified liquid in the membrane side chamber of the molecular sieve membrane passes through the intergranular pore channel and undergoes hydrolysis reaction with water detained on the pore channel to generate SiO2 groups, therefore, the intergranular pore channel of the molecular sieve membrane is effectively reduced. The molecular sieve membrane modified by adopting the method has remarkably-increased separation selectivity, high finished product ratio and good repeatability.
Description
Technical field
The present invention relates to the intergranular pore channel of molecular screen membrane is repaired, improve the intergranular pore channel method of a kind of molecular screen membrane of its separation selectivity.
Background technology
It is a kind of isolation technics that development in recent years is got up that film separates, it can separate according to the molecular dynamics diameter difference of material, have low energy consumption, do not pollute, be easy to and characteristics such as other PROCESS COUPLING and industry amplification, can separate the more approaching various materials of physicochemical property especially effectively, this is that traditional separated technology is beyond one's reach, therefore, film separates more and more to be paid close attention to by people, also is acknowledged as 21 century one of the most promising industrial technology.
Zeolite molecular sieve is a kind of porous crystalline body of alumino-silicate, crystal has the pore passage structure of rule, the aperture is less than 1nm, and have that aperture homogeneous, duct are periodic arrangement, adsorptivity is strong, high temperature resistant and the characteristics of resist chemical, the industrial modal kinds such as MFI type, LTA type, FAU type that have.Zeolite molecular sieve film is the dense film that is made of molecular sieve, separate performance because of having good molecule screening, dissolving diffusion etc., and in the film separation system, have broad application prospects, for example at the film separation field of organic gas system, people such as Lai have adopted the diauxic growth method at α-Al
2O
3The ZSM-5 molecular screen membrane of synthetic b orientation on the supporter, the separation selectivity of this film paraxylene/ortho-xylene reaches more than 100; People such as Wang adopt dip-coating-swabbing process synthetic LTA molecular screen membrane on doughnut, and this film is to H
2O/C
2H
5The OH separation factor reaches 10000, and water flux is up to 9.0kg/m
2
Yet, the regular pore canal (i.e. separation to predetermined substance has optionally duct) of the molecular sieve rete of polycrystalline structure in containing zeolite crystal, also comprise space and these non-selective ducts such as pin hole that in synthetic and sintering process, produces and crack between the crystal.These defective ducts make molecular screen membrane obviously descend to the separation selectivity of separation system.Therefore, in some cases, the defective that reduces intergranular pore channel plays crucial effect to the separating property that improves molecular screen membrane.
Summary of the invention
The objective of the invention is the molecular sieve intergranular pore channel to be repaired, these nonselective intergranular pore channels are reduced, to improve its separation selectivity separation system by a kind of method for repairing and mending of intergranular pore channel of molecular sieve membrane is provided.
The said molecular screen membrane of the present invention comprises molecular sieve rete and support body layer, and the method for modifying of intergranular pore channel of molecular sieve membrane is as follows:
Molecular screen membrane is packed into behind cleaning surfaces in the permeator, and molecular screen membrane will be separated into the film side of isolating fully and support two Room, side in the device; With silane is decorating liquid, and the end of decorating liquid from the film side room pumped into, and the other end outflow from the film side room is constantly flow through decorating liquid from face; Meanwhile, the end of deionized water from the supporter side room pumped into, the other end outflow from the supporter side room is constantly flow through deionized water from supporting body surface; Above modification continues 0.5～3h, and molecular screen membrane is taken out in termination of pumping, puts into the baking oven inner drying, and 450～500 ℃ of sintering 4～5h in Muffle furnace lower the temperature and cool off then; The sintering heating rate and the speed that cools are 1～2 ℃/min.
The rete of said molecular screen membrane is that the duct size is 2.8～7.4
Between the molecular sieve rete of any type.
Said hydride modified liquid is preferably average kinetic diameter greater than 4.0
And organosiloxane greater than the molecular screen membrane intracrystalline duct of being repaired.
Said decorating liquid is preferably tetraethoxysilane (TEOS), tetramethoxy-silicane (TMOS) or dimethyldimethoxysil,ne (DMDS).
Above-mentioned mending course can repeat 1-2 time.
The supporter pattern of said molecular screen membrane is chip, tubular type or doughnut supporter.
As the decorating liquid that the silicon source is provided, the molecular dynamics diameter of these organosilans determines that it can only be by the intergranular pore channel of molecular screen membrane, and can't pass through the intracrystalline duct with organosilan in the present invention.When the organosilan decorating liquid in film side room arrives described interface by intergranular pore channel,, produce SiO promptly with the water generation hydrolysis that is trapped on the interface
2Group deposits on intergranular pore channel of molecular sieve membrane, and intergranular pore channel is reduced, thereby reaches the purpose of repairing the intergranular pore channel defective.
This method is easy and simple to handle, and the time spent is short, does not need the experimental provision of special processing, is applicable to the repairing of intracrystalline pore of the molecular screen membrane of the rete that contains any molecular sieve type and any supporter type, is specially adapted to the duct size 2.8～7.4
Between the duct of molecular screen membrane repair, the most suitable molecular sieve rete is MFI type, LTA type, FAU type or DDR type equimolecular sieve membrane type.
The separation selectivity of the molecular screen membrane after this method is modified can be significantly improved the yield rate height of repairing, good reproducibility.The scale system of can be applicable to film has very high commercial Application potentiality.
Description of drawings
Fig. 1 is for before and after modifying, and the chip molecular screen membrane is to the installation drawing of PX/OX separating property test.
The fundamental diagram of Fig. 2 for adopting the organosilan hydrolytic process that molecular screen membrane is repaired.
Fig. 3 is for before and after modifying, and the chip molecular screen membrane is to H
2, SF
6One pack system testing permeability installation drawing.
Fig. 4 is MFI molecular screen membrane surface electromicroscopic photograph before modifying.
Fig. 5 is an electromicroscopic photograph of modifying the MFI molecular screen membrane surface of 1h with tetraethoxysilane.
Fig. 6 is a MFI molecular screen membrane surface electromicroscopic photograph of modifying 1h with dimethyldimethoxysil,ne, and the part amplification of this photo is represented in the upper left corner.
Fig. 7 is the modification source for adopting dimethyldimethoxysil,ne, and along with the modification time increases, molecular screen membrane is to the change curve of PX/OX separating property.
Among Fig. 1: 1-carrier gas pipeline, 2-bubbling gas pipeline, 3-sweep gas pipeline, 4-dimethylbenzene/ortho-xylene head tank, the 5-baking oven, 6-stainless steel permeator, 6-1-film side room, 6-2-supporter side room, the 7-resistance furnace, 8-chip molecular screen membrane, 8-1-film side room, 8-2-supporter side room, the 9-graphite gasket;
Among Fig. 2, the 7-resistance furnace, 8-1-film side room, 8-2-supporter side room, 10-gathers the tetrafluoro permeator, 10-1-film side room, 10-2-supporter side room, 11-modifies the source, 12-dual flow path digital display peristaltic pump, 13,14,15,16-silica gel pipeline;
Among Fig. 3,8-chip molecular screen membrane, 8-1-film side room, 8-2-supporter side room, 9-graphite gasket, 17-deionized water, 18-steel cylinder gas (hydrogen or sulfur hexafluoride), 19-Pressure gauge, 20-soap bubble flowmeter.
The specific embodiment
The repairing of embodiment 1 all-silica MFI type molecular screen membrane reaches the separating property test to paraxylene (PX)/ortho-xylene (OX) system
MFI type molecular screen membrane duct average diameter is 5.5
(be about 5.8 with the molecular dynamics diameter of paraxylene (PX)
) very close, more easily see through the molecular screen membrane duct, and the molecular dynamics diameter of its isomers ortho-xylene (OX), meta-xylene (MX) is 6.8
Therefore, can adopt the MFI molecular screen membrane that paraxylene (PX) is separated from the mixture of ortho-xylene (OX) and meta-xylene (MX).
As seen from Figure 4, all-silica MFI type molecular screen membrane surface also comprises many intergranular pore channels before repairing except that containing a large amount of sieve particles.
One. the MFI type molecular screen membrane before repairing is tested the separating property of paraxylene (PX)/ortho-xylene (OX) system:
As Fig. 1, chip MFI molecular screen membrane is made up of chip supporter 8-2 and molecular sieve rete 8-1, and the film effective area is 2.6cm
2Molecular sieve chip film before modifying is packed in the stainless steel permeator 6, adopts graphite gasket 9 sealings.The mixture of paraxylene/ortho-xylene (volume ratio 1: 1) is housed in the head tank 4, one nitrogen is from pipeline 1 input (1.6ml/min) head tank 4, raw material behind nitrogen dilution enters the film side room 6-1 of (15.7ml/min) permeator 6, control dimethylbenzene dividing potential drop 448Pa, the dimethylbenzene saturated vapor maintains 50 ℃.Supporter side room 6-2 uses the nitrogen from pipeline 2 to purge (18.7ml/min), the sweep gas outlet connects gas chromatograph (available from day island proper Tianjin, the GC-2014 type), by the hydrogen flame detector on-line analysis, the molecular screen membrane when recording 300 ℃ is 4.1 to the PX/OX separation.
The repairing of two .MFI type intergranular pore channel of molecular sieve membrane
With the above-mentioned MFI molecular sieve diaphragm (molecular screen membrane that the chip supporter is promptly arranged, adopting tetraethoxysilane (TEOS) down together) is decorating liquid, mending course is seen Fig. 2, and in the permeator 10 that MFI molecular screen membrane sheet is packed into, the sealing of silica gel O type circle is adopted at molecular sieve diaphragm two ends.Under peristaltic pump 12 effects, decorating liquid 11 circulates in the loop that pipeline 14, film side room 10-1, pipeline 13 are formed, and decorating liquid is constantly flow through from the face of molecular sieve rete 8-1.In like manner, deionized water 17 circulates in the loop that pipeline 16, supporter side room 10-2, pipeline 15 are formed, and deionized water constantly flows through from the surface of road supporter 8-2.The above modification time is 1h.Peristaltic pump 12 is a dual flow path digital display pump, and flow velocity is 75ml/min.Put into 110 ℃ of baking oven inner dryings with modifying good molecular screen membrane, then in Muffle furnace, be warming up to 500 ℃ with the speed of 1 ℃/mi, sintering 5h is with the speed cooling of 1 ℃/mi.
Repeat above-mentioned modification step 1 time.
Molecular sieve diaphragm Electronic Speculum figure after the repairing as shown in Figure 5.From Fig. 5 as seen, form tangible hydrolysate in the intergranular pore channel on molecular screen membrane surface after the TEOS modification time is the repairing of 1h, compare with Fig. 4, Fig. 5 intergranular pore channel of molecular sieve membrane effectively reduces.
Three. the MFI molecular screen membrane after the repairing is investigated the separating property of paraxylene (PX)/ortho-xylene (OX) system:
MFI molecular sieve diaphragm after the repairing carries out separating property with device shown in Figure 1 to the PX/OX mixture and detects.Table 1 expression without the molecular screen membrane of repairing with modify 1h through TEOS and modify 1h for the second time after molecular screen membrane to the comparison of PX/OX mixture separation factor.
Table 1
Figure 7 shows that molecular screen membrane is to the permeability of the PX/OX Changing Pattern with the time of modification.By shown in Figure 7, along with the increase of the time of modification, the separation factor of PX/OX improves gradually, and the permeability of PX, OX descends gradually.Mainly be because, in the modification, because the source of modification molecular dynamics diameter is greater than molecular screen membrane intracrystalline duct, thereby the modification source is only in the intergranular pore channel place's hydrolysis of molecular screen membrane surface, hydrolysate has effectively stopped up defectives such as intergranular pore channel of molecular sieve membrane, has improved the selecting property selectivity of molecular screen membrane to PX.Yet along with the continuation of the time of modification prolongs, the molecular screen membrane surface forms the unbodied SiO of one deck
2Thin layer, this thin layer has not only stopped up intergranular pore channel but also stopped up the intracrystalline duct, thereby causes the selecting property selectivity of molecular screen membrane PX/OX significantly to descend.
The repairing of embodiment 2MFI molecular screen membrane reaches to be investigated the separating property of paraxylene (PX)/ortho-xylene (OX) system
One. the test of the MFI molecular screen membrane separating property before repairing
Detection method is with embodiment 1, and recording molecular screen membrane is 3.6 to the PX/OX separation.
Two. the repairing of intergranular pore channel of molecular sieve membrane
Be the modification source with TEOS and DMDS successively, adopt the method identical with embodiment 1 that the MFI molecular screen membrane is modified, the modification time in modification source is respectively 1h.MFI molecular screen membrane after twice modification and see Table 2 without repairing the separating property of MFI molecular screen membrane to PX/OX.
Table 2
Adopting the method identical with embodiment 1, is 2.3 to the PX/OX separation before recording the MFI molecular screen membrane and repairing, and adopts DMDS to repair twice, 1h at every turn, and the MFI molecular screen membrane that records after the repairing is respectively 5.5 and 10.8 to the PX/OX separation, sees Table 3.
Table 3
With the Electronic Speculum figure behind the DMDS repairing 1h as shown in Figure 6.As seen from Figure 6, after DMDS modified 1h, the DMDS hydrolysate mainly concentrated on intergranular pore channel place less relatively under the molecular screen membrane surface porosity layer.Mainly be because, compare with TEOS, DMDS has littler kinetic diameter, rests on less intergranular pore channel everywhere easilier, thereby intergranular pore channel of molecular sieve membrane is had better repairing effect.
The repairing of embodiment 4DDR molecular screen membrane and repairing front and back are to H
2/ SF
6The one pack system permeance property is investigated
DDR molecular screen membrane channel diameter is 3.6 * 4.4
About, apparently higher than H
2Molecular dynamics diameter (2.9
) and be lower than SF
6(be approximately 5.5
) the molecular dynamics diameter.According to the molecule screening mechanism, the DDR molecular screen membrane can be used for H
2And SF
6Separation.
One .DDR molecular screen membrane is repaired preceding to H
2/ SF
6The test of system one pack system permeance property:
With H
2/ SF
6As separation system, to investigate and modify front and back, the DDR molecular screen membrane is to H
2/ SF
6System one pack system permeance property.
As Fig. 3, chip DDR molecular screen membrane is made up of supporter 8-2 and molecular sieve rete 8-1, and the film effective area is 3.8cm
2Molecular sieve chip film before modifying is packed in the stainless steel permeator 6, adopts graphite gasket 9 sealings.Under 500 ℃, feed side pressure is kept 0.1MPa (gauge pressure), and per-meate side is a normal pressure, detects the infiltration gas flow by soap bubble flowmeter.Investigate molecular screen membrane respectively to H
2, SF
6The one pack system permeability, calculate H according to formula (1)
2/ SF
6Ideal selectivity, record modify before molecular screen membrane to H
2/ SF
6Ideal selectivity be 10.0.
Wherein, α
12Be H
2/ SF
6Ideal selectivity, P
1Be H
2Permeability, P
2Be SF
6Permeability.
The repairing of two .DDR type intergranular pore channel of molecular sieve membrane
With the inventive method DDR type molecular screen membrane is modified with TEOS, test membrane is to H then
2/ SF
6The single-component gas permeance property, result such as table 5 before and after repairing:
Table 5
Annotate:
aRepresent that per-meate side detects less than SF6 under this condition, the DDR type molecular screen membrane after repairing is described, SF6 can not see through fully, to H
2/ SF
6Selectivity reach infinitely great.
Claims (7)
1. the method for repairing and mending of intergranular pore channel of molecular sieve membrane, said molecular screen membrane comprises molecular sieve rete and support body layer, it is characterized in that modification step is as follows:
With the molecular screen membrane of the cleaning surfaces container of packing into, and permeator become the film side of isolating fully and support two Room, side; With silane is decorating liquid, and the end of decorating liquid from the film side room advanced to pump into, and the other end outflow from the film side room is constantly flow through decorating liquid from face; Meanwhile, the end of deionized water from the supporter side room pumped into, the other end outflow from the supporter side room is constantly flow through deionized water from supporting body surface; Above modification continues 0.5～3h, and molecular screen membrane is taken out in termination of pumping, puts into the baking oven inner drying, lowers the temperature behind 450～500 ℃ of sintering 4～5h in Muffle furnace then.
2. the method for repairing and mending of intergranular pore channel of molecular sieve membrane according to claim 1 is characterized in that said sintering heats up and the speed of cooling is 1～2 ℃/min.
3. the method for repairing and mending of intergranular pore channel of molecular sieve membrane according to claim 1, the rete that it is characterized in that said molecular screen membrane are the duct size 2.8～
Between the molecular sieve rete of any type.
4. the method for repairing and mending of intergranular pore channel of molecular sieve membrane according to claim 2, it is characterized in that said hydride modified liquid be average kinetic diameter greater than
And organosiloxane greater than the molecular screen membrane intracrystalline duct of being repaired.
5. the method for repairing and mending of intergranular pore channel of molecular sieve membrane according to claim 4 is characterized in that said hydride modified liquid is tetraethoxysilane, tetramethoxy-silicane or dimethyldimethoxysil,ne.
6. the method for repairing and mending of intergranular pore channel of molecular sieve membrane according to claim 4 is characterized in that mending course repeats 1-2 time.
7. according to the method for repairing and mending of claim 1 or 2 or 3 or 4 or 5 or 6 described intergranular pore channel of molecular sieve membrane, the supporter pattern that it is characterized in that said molecular screen membrane is chip, tubular type or doughnut supporter.
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| CN103551040A (en) * | 2013-11-15 | 2014-02-05 | 中国海洋石油总公司 | Online repairing method of NaA molecular sieve membrane |
| CN107638808A (en) * | 2017-10-23 | 2018-01-30 | 南京工业大学 | A kind of method of ultra-thin two-dimension nano material repairing molecular screen membrane defect |
| CN110902691A (en) * | 2019-11-25 | 2020-03-24 | 北京化工大学 | Hydrophobic modification method for Y-type molecular sieve |
| CN112337320A (en) * | 2019-08-08 | 2021-02-09 | 中国石油天然气股份有限公司 | Sealing method of carbon molecular sieve membrane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343067B (en) * | 2008-09-04 | 2010-11-10 | 天津大学 | Method for renovating molecular sieve membrane defection by means of liquid-liquid interfacial chemical liquid deposition |
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| CN103551040B (en) * | 2013-11-15 | 2015-06-24 | 中国海洋石油总公司 | Online repairing method of NaA molecular sieve membrane |
| CN107638808A (en) * | 2017-10-23 | 2018-01-30 | 南京工业大学 | A kind of method of ultra-thin two-dimension nano material repairing molecular screen membrane defect |
| CN107638808B (en) * | 2017-10-23 | 2019-10-15 | 南京工业大学 | A kind of method of ultra-thin two-dimension nano material repairing molecular screen membrane defect |
| CN112337320A (en) * | 2019-08-08 | 2021-02-09 | 中国石油天然气股份有限公司 | Sealing method of carbon molecular sieve membrane |
| CN110902691A (en) * | 2019-11-25 | 2020-03-24 | 北京化工大学 | Hydrophobic modification method for Y-type molecular sieve |
| CN110902691B (en) * | 2019-11-25 | 2021-07-20 | 北京化工大学 | Hydrophobic modification method for Y-type molecular sieve |
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