AU2001273734B2 - Improved silica membranes and process of production thereof - Google Patents
Improved silica membranes and process of production thereof Download PDFInfo
- Publication number
- AU2001273734B2 AU2001273734B2 AU2001273734A AU2001273734A AU2001273734B2 AU 2001273734 B2 AU2001273734 B2 AU 2001273734B2 AU 2001273734 A AU2001273734 A AU 2001273734A AU 2001273734 A AU2001273734 A AU 2001273734A AU 2001273734 B2 AU2001273734 B2 AU 2001273734B2
- Authority
- AU
- Australia
- Prior art keywords
- teos
- membranes
- ethanol
- sol
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Description
WO 01/93993 PCT/AU01/00692 "IMPROVED SILICA MEMBRANES AND PROCESS OF PRODUCTION
THEREOF"
THIS INVENTION relates to a method of producing weakly branched silica membranes by a two-step catalysed hydrolysis process.
BACKGROUND TO THE INVENTION Molecular membranes, otherwise known as molecular sieves, are widely known in their use to separate mixtures of gas. Weakly branched molecular sieving silica membranes are of particular interest for use in fuel cells and petrochemical applications for their ability in selectively separating hydrogen and helium from gas mixtures. Environmental applications are also possible with these types of membranes to separate and enrich the methane (CH 4 component from landfill gas and biogas.
Ideally to fulfil these types of uses the membranes need to have both good pore size control and high permselectivity for hydrogen and helium, that is molecules with a kinetic diameter of less than 3.4A.
Sol-gel reaction process are widely employed to form molecular sieves. The use of sol-gel reaction processes are favoured for the formation of microporous dimensions, that is pore size less than 20 A, in a molecular sieve. Brinker C. J. Scherer G. W. ("Sol-Gel Science: the physics and chemistry of the sol gel processing", Academic Press, San Diego, USA (1990)), outline that polymeric silicate gels are often synthesised by hydrolysing monomeric tetrafunctional alkoxide precursors, using a mineral acid (HCI) or a base (NH 3 as a catalyst. The hydrolysis is then followed by the condensation reactions, an alcohol WO 01/93993 PCT/AU01/00692 2 condensation and/or a water condensation. The resultant product is the formation of siloxane bonds (Si-O-Si), silanols (Si-OH), alcohol and water, as outlined in the equations below.
=Si-OR H 2 -Si-OH ROH -Si-OR HO-Si Si-O-Si ROH =Si-OH HO-Si =Si-O-Si H 2 0 The formation used in the sol-gel process must be finely tuned in order to control the pore size to molecular dimensions. The disadvantages of this process is that the matrix of the weakly branched silica film may be so dense that it results in no or very low permeation of gases.
Raman and Brinker, ("Organic template approach to molecular sieving silica membranes", Journal of Membrane Science, 105, 273-279 (1995)), used tetraethylorthosilicate (TEOS) and methyltriethylsilane (MTES), absolute ethanol (EtOH), distilled water and HCI as the catalyst, to produce intermediate film layers. Subsequently, they used several layers of non-hydrolysed TEOS to produce the top film. Raman and Brinker produced membranes with good poor size control for CO, and
CH
4 separation, but with low permselectivity to He/CO 2 The use of HCI as a catalyst in the preparation of the MTES/TEOS intermediate layer, Raman and Brinkler does not provide for fine control over the pore size.
Kusakabe Sakamoto Sale and Morooka ("Pore structure of silica membranes formed by a sol-gel technique using tetraethyloxysilane and alkyltriethyloxysilanes" Sep. and Pur. Tech., 16, 139-146 (1999)), prepared templated membranes from TEOS and alkyltriethyloxysilianes. These membranes had reasonable pore size WO 01/93993 PCT/AU01/00692 3 control and higher permeation but lower permselectivities for molecules with a kinetic diameters less that 3.4A.
De Vos R. M. and Verweij H. ("Improved performance of silica membranes for gas separation", Journal of Membrane Science, 143, 37- 51, (1998)) produced membranes using a single step catalysed hydrolysis sol-gel process and calcined at 400°C, with high permeancance to indicating that the permselectivity ability of these membranes is low for H 2 and CO 2 permeation. However when these membranes where calcined at 600 0 C the permselectivity for H 2 and CO 2 increased by tenfold. The increase in permselectivity is mainly caused by pore reduction due to heat treatment but it also reduces permeation of gases.
Another technique for producing silica membranes is through the use of chemical vapour deposition (CVD) process as outlined by Lin C. L., Flowers D. and Liu P. K. ("Characterisation of ceramic membranes II. Modified commercial membranes with pore size under 40A", Journal of Membrane Science, 92, 45-58, (1994)) and Wu J. C. Sabol Smith G. Flowers D. L. and Liu P. K. ("Characterisation of hydrogenpermselective microporous ceramic membranes", Journal of Membrane Science, 96, 275-287, (1994)). Ha H. Woo-Nam Hong S. A. and Lee W. ("Chemical vapour deposition of hydrogen-permselective silica film on porous glass support from tertraethylorthosilicate", Journal of Membrane Science, 85, 279-290, (1993)) and Tsapatsis M. and Gavalas ("Structure and aging characteristics of H 2 permselective SiO, Vycor membranes", Journal of Membrane Science, 87, 282-296, (1994)) used WO 01/93993 PCT/AU01/00692 4 chemical vapour deposition using vycor glass tubes as substrates. The membranes produced by chemical vapour deposition have high permeance for H 2
/N
2 and good separation capabilities for He/H 2 Chemical vapour deposition requires considerably more equipment and may be more expensive than film dip coating processes.
OBJECT OF THE INVENTION It is an object of the present invention to provide a two-step catalysed hydrolysis process for the production of weak branched silica molecular sieves with high permselectivity to hydrogen and helium, which overcomes or ameliorates one or more disadvantages of the prior art.
Further objects will be evident from the following description.
DISCLOSURE OF THE INVENTION In one form, although it need not be the only or indeed the broadest form, the invention resides in a method of producing weakly branched silica membranes coated onto a substrate using a two-step catalysed hydrolysis sol-gel process including: forming a tetraethylorthosilicate (TEOS)/ethanol solution; placing the TEOS/ethanol solution in an ice bath; forming an acid/water solution; adding the acid/water solution to the TEOS/ethanol solution to form a TEOS/ethanol/acid/water solution; refluxing the TEOS/ethanol/acid/water solution; preparing a two-step sol by adding water and nitric acid to the refluxed TEOS/ethanol/acid/water solution and initiating a two-step WO 01/93993 PCT/AU01/00692 sol-gel process; depositing a membrane film layer on a substrate from the two-step sol to form a substrate coated with weakly branched silica membranes.
In preference the TEOS/ethanol/acid/water solution prior to refluxing has a molar composition of 1.0 TEOS:3.8 ethanol:1.0 water:7.0 x nitric acid. Suitably the two-step sol would have a molar composition of 1.0 TEOS:3.8 ethanol:6.0 water:0.1 nitric acid.
The refluxing step is preferably carried out at approximately o0 for about 180 minutes in a water bath.
Suitably the substrate is prepared with one or more prime layers and/or one or more intermediate layers. Preferably the membrane is formed by coating the substrate with the two-step sol either with or without the prime and intermediate layers. In addition it is preferably that the substrate coated with the membrane is heat treated. The heat treatment step is suitable carried out at temperatures between 4000C and 600°C with an air flow of 100ml per minute. Preferably the heat treatment is carried out at about 5000C In another form the invention resides in a weakly branched silica membrane produced from the above two-step catalysed hydrolysis sol-gel process.
In preference, the weakly branched membrane has a pore an average size of less than 3A and a film thickness of between 0.1 and In yet another form, the invention resides in a method of selectively WO 01/93993 PCT/AU01/00692
G
separating hydrogen and helium from a gas mixture using a weakly branched silica membranes.
BRIEF DETAILS OF THE DRAWINGS To assist in understanding the invention, preferred embodiments will now be described with reference to the following figures in which FIG. 1A FTIR spectra of two-step membrane.
FIG. 1B FTIR spectra of single-step membrane.
FIG. 2A Permeance of single-step membrane to various gases as a function of temperature.
FIG. 2B Permeance of various membranes to CO2 as a function of temperature.
Hereinafter the term "single-step membrane" will be used to describe those membranes of the example that are produced by a single step catalysed hydrolysis sol-gel process. Similarly the term "two-step membrane" is used to describe those membranes of the example that are produced by the two-step catalysed hydrolysis sol-gel process of the invention.
DETAILED DESCRIPTION OF THE DRAWINGS In general, FIG. 1A and B show the FTIR spectra for the membranes produced in the Example and outlined in Table 1 by the twostep and a single-step catalysed hydrolysis process, respectively.
FIG. 2A and B show the permeance of two step and single step membranes to various gases as a function of temperature.
EXAMPLE
The membrane films are formed by a two-step catalyses hydrolysis WO 01/93993 PCT/AU01/00692 7 solution. The single step catalysed hydrolysis process and the resulting membranes are produced for comparison purposes. A range of membranes are synthesised and their formation and layering characteristics are outlined in Table 1. The top film layers of the J membranes are films produced from the two-step process, whilst the K membranes are produced from a mix of two-step films coated on the top of a single-step film and the S membranes are produced solely from the single-step films.
Two-step Catalysed Hydrolysis Process Tetraethylorthosilicate (TEOS) and absolute ethanol are placed in an ice bath. 1M nitric acid and distilled water is added dropwise to the TEOS/ethanol solution, with constant stirring. The resultant molar ratio of the respective reactants is 1 TEOS:3.8 ethanol:1 water:7xl0 4 M nitric acid. The solution is then refluxed with constant stirring at 60 0 C for 180 minutes in a water bath.
Additional water and nitric acid are added until a molar ratio of 1 TEOS:3.8 ethanol:6 water:0.1 nitric acid is achieved. This sol-gel process provides sols with reasonably low water:silica ratios which inhibit condensation reactions and produce a weakly branched system sol-gel.
Single step catalysed hydrolysis TEOS, absolute ethanol, 1M nitric acid and distilled water are mixed to form a molar ratio of 1.0 TEOS:3.8 nitric acid:0.1 water. The resultant solution is aged at 50°C in a temperature controlled oven for 0.
3 3t, which is equivalent to 33% of the time required to gel the single-step sol.
Dilution Both the two-step and single-step catalysed sols where volumetrically diluted to 1:19 with ethanol before forming membrane films.
WO 01/93993 PCT/AU01/00692 8 Dilution is used to obtain a suitable sol for substrate coating, that is forming films which do not have defects such as developing micro cracks during heat treatment.
Substrate The silica membranes are formed on a-alumina support substrates, 99.8% purity, 2cm thick and with an average pore size of 0.5-1 ,um and a porosity of 30%. The supports are smoothed using sandpaper, cleaned in ethanol and calcined up to 600 0 C for 4 hours. The calcining and subsequent cooling is carried out at a rate of 1°C per minute.
The support is then coated with either two layers of; a) modified Locron alumina solution (supplied by Bayer), diluted 1:4 in ethanol; or b) two layers of template sols and methyltriethyloxysilane (MTES) and tetraethylorthosilicate (TEOS) containing a x/y (MTES/TEOS) molar ratio, which is then calcined at temperature range of 400-600oC, and maintained at the desired temperature for 4 hours, with ramping and cooling down rates of 1 °C per minute.
Membrane deposition is achieved by dip coating the support into the diluted sol for a period of 60 seconds, and removing it at a rate of per minute. The dip coating is carried out in a clean cupboard to avoid dust affecting the membrane and increasing the risk of defects in the membrane.
The membranes are placed on the inside of a quartz glass tube, before being placed in a cylindrical furnace for heat treatment with an air flow at 100ml per minute.
Table 1 shows the layer compositions of membrane samples WO 01/93993 PCT/AU01/00692 9 produced and their respective heat treatment temperatures.
TABLE 1: Membrane synthesis including number of tvye and calcination temoerature.
layers, material Code Top layer Intermediate layer Prime layer J1 6 TS 500°C 2 10/90 a 600 0 C 2 LM 6000C J2 6 TS 500°C 2 10/90 a 600 0 C 2 LM 600 0
C
J4 5 TS 500°C 2 10/90 a 6000C 2 50/50 6000C 2 LM 6000C K1 2 TS 500 0 C 2 SS b 500 0 C 2 10190 a 600 0 C 2 LM 6000C K2 2 TS 5000C 2 SS b 5000C 2 10/90 a 6000C 1 LM 6000C K3 2 TS 5000C 2 SS b 5000C 2 10/90 a 6000C 1 LM 6000C K4 1 TS 500°C 1 SS b 500°C 2 10/90 600 0 C 2 LM 600 0
C
1 TS 500 0 C 1 SS b 500°C 2 10/90 a 6000C 1 LM 6000C S1 6 SS 400°C 2 1 0/ 90 b 400°C surface treatment (HNO 3 2L 4000C S2 6 SS 400°C 2 10/90 400°C surface treatment (HCI) 2L 400°C S3 6 SS 400°C 2 10/90b 400°C surface treatment (HCI) 2L 400°C S4 6 SS 4000C 2 10/90b 400°C surface treatment (HNO 3 2L 4000C 6 SS 400°C 2 10/90 550°C surface treatment (HNO 3 2L 400°C S6 6 SS 400°C 2 10/90" 550°C surface treatment (HNO 3 2L 400°C SS single step L= locron a aged for t. 0.04 at 500C TS two step LM locron modified sol-gel b aged for t, 0.25 at In each of the columns 2, 3 and 4 of Table 1 above, the first number is the number of layers present; the following part in the column is the composition of the layers being either a) the sol-gel process used, either two-step (TS) or single step b) the MTES/TEOS molar ratio (10/90 or 50/50), or c) whether the prime layer is locron or locron modified sol-gel followed by the calcination temperature for each of the layers. The layers are deposited and sequentially calcined. This means that the prime layer is deposited on the substrate support and then calcined after each subsequent film deposition.
WO 01/93993 PCT/AU01/00692 Characterisation of the membrane films produced in Table 1 A range of characterisation tests were carried out on the membranes produced in Table 1, including FTIR, NMR, permeation comparisons, permselectivity and determining the energy of mobility.
FTIR Spectra The FTIR spectra are shown in FIG. 1A and B. It can be seen from a comparison of FIG. 1A and B that the spectra show a similar structural evolution with the increase in temperature. The siloxane groups peak at approximately 1090cm- 1 becomes more prominent with an increase in temperature, for the two-step membranes above 500°C whilst for the single step membranes the shoulder becomes more predominant at above 400"C. The spectra also show a significant reduction in the formation of siloxane groups in the two-step membranes from the singlestep membranes.
NMR characterisation NMR spectra on the membranes produced in Table. 1 were carried out. The characterising features of the NMR spectra for the membranes of Table. 1 are summarised below in Table. 2.
Both the single and two-step membrane showed a high concentration of silanols (shown as Q 2 and Q 3 in the table), while siloxanes (Q 4 in the table) are in lower concentrations for the two-step membranes than in the single step membranes. This highlights the formation of a rather weaker branched system in the two-step process compared to the single-step.
WO 01/93993 WO 0193993PCT/AU01/00692 1 1 TABLE 2: Breakdown of NMR spectra for single and two-step membrane Sample QW peak centre* I Q 3 peak centre* I 2 peak centre ,I Temperature Area Area Area single step 400'C -110.8 25.92 -101.4 67.00 -91.68 1 7.08 single step -500TC -111.0 27.84 -101.6 63.26 -92.19 8.90 single step -600'C -111.1 31.49 -101.6 I61.74 -91.98 1 6.77 two step -400TC -110.9 23.44 -101.4 I69.16 -91.8 7.44 two step -500TC -110.4 23.78 -101.1 1 65.58 -91.84 10.64 two step -600TC -110.7 (25.75- -101.2 1 63.97 -91.7 10.56 *peak centres are in chemical shift units ppm.
Permeation Comparison The gas permeation of the sample membranes from Table 1 where measured for a range of temperatures and pressures, the results are outlined in Table 3, below.
TABLE 3: Typical permeance results is Membrane Gas Pressure 22 0 C 50 0 C 100 0 C 15000 (KPa) K1 He 200 4.74E-09 9,11IE-09 2.27E-08 3.90E-08 K3 H 2 300 5.26E-10 7.74E-10 1.43E-09 2.52E-09 K(1 002 300 7.38E-1 1 7.97E-1 1 1.01E-10 1.17E-10 K4 OH 4 300 3.68E-11I 4.06E-11I 4.38E-11I 6.37E-1 1 K3 02 300 6.36E-11I 7.07E-1 1 9.6E-1 1 K3 N 2 300 5.5E-11I 7.87E-1 1 Ji He 100 1.E-08 1.96E-08 3.51 E-08 5.09E-08 Ji H 2 100 3.28E-09 4.67E-09 9.74E-09 1.78E-08_ SI He 100 7.93E-09 1.75E-08 2.1IE-08 SI 002 100 7.09E-09 8.41 E-09 7.18E-09 S2 002 100 5.13E-09 3.64E-09 3.9E-09 4.13E-09 S6 C02 150 7.01E-10 1.2E-09 8.63E-10 14.89E-10 FIG. 2A shows the permeance of membrane J1 as a function of temperature. This figure shows the general trend that as temperature increases the permeance of the JI membrane to He, OH 4 and CO 2 WO 01/93993 PCT/AU01/00692 12 also increases.
FIG. 2B shows the permeance of a range of single and two-step membrane to CO 2 as a function of temperature. The single step membrane all increase in permeance for temperatures up to 100°C and then decrease. The significant difference between the single and twostep membranes is that the permeance of the two-step membranes for
CO
2 is an order of magnitude lower.
These permeation studies highlight that the two-step process produced films that have better pore size control for pores sizes less than 3.4A.
Permselectivity The permselectivity of the membranes of Table 1 are determined and represented below in Table 4. Table 4 also includes the ideal Knudsen separation factor for additional comparison. Having a permselectivity result higher than the Knudsen separation factor is considered a measure of the quality of a membrane. As all the results in Table 4 are higher than the corresponding Knudsen separation factor it can be concluded that all the membranes produced by both the single and two step processes are of high quality.
The Table. 4 indicates that the K and J membranes, produced by the two step catalysed process have a higher permselectivity for the gases with molecular kinetic diameters dk 3A, such as helium and hydrogen, and conversely lower permaselectivity for the gases with dk 3A, such as CO 2 02, Ar, N 2 and CH 4 The single step membranes all show the opposite trend with the poor permselectivity for the gases with molecular kinetic diameters dk 3A and higher permaselectivity for WO 01/93993 PCT/AU01/00692 13 the gases with dk 3A.
TABLE 4: Permselectivity He/H 2 He/CO, He/O 2 HelN, He/CH 4
H
2 CO, H 2
/CH
4
COICH
4 CO/Ar a* 1.41 3.32 2.83 2.65 2.00 4.69 2.83 1.66 1.05 K1 3.8-6.1 66-328 692 906 14-37 210 2.8 K2 1,9-50 296 59 K3 7.1-8.1 77-138 96-210 212-256 9.8-19 K4 2.5-5.0 34-98 303-312 13-26 61-81 3.2-3.5 5.5-6.0 121 21 J1 2.7-4.6 165 860 58 301 5.2 J2 336 511 41 63 1.5 S1 1.3-3.0 146 55 16 S2 2.1-6.7 6.1 17 34 S3 1.1 4.6 6.5 6.1 4.6 S4 2.2 148 283 130 16-19 S6 1.4-3.7 6.3-14 4.0-5.3 The membranes produced by the two-step catalysed hydrolysis process have been found to have extremely high separation factors for hydrogen and/or helium. For example the permselectivity of the two-step catalysed hydrolysis processed film produced separation rates of 860 (He/CH 4 whilst the single-step processed film had separation rates of 283. These results can be largely attributed to a higher pore control at the region of 3A due to a large contribution of the silanol groups (Q 2 and Q 3 species in Table Silanol groups collapse during film formation due to capillary stress this results in a finer pore control, as exhibited in the to the two-step membranes. Siloxane groups (Q 4 species in Table 2) stiffen the silica matrix opposing capillary stress resulting in slightly large pore size as exhibited by the single step membranes.
WO 01/93993 PCT/AU01/00692 14 Energy of Activation and Energy of Mobility The energy of activation and the energy of mobility (Em) for a range of gases is determined for the sample membranes formed in Table 1, are shown in Table 5. It can be seen from Table 5 that the energy of mobility and activation for the two step membranes is higher than the single step films. This correlates directly to the respective pore sizes of the membranes, that is the mobility is lower for the larger pores of the single step membranes and higher for the smaller pores of the two-step membranes. This reinforces the ability of the two-step process to control pores size at less than 3.4A.
TABLE 5: Indicative energy of mobilit
H
2 CO, 02 N 2 CH, H 2
CO
2 02 N 2
CH
4 Ea Ea Ea Ea Ea Memb E, E, E, E, Em 16.8 4.4 K1 23.8 22.4 10.5 K2 17.5 15.1 7.0 8.0 9.4 K3 22.1 25.0 24.0 24.4 11.4 5.0 9.6 K4 18.4 23.0 28.6 14.5 J1 21.5 S1 14.0 1.9 S2 19.9 The sol-gel formulation and process of the invention is designed to provide the right balance between high separation (permselectivity) while maintaining high permeation (flux) of gases.
The membranes produced by the two-step catalysed process result in the presence of both good pore size control and high permselectivity for molecular diameters of less than 3A. The membranes of the invention also exhibit higher energies of activation and mobility than the single-step membranes.
WO 01/93993 PCT/AU01/00692 Control of the pore size within the membranes is a key component to achieving the desired permselectivity. It is believed that the formation of silanol groups (Q 2 and Q 3 during the membrane fabrication contribute highly to the formation of the weakly branched silica chains. It is thought that the two-step catalysed process of membrane formation coupled with low silica:water molar ratios inhibits the condensation reactions thus resulting in a lower formation of the fully condensed species (Q 4 It is the formation of the weakly branched silica chains (Q 2 and Q 3 species) that are a significant contributing control factor on the pore size of the film.
The higher contribution of the uncondensed species (Q2 and Q 3 or the lesser contribution of the condensed species (Q 4 form mutually transparent structures which inter-penetrate one another resulting in densification of the membrane matrix and therefore reduced the pore size of the membrane. During the heat treatment step not only is the solvent removed but the surface tension created in the gel causes the network to collapse.
Furthermore, it has been found that the use of nitric acid as a catalyst in the two-step catalysed hydrolysis process contributes to finer pore control than other known catalysts such as hydrogen chloride.
Throughout the specification the aim has been to describe the preferred embodiments of the invention without limiting the invention to any one embodiment or a specific collection of features.
Claims (13)
1. A method of producing weakly branched silica membranes coated onto a substrate using a two-step catalysed hydrolysis sol-gel process including the steps of: forming a tetraethylorthosilicate (TEOS)/ethanol solution; placing the TEOS/ethanol solution in an ice bath; forming an acid/water solution; adding the acid/water solution to the TEOS/ethanol solution to form a TEOS/ethanol/acid/water solution; refluxing the TEOS/ethanol/acid/water solution; preparing a two-step sol by adding water and nitric acid to the refluxed TEOS/ethanol/acid/water solution and initiating a two- step sol-gel process; depositing a membrane film layer on a substrate from the two-step sol to form a substrate coated with weakly branched silica membranes.
2. The method of claim 1, wherein the refluxing step is carried out on the TEOS/ethanol/acid/water solution having a molar composition of 1.0 TEOS:3.8 ethanol:1.0 water:7.0 x 10 4 M nitric acid.
3. The method of claim 1, wherein the refluxing step is conducted at approximately 600C for about 180 minutes in a water bath.
4. The method of claim 1, wherein the step of preparing a two-step sol results in the formation of a two-step sol having a molar composition of 1.0 TEOS:3.8 ethanol:6.0 water:0.1 nitric acid.
5. The method of claim 1, wherein the substrate is prepared with one WO 01/93993 PCT/AU01/00692 17 or more prime layers.
6. The method of claim 1, wherein the substrate is prepared with one or more intermediate layers.
7. The method of claim 1, wherein the substrate is prepared with one or more prime layers and one or more intermediate layers.
8. The method of claim 1, further including the step of heat treating the substrate coated with weakly branched silica membranes.
9. The method of claim 8, wherein the heat treatment step is carried out at temperatures between 400°C and 600°C with an air flow of 100ml per minute.
The method of claim 8, wherein the heat treatment is carried out at approximately 500 0 C
11. A weakly branched silica membrane when produced by the method of claim 1.
12. A weakly branched silica membrane when produced by the method of claim 1, wherein the weakly branched silica membrane has an average pore size of less than 3A and a film thickness of between 0.1 and
13. A weakly branched silica membrane of claim 12, wherein the weakly branched silica membrane has a high permselectivity for gases with molecular kinetic diameters (dk) less than 3A.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2001273734A AU2001273734B2 (en) | 2000-06-09 | 2001-06-12 | Improved silica membranes and process of production thereof |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPQ8113A AUPQ811300A0 (en) | 2000-06-09 | 2000-06-09 | Improved silica membrane and process of production therefor |
AUPQ8113 | 2000-06-09 | ||
PCT/AU2001/000692 WO2001093993A1 (en) | 2000-06-09 | 2001-06-12 | Improved silica membranes and process of production thereof |
AU2001273734A AU2001273734B2 (en) | 2000-06-09 | 2001-06-12 | Improved silica membranes and process of production thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
AU2001273734A1 AU2001273734A1 (en) | 2002-03-07 |
AU2001273734B2 true AU2001273734B2 (en) | 2005-04-07 |
Family
ID=39272620
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU2001273734A Ceased AU2001273734B2 (en) | 2000-06-09 | 2001-06-12 | Improved silica membranes and process of production thereof |
Country Status (1)
Country | Link |
---|---|
AU (1) | AU2001273734B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112510255A (en) * | 2020-12-23 | 2021-03-16 | 长春工业大学 | Gel electrolyte of zinc-based battery and preparation and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991012879A1 (en) * | 1990-02-21 | 1991-09-05 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Inorganic membranes and a process for making inorganic membranes |
WO2000039028A1 (en) * | 1998-12-23 | 2000-07-06 | Battelle Memorial Institute | Mesoporous silica film from a solution containing a surfactant and methods of making same |
-
2001
- 2001-06-12 AU AU2001273734A patent/AU2001273734B2/en not_active Ceased
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991012879A1 (en) * | 1990-02-21 | 1991-09-05 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Inorganic membranes and a process for making inorganic membranes |
WO2000039028A1 (en) * | 1998-12-23 | 2000-07-06 | Battelle Memorial Institute | Mesoporous silica film from a solution containing a surfactant and methods of making same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112510255A (en) * | 2020-12-23 | 2021-03-16 | 长春工业大学 | Gel electrolyte of zinc-based battery and preparation and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2411201C (en) | Improved silica membranes and process of production thereof | |
Da Costa et al. | Novel molecular sieve silica (MSS) membranes: characterisation and permeation of single-step and two-step sol–gel membranes | |
Gu et al. | Hydrothermally stable silica–alumina composite membranes for hydrogen separation | |
Nair et al. | Sol-gel synthesis of molecular sieving silica membranes | |
Hedlund et al. | ZSM-5 membranes synthesized without organic templates using a seeding technique | |
Bhuwania et al. | Engineering substructure morphology of asymmetric carbon molecular sieve hollow fiber membranes | |
Nomura et al. | Silicalite membranes modified by counterdiffusion CVD technique | |
Ohta et al. | Development of pore size-controlled silica membranes for gas separation by chemical vapor deposition | |
US20020142172A1 (en) | Inorganic dual-layer microporous supported membranes | |
US20090090241A1 (en) | Gas separation membranes containing a microporous silica layer based on silica doped with a trivalent element | |
Kanezashi et al. | Experimental and theoretical study on small gas permeation properties through amorphous silica membranes fabricated at different temperatures | |
US20050172811A1 (en) | Hydrogen-selective silica-based membrane | |
WO2003101593A1 (en) | Hydrogen-selective silica-based membrane | |
Araki et al. | Pervaporation of organic/water mixtures with hydrophobic silica membranes functionalized by phenyl groups | |
Ahn et al. | Synthesis and characterization of hydrogen selective silica membranes prepared by chemical vapor deposition of vinyltriethoxysilane | |
Naito et al. | Process conditions on the preparation of supported microporous SiO2 membranes by sol-gel modification techniques | |
EP2589428A1 (en) | Silica film filter and process for producing silica film filter | |
US20190070568A1 (en) | Permeation membrane and method for producing a permeation membrane | |
JP2008247654A (en) | Method for separating ammonia, method for producing ammonia, and gas separation membrane | |
AU2001273734B2 (en) | Improved silica membranes and process of production thereof | |
Nair et al. | Structure and separation properties of silica membranes | |
Da Costa et al. | Novel composite membranes for gas separation: preparation and performance | |
AU2001273734A1 (en) | Improved silica membranes and process of production thereof | |
Kang et al. | γ-Alumina composite membranes modified with microporous silica for CO2 separation | |
Lawal et al. | Facile development of microstructure-engineered, ligand-chelated SiO 2–ZrO 2 composite membranes for molecular separations |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FGA | Letters patent sealed or granted (standard patent) | ||
MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |