CN1262339C - New type nano SiO2 separation membrane and preparation method - Google Patents
New type nano SiO2 separation membrane and preparation method Download PDFInfo
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- CN1262339C CN1262339C CN 200410017206 CN200410017206A CN1262339C CN 1262339 C CN1262339 C CN 1262339C CN 200410017206 CN200410017206 CN 200410017206 CN 200410017206 A CN200410017206 A CN 200410017206A CN 1262339 C CN1262339 C CN 1262339C
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Abstract
The present invention relates to a nano amorphous metal oxide SiO2 separation membrane used for water/organic matter systems and a preparation method thereof. The existing inorganic separation membrane loads an A type zeolite molecular sieve membrane on a porous carrier, the preparation processes are complicated and have high cost, and chemical and thermal stability of high polymer separation membranes is poor. Dense nano amorphous SiO2 particles of the separation membrane of the present invention are prepared by an LTCVD method, volatilizable organic or inorganic silicide precursors are deposited on a porous ceramic surface under catalyst action. Abundant Si-OH on the membrane surface makes the membrane have the characteristic of prior penetration of water, and the membrane is effectively used for dewatering organic matter/ water systems. Meanwhile, the silylation or the coupling graft reaction of the surface Si-OH can adjust the hydrophilic or hydrophobe properties of the membrane so as to change separation characteristics.
Description
Technical field
The invention belongs to technical field of function materials, be specifically related to inorganic separating film material of a kind of novelty and preparation method thereof.The silicon hydroxyl (Si-OH) that this separation membrane surface is abundant is to hydrone (H
2O) have preferential selectivity, can be used for branch dried up/organic-compound system in a spot of water, be a kind of hydrophilic membrane of function admirable.
Background technology
Two thing phase spaces are separated and make it again connect each other, the intermediate medium that transmission courses such as quality, energy can take place is called film (membrane or film).According to the difference of film composition material, it can be divided into organic film, inoranic membrane, organic/inorganic composite membrane etc.Inoranic membrane high high-temp stability good (use of organic film generally is no more than 423K), chemical resistance of concrete and antimicrobial degraded, easy cleaning, withstand voltage height and the good mechanical stability (G.Saracco of falling, etc., J.Membrane Sci., 95,105 (1994)), has more wide application prospect than organic polymer film.Inoranic membrane can make separation process realize (being generally pervaporation) under situation about not undergoing phase transition, significantly energy savings, simplification technological process and operation, and development in nearly ten years is very fast.Membrane material is applied to catalysis, and catalytic reaction and separation process are combined, and obtains conversion ratio and the selectivity higher than thermodynamical equilibrium.But preparation difficulty, difficulty are accomplished scale production, higher development and the application thereof that has restricted inoranic membrane of cost.Existing abroad multiple commercial inoranic membrane, but technically still there are a lot of weak points in it and still do not have commercial inorganic separating film (except the ceramic-film tube micro-filtration membrane of porous) at present.
Zeolite molecular sieve film has with the aperture of molecular dimension sizableness and homogeneous, ion-exchange performance, high-temperature thermal stability performance, good shape selective catalysis performance, easily be modified, have advantage such as the zeolite of number of different types and structure is available, be that desirable film separates and the film catalysis material, once be considered to a revolutionary breakthrough in inoranic membrane field, the preparation of especially directed zeolite molecular sieve film becomes the focus of research in recent years.Zeolite molecular sieve film separates and catalytic reaction, mainly utilizes the rule that zeolite molecular sieve itself had and the pore passage structure of size homogeneous, and its prerequisite is that zeolite crystal must be continuous (the crystal adhesion is good), free of pinholes, free from flaw.In addition, because zeolite crystal has anisotropic characteristics, the control crystal is all extremely useful for film separation, film catalysis, film sensing etc. at the oriented growth of carrier surface.And crystal has randomness in the carrier surface growth, and the control crystal is often very strict along the preparation condition of certain orientation at carrier surface, preferential growth.Because zeolite molecular sieve film all has very strict dependence to synthesis condition, used carrier, initiation material etc. in preparation process; synthetic film is easy to generate crack and pin hole; the scale preparation that the randomness that poor repeatability, zeolite crystal are grown on carrier etc. has restricted zeolite molecular sieve film to a great extent with and in the application and development in fields such as catalysis, separation.The perforated membrane of this densification of zeolite molecular sieve film, its separating mechanism is as parallel diffusion (N.Nishiyama, K.Ueyama, M.Matsukata, AIChE J., 43,2724 (1997)), Maxwell-Stefan model (J.M.Graaf, F.Kapteijn, J.A.Moulijn, AIChE J., 45,497 (1999)), adsorption and diffusion model (M.Nomara, T.Yamaguchi, S.Nakao, J.Membrane Sci., 144,161 (1998)) all be that intracrystalline hole (intracrystalline pores) with zeolite plays a major role to separation process and is theoretical foundation etc..Speed by intracrystalline hole diffusion depends primarily on the distance that molecule passes through, and because of molecule very slow in the diffusion process in intracrystalline hole, so permeation flux is very limited.
SiO
2Film is the focus that people pay close attention to and study always.Its preparation method is easier, cost is low, is mainly used in the photoelectric material of function admirable.Prepare the controlled porous in aperture (or mesoporous) silica (porous silica) or silicon oxide film ([1] A.Carati, G.Ferraris, M.Guidotti with the different templates agent, G.Moretti, R.Psaro, C.Rizzo, Catal.Today, 77 (4), 315 (2003); [2] N.Nishiyama, S.Tanaka, Y.Egashira, Y.Oku, K.Ueyama, Chem.Mater., 15 (4), 1006 (2003); [3] K.Yu, B.Smarsly, C.J.Brinker, Adv.Funct.Mater.13 (1), 47 (2003); [4] J.T.Jiu, K.Kurumada, M.Tanigaki, Mater.Chem.Phys., 78 (1), 177 (2003); [25] A.W.Xu, J.C.Yu, Y.P.Cai, H.X.Zhang, L.Z.Zhang, J.Chem.Soc., Chem., Commun., (15), 1614 (2002)), can obviously increase the surface area of film.Preparation SiO
2The silicon source that film is commonly used is ethyl orthosilicate (TEOS), and used catalyst can be divided into acidic catalyst (as H
2SO
4, HCl etc.) or base catalyst (as NaOH, NH
3Water etc.).The preparation SiO that is reported on the document
2The method of film mainly contains sol-gel process (sol-ge1) ([1] M.A.Fardad, J.Mater.Sci, 35,1835 (2000); [2] R.Sch fer, M.Noack, etc., Separation and Purification, 25,3 (2001); [3] Y.Liu, H.Chen, etc., Journal of Sol-Gel Science and Technology, 25,95-101,103-111 (2002); [4] P.T.Gilmar, A.S.Oliveira, etc., Journal of Non-Crystalline, 273,124 (2000); [5] Y.Miao, S.N.Tan, Analytic Chimica Acta, 437,87 (2001); [6] H.H.Yu, H.B.Wu, etc., Acta Phys.-Chim.Sin., 17 (12), 1057 (2001) (in Chinese)) and chemical vapour deposition technique (CVD) ([1] K.Kurosawa, N.Takezoe, etc., Applied Surface Science, 168,37 (2000); [2] K.Kamimura, D.Kobayashi, etc., Applied SurfaceScience, 84,346 (2001); [3] N.Takahashi, M.Hoshogi, etc., J.Mater.Chem., 12,719 (2002); [4] Y.Chung, U.K.Hyo, W.R.Shi, J.Electr.Soc., 148 (10), C679 (2001)) etc.
Larbot (A.Larbot, etc., J.Membrane Sci., 44,289 (1989)) describes in detail with sol-gel process and prepares micropore SiO
2The technical process of film.SiO
2Colloidal sol with the silicate preparation of solubility, uses acid to regulate the pH value of silicate usually.In this method, poly-silicic acid is generated through polycondensation and polymerization by silicate, grows up into the colloidal solid of 1～100mm then.Therefore need to make it stable with special method.Change studies show that collosol stability influences by pH, the pH value forms gel rapidly between 4～8, and the pH value then helps particulate and grows up between 8～11.
Chemical vapour deposition technique is a method most important and commonly used in the Film forming method, its cardinal principle is to constitute one or more compounds, the elementary gas supply carrier that needs element containing, and prepares desired film by the chemical reaction of gas phase action on carrier surface.Chemical vapour deposition reaction must satisfy following three conditions: under (1) depositing temperature, reactant must have sufficiently high vapour pressure; (2) product except that the deposit of needs be solid-state, all the other all must be gaseous states; (3) sedimental vapour pressure is enough low, carries out maintaining on the carrier of heating in the process in whole deposition reaction guaranteeing.The process of chemical vapour deposition technique system film generally includes following three steps: (1) reaction species spreads in carrier surface and hole; (2) reactant reacts in carrier surface or hole; (3) solid product deposits on carrier surface and hole wall, and gaseous product then diffuses out.Ethyl orthosilicate (TEOS) is that the CVD method prepares SiO
2The raw material that film is the most frequently used.
A.W.Verkerk (A.W.Verkerk, P.van Male, M.A.G.Vorstman, J.T.F.Keurentjes, J.Membrane Sci., 193,227 (2001)) etc. robot system has been studied the amorphous silica film divides dried up (dehydration) to the isopropanol system process, in theory match various conditions, as temperature, pressure, material liquid proportioning etc. to the pervaporation flux and optionally the influence.Amorphous silica film used in the article has high permeation flux and high selectivity to the isopropanol system, but the structure of its preparation method, film and rerum natura sign there is no report.
Our invention is a kind of nanometer amorphous oxide diffusion barrier and low cost thereof, nontoxic pollution-free, simply preparation and method of modifying of being carried on the porous carrier, and this film has good separating property to organic matter/aqueous systems.The abundant active Si-OH in film surface is modified easily, to regulate hydrophilic/hydrophobic performance, separation selectivity and the permeation flux etc. of diffusion barrier, to be used for the separation of different systems.This diffusion barrier is applicable to the dehydration of various organic matters/aqueous mixtures system, to effective especially with the organic dehydration of water formation azeotropic mixture.The mechanical strength height of this inorganic separating film, heat endurance and chemical stability are good, anti-strong acid corrosion.Therefore, also be applicable to hyperfiltration to saliferous with contain the purified treatment that aqueous acid carries out desalination depickling processing and saliferous acid-bearing wastewater.Simultaneously, the low temperature chemical vapor deposition method (LTCVD) that we invented also can be used to prepare the preparation for other metal oxide film of presoma such as the organic metal ester class that is easy to gasify and metal halide under cryogenic conditions, as Al
2O
3Film, TiO
2Film, ZrO
2Film etc.
Summary of the invention
The objective of the invention is to propose a kind of permeation flux height, selectivity is good, inorganic separating film of low cost of manufacture and preparation method thereof.
The inorganic separating film that the present invention proposes is to be carrier with the porous ceramics, under the catalyst existence condition, and the nanometer amorphous metal oxide S iO that obtains by low temperature chemical vapor deposition
2Film.This film has good separating property to organic matter/aqueous systems.There is abundant active Si-OH on the film surface, is modified easily, thus the hydrophilic/hydrophobic performance that can regulate diffusion barrier, separation selectivity and permeation flux etc. are for use in the separation of different systems.
Above-mentioned nanometer amorphous metal oxide S iO
2The preparation method of film is: is in the acid or aqueous slkali catalyst of 5%-35% with cellular ceramic substrate in concentration, floods 6-24 hour, takes out dry; To insert the gas-phase reaction device through pretreated carrier, and carry out the gas phase catalysis deposition in organic or inorganic metal oxide precursor steam, depositing temperature is 100-250 ℃, and the time is 6-24 hour; With post-depositional carrier washing and oven dry, roasting again, temperature is 200-600 ℃, the time is 1-6 hour, can make nanometer amorphous metal oxide S iO
2Film.Because depositing temperature is 100-250 ℃, so claim that this method is low temperature chemical vapor deposition method (LTCVD).
In the said method, used cellular ceramic substrate can be α-Al
2O
3, cordierite, cellular glass, porous stainless steel etc., the aperture of porous carrier is 50nm-10 μ m.
In the said method, the immersion condition of porous ceramics in catalyst is: temperature 10-30 ℃, pickup is 1-5wt% (is the amount of impregnated catalyst in the porous ceramics, is weight percentage).
In the said method, used catalyst can be dissimilar and acid (as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid etc.) concentration, or alkali is (as NaOH, KOH, quaternary ammonium base, NH
4OH etc.).Used metal oxide precursor silicon source can be different silicate class or halosilanes class, as methyl silicate, ethyl orthosilicate, butyl silicate, trim,ethylchlorosilane, trichlorosilane etc.
The prepared nanometer SiO of the present invention
2Film, its metal oxide are the amorphous state particle.
Nanometer SiO provided by the present invention
2The feature of separation membrane material can characterize with the following method:
1. powder x-ray diffraction (XRD).This material is the nanometer amorphous Si O of deposition one deck densification on carrier
2Film in the powder x-ray diffraction spectrum, can provide the diffraction maximum of this amorphous substance about 20 ° (2 θ), the crystalline phase X-ray diffraction peak relative intensity of original vector obviously descends, and characterizes the generation of amorphous oxide with this.
2. reflection absorption ftir spectroscopy.Because nanometer amorphous Si O
2Be attached on the porous carrier, can only determine some group by its surperficial reflective infrared signal, as T-O-T, T-OH etc. to verify the material and the state thereof of the amorphous metal oxide that the surface forms.
3.EDX。By elementary analysis contrasts such as film and original vector surface Si, Al, O, determine to be deposited on the chemical composition of film surface metal oxide.
4. ESEM (SEM).Relatively intuitively observe particle size, compactness extent and the thickness thereof of formed nanometer amorphous metal oxide on carrier.
5. pervaporation experiment.Measure the pervaporation of the prepared nanometer amorphous metal of said method oxidation film, can obtain the data of its pervaporation flux and separation selectivity respectively different organic matter/aqueous systems.
Accompanying drawing 1,2 is respectively tabular cordierite carrier and α-Al
2O
3Carrier with at its Surface L TCVD deposition SiO
2XRD figure spectrum contrast behind the film.As can be seen, vapour deposition SiO
2After carrier, the intensity of its XRD figure spectrum diffraction maximum reduces greatly, illustrates that the surface is by the unbodied SiO of one deck
2Cover.But because the SiO of vapour deposition
2Layer thickness very little (being about 2 μ m), and its main component is the nanometer amorphous particle, the main diffraction maximum of carrier crystalline phase still exists, but the diffraction maximum of this amorphous substance can show about 20 ° (2 θ).
Accompanying drawing 3,4 is respectively cordierite carrier and α-Al
2O
3Carrier and at its Surface L TCVD deposition SiO
2The reflection absorption ftir spectroscopy of sample contrast behind the film.Infrared absorption peak (the 1100cm that tangible Si-O-Si asymmetric stretching vibration is arranged on its surface as can be seen,
-1About), the outer residual SiO of film
2Product is then at 3400cm
-1Near the infrared absorption peak of tangible O-H stretching vibration is arranged, the such catalysate of this explanation is the amorphous Si O that contains a large amount of Si-OH
2
Accompanying drawing 5 is cordierite carrier and load SiO thereon
2The stereoscan photograph of film.Fig. 5 a, 5b are respectively cordierite carrier surface and cross section, connect mutually between the inhomogeneous and duct of the pore-size distribution of carrier as can be seen.Fig. 5 c is cordierite carrier vapour deposition SiO
2Surface behind the film.As can be seen, on the carrier uneven macropore basically by nanometer SiO
2Cover.Can know that from the experiment of pervaporation these cracks and carrier do not connect, otherwise this film just can not produce separating effect to alcohol/aqueous systems.Fig. 5 d is SiO
2The cross section of film this shows, prepared SiO
2What film was firm loads on the cordierite carrier, and its thickness is about 2 μ m.
Accompanying drawing 6 is α-Al
2O
3Carrier and load SiO thereon
2The stereoscan photograph of film.Fig. 6 a, 6b are respectively α-Al
2O
3Carrier surface amplifies the electromicroscopic photograph of different multiples, and its pore-size distribution is than cordierite even compact (average pore size 50nm) α-Al as can be seen
2O
3Carrier vapour deposition SiO
2Electromicroscopic photograph behind the film (Fig. 6 c) shows that post-depositional film presents nanometer SiO sheet, that connect densification through roasting
2, do not form big crack.The pervaporation experiment also shows, loads on α-Al
2O
3The SiO of carrier
2Film is fine and close more, and its permeation flux is littler, and is also higher to the selectivity of water in alcohol/aqueous systems; Fig. 6 d is SiO
2The electromicroscopic photograph in film cross section, the fine and close SiO uniformly of its surface coverage one deck as can be seen
2
Table 1 is carrier and film surface EDX data thereof.As can be seen, cordierite carrier surface Si/Al is 1.55, carrier surface SiO
2The Si/Al of film is 3.41, and the Si constituent content obviously increases, and the Si/O ratio is 0.48, is 87.34% (Si+O); α-Al
2O
3Carrier surface Si/Al ratio is 0.007, and carrier surface SiO
2The Si/Al ratio of film is 7.58, and Si content increases, and the Si/O ratio is 0.41, (Si+O) is 95.93%.The Si constituent content of this explanation through vapour deposition caudacoria surface obviously improves, and the Si/O ratio approaches 0.50, proves that the product that generates at the carrier outer surface is amorphous Si O
2
Table 2 is carrier and SiO
2Film is to the pervaporation result of different systems.This pervaporation experiment, preliminary proof: 1) with cordierite and α-Al
2O
3Be carrier, can prepare densification, uniform SiO by the LTCVD method
2Film.Because used α-Al
2O
3Carrier is littler than the average pore size of cordierite, pore size distribution is even, SiO
2The duct of the more effective filling carrier of granule energy forms dense film on its surface, makes its permeation flux littler, and selectivity compares higher; 2) by the prepared SiO of LTCVD
2Film has penetrated preferably to the glassware for drinking water in the different systems, is the hydrophilic inorganic film.
Description of drawings
Fig. 1 is a powder X-ray RD spectrogram.A. cordierite carrier wherein, b. is carried on the SiO on the cordierite carrier
2Film.
Fig. 2 is a powder X-ray RD spectrogram.A. α-Al wherein
2O
3Carrier, b. is carried on α-Al
2O
3SiO on the carrier
2Film.
Fig. 3 is the reflection absorption ftir spectroscopy spectrogram.A. cordierite carrier wherein, b. is carried on the SiO on the cordierite carrier
2Film, c.SiO
2Powder.
Fig. 4 is the reflection absorption ftir spectroscopy spectrogram.A. α-Al wherein
2O
3Carrier, b. is carried on α-Al
2O
3SiO on the carrier
2Film.
Fig. 5 is cordierite and SiO
2The SEM photo of film.Wherein, a. cordierite carrier surface, b. cordierite carrier cross section, c. is carried on the SiO on the cordierite carrier
2The film surface, d. is carried on the SiO on the cordierite carrier
2The film cross section.
Fig. 6 is α-Al
2O
3Carrier and SiO
2The SEM photo of film.A wherein, b. α-Al
2O
3Carrier surface, c. is carried on α-Al
2O
3SiO on the carrier
2The film surface, d. is carried on α-Al
2O
3SiO on the carrier
2The film cross section.
The specific embodiment
The invention is further illustrated by the following examples:
Embodiment 1: tabular cordierite carrier is soaked drying at room temperature 6hr behind the 24hr in 5%HCl solution, place the 200 ℃ of vapour deposition 24hr of device that fill TEOS.
Embodiment 2: with tabular α-Al
2O
3Carrier soaks drying at room temperature 6hr behind the 24hr in 5%HCl solution, place the 200 ℃ of vapour deposition 24hr of device that fill TEOS.
Embodiment 3: with tabular cordierite carrier at 25%H
2SO
4Drying at room temperature 8hr behind the immersion 10hr places the 200 ℃ of vapour deposition 24hr of device that fill trim,ethylchlorosilane in the solution.
Embodiment 4: with tabular α-Al
2O
3Carrier is at 25%H
2SO
4Drying at room temperature 4hr behind the immersion 6hr places the 100 ℃ of vapour deposition 24hr of device that fill down methyl silicate in the solution.
Embodiment 5: tabular cordierite carrier is soaked drying at room temperature 6hr behind the 24hr in 10%HCl solution, place the 200 ℃ of vapour deposition 6hr of device that fill TEOS.
Embodiment 6: with tabular cordierite carrier at 10%H
2SO
4Drying at room temperature 6hr behind the immersion 24hr places the 200 ℃ of vapour deposition 24hr of device that fill TEOS in the solution.
Embodiment 7: with tabular cordierite carrier at 35%H
2SO
4Drying at room temperature 6hr behind the immersion 8hr places the 180 ℃ of vapour deposition 24hr of device that fill positive silicic acid propyl ester in the solution.
Embodiment 8: with tabular cordierite carrier at 20%H
3PO
4Drying at room temperature 6hr behind the immersion 24hr places the 180 ℃ of vapour deposition 6hr of device that fill TEOS in the solution.
Embodiment 9: tabular cordierite carrier is soaked drying at room temperature 6hr behind the 12hr in 35%NaOH solution, place the 250 ℃ of vapour deposition 18hr of device that fill trichlorosilane.
Embodiment 10: with dash board shape cordierite carrier at 5%NH
3H
2Drying at room temperature 6hr behind the immersion 24hr places the 200 ℃ of vapour deposition 24hr of device that fill TEOS in the O solution.
Embodiment 11: with tabular cordierite carrier at 5%H
2SO
4Drying at room temperature 6hr behind the immersion 24hr places the 200 ℃ of vapour deposition 12hr of device that fill TEOS in the solution.
The film of method for preparing all shows amorphous nanometer SiO
2Architectural feature.
Table 1 EDX is to carrier and film surface-element content analysis
| Carrier or film | Si content (%) | Al content (%) | O content (%) | The Si/Al ratio | The Si/O ratio | The Al/O ratio |
| Cordierite SiO 2Film | 19.39 28.47 | 12.54 8.35 | 60.39 58.87 | 1.55 3.41 | 0.32 0.48 | 0.21 0.15 |
| α-Al 2O 3 SiO 2Film | 0.28 27.73 | 42.14 3.66 | 57.56 68.20 | 0.007 7.58 | 0.005 0.41 | 0.73 0.05 |
25 ℃ of following SiO of table 2
2Film is to different system pervaporation experimental datas
| Film | 41.2% isopropyl alcohol/58.8% aqueous systems | 5% ethanol/95% aqueous systems | The 1# sample | The 2# sample | ||||
| Flux | Selectivity | Flux | Selectivity | Flux | Selectivity | Flux | Selectivity | |
| Cordierite-SiO 2Film α-Al 2O 3-SiO 2Film | 42.0 72.0 | 19.48 20.31 | 2.17 0.50 | 17.44 877.3 | 1.21 0.042 | 5212 100％H 2O | 3.25 0.248 | 0.709 100％H 2O |
Illustrate: 1, the computational methods of permeation flux are J (kg/m in the form
2Hr)=amount of liquid (kg)/membrane area (m of seeing through
2) * see through the time (hr), its unit is kg/m
2Hr;
2, selectivity is a selectivity to water in the system in the form, and its computational methods are α=(Y
A/ Y
B)/(X
A/ X
B) (Y, X are respectively the weight fractions of infiltration product and raw material in the formula, and A is a penetrated preferably component in the binary mixture);
3, wt (H in the 1# sample in the form
2O)=7.23%, water/methyl acetate ratio is 0.078; 2# sample wt (H
2O)=13.68%, water/methyl acetate ratio is 0.159.
Claims (9)
1, a kind of inorganic separating film is characterized in that for being carrier with the porous ceramics, under the catalyst existence condition, and the nanometer amorphous metal oxide S iO that obtains by the low temperature chemical vapor deposition
2Film; The step of low temperature chemical vapor deposition described here is as follows: is in the acid or aqueous slkali catalyst of 5%-35% with cellular ceramic substrate in concentration, floods 6-24 hour, takes out dry; To insert the gas-phase reaction device through pretreated carrier, and carry out the gas phase catalysis deposition in organic or inorganic metal oxide precursor steam, depositing temperature is 100-250 ℃, and the time is 6-24 hour; With post-depositional carrier washing and oven dry, roasting again, temperature is 200-600 ℃, the time is 1-6 hour.
2, inorganic separating film according to claim 1 is characterized in that described metal oxide is the amorphous state particle.
3, a kind of preparation method of inorganic separating film as claimed in claim 1 is characterized in that concrete steps are as follows: is in the acid or aqueous slkali catalyst of 5%-35% with cellular ceramic substrate in concentration, floods 6-24 hour, takes out dry; To insert the gas-phase reaction device through pretreated carrier, and carry out the gas phase catalysis deposition in organic or inorganic metal oxide precursor steam, depositing temperature is 100-250 ℃, and the time is 6-24 hour; With post-depositional carrier washing and oven dry, roasting again, temperature is 200-600 ℃, the time is 1-6 hour, can make nanometer amorphous metal oxide S iO
2Film.
4, the preparation method of inorganic separating film according to claim 3 is characterized in that described metal oxide precursor silicon source is silicate class or halosilanes class.
5, the preparation method of inorganic separating film according to claim 4 is characterized in that described silicate class is methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, and described halosilanes class is trim,ethylchlorosilane, trichlorosilane.
6, the preparation method of inorganic separating film according to claim 3 is characterized in that described acid catalyst is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, and described base catalyst is NaOH, KOH, quaternary ammonium base, NH
4OH.
7, the preparation method of inorganic separating film according to claim 3 is characterized in that described porous carrier is a-Al
2O
3, cordierite, cellular glass, porous stainless steel.
8, the preparation method of inorganic separating film according to claim 3, the aperture that it is characterized in that described porous carrier is 50nm-10 μ m.
9, the preparation method of inorganic separating film according to claim 3 is characterized in that described catalyst soakage condition is:
(1) dipping temperature is 10-30 ℃;
(2) pickup is 1-5wt%.
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| KR100814571B1 (en) * | 2004-03-17 | 2008-03-17 | 가부시키가이샤 붓산 나노테크 겐큐쇼 | Separation membrane |
| CN100358616C (en) * | 2006-05-30 | 2008-01-02 | 天津大学 | Process for preparing silicon separating films with specialized selectivity to natural products |
| CN101502807B (en) * | 2009-03-05 | 2011-06-01 | 天津大学 | Modified nano molecular sieve catalyst for cracking endothermic hydrocarbon fuels and preparation method |
| CN101856595B (en) * | 2010-06-10 | 2012-12-19 | 南京工业大学 | Metal-doped organic-inorganic composite SiO2Method for producing film |
| CN102641666A (en) * | 2012-04-28 | 2012-08-22 | 常州大学 | Porous nano silicon ion separation film |
| CA2911398C (en) * | 2013-06-12 | 2017-08-08 | Toyo Tire & Rubber Co., Ltd. | Separation membrane for treating acid gas-containing gas, and method for manufacturing separation membrane for treating acid gas-containing gas |
| CN106823843B (en) * | 2017-01-13 | 2019-03-22 | 常州大学 | A kind of regulation method and its application of silica membrane aperture |
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