CN101856595B - Preparation method of metal doped organic-inorganic composite SiO2 film - Google Patents
Preparation method of metal doped organic-inorganic composite SiO2 film Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 title abstract description 12
- 229910052681 coesite Inorganic materials 0.000 title abstract 6
- 229910052906 cristobalite Inorganic materials 0.000 title abstract 6
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 6
- 229910052682 stishovite Inorganic materials 0.000 title abstract 6
- 229910052905 tridymite Inorganic materials 0.000 title abstract 6
- 239000007789 gas Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000010304 firing Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 238000009938 salting Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims 2
- 125000006606 n-butoxy group Chemical group 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007246 mechanism Effects 0.000 abstract description 3
- 238000007873 sieving Methods 0.000 abstract description 2
- 238000007171 acid catalysis Methods 0.000 abstract 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 1
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 238000000629 steam reforming Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- 239000010955 niobium Substances 0.000 description 7
- -1 Siloxanes Chemical class 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002454 metastable transfer emission spectrometry Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- CXLATMDDROQJAI-UHFFFAOYSA-N CCCCO[Nb] Chemical compound CCCCO[Nb] CXLATMDDROQJAI-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of a metal doped organic-inorganic composite SiO2 film, which is characterized by using siloxane as a precursor, carrying out hydrolysis under acid catalysis, adding ethanol solution of salt (alkoxide or nitrate) containing metal M into ice bath to synthesize metal doped organic-inorganic composite SiO2 sol, after film coating and drying, obtaining the metal doped organic-inorganic composite SiO2 film through firing under inert atmosphere. The composite SiO2 film effectively solves the problem of efficient separation of H2(He)/CO2 in the industrial gases (H2, CO2, O2, N2, CH4 and CO) and obviously improves the separation effect of H2(He)/CO2 through double effects of molecular sieving mechanism and adsorption. The composite SiO2 film has good application prospects in such environments containing water vapor and various mixed gases (H2, CO2, CO and CH4) as water gas shift reaction, methane steam reforming reaction and the like.
Description
Technical field:
The present invention relates to the compound SiO of a kind of metal-doped organic-inorganic
2The preparation method of film relates in particular at H
2(He)/CO
2The compound SiO of organic-inorganic of the metal-doped modification in the gas separation field
2The preparation method of film.This composite S iO
2Film will be with a wide range of applications in large-scale commercial Application, like methane vapor reforming reaction, water gas shift reaction etc.
Background technology:
At present, because the pressure of global warming, in the world to CO
2Emission problem given increasing concern, in energy-saving and emission-reduction, CO how to having discharged
2Capturing and seal up for safekeeping, is one of focus of current chemical field research.The CO that generally adopts at present
2Trapping technique has chemical absorbing, physical absorption etc., but all comes with some shortcomings.Film separates owing to have advantages such as process is continuous, energy consumption is low, is the gas separation that has very much prospect.Compare with organic film, advantage such as it is high temperature resistant, high pressure resistant, corrosion-resistant that inoranic membrane has, and have extraordinary permeability and selectivity, huge application potential is arranged in gas separation field and membrane catalytic reactor.Micropore SiO
2Film conduct a kind of inorganic material film wherein has unique Si-O-Si network structure, is one of gas separation membrane material that has very much prospect.At present, micropore SiO
2The mechanism of film separating mixed gas mainly is the molecule sieving actoion, and promptly the permeability of gas reduces along with the increase of Gas Molecules Kinetics diameter.World patent WO 99/61140 disclosed hydrophobic SiO
2The preparation method of gas separation membrane, the method for modifying through colloidal sol the presoma ethyl orthosilicate (be called for short: introduce in hydrolytic process TEOS) the hydrophobic group MTES (be called for short: MTES), through the film behind the hydrophobically modified to H
2, CO
2, O
2, N
2, CH
4And SF
6These six kinds of gases are tested, and along with the increase of Gas Molecules Kinetics diameter, the permeation flux of gas reduces gradually.H wherein
2/ CO
2Separation factor only have only 5.5, a little more than the desired separated factor (4.7) of Knudsen diffusion, separating effect is not obvious.The disclosed amorphous Si O that is used for the gas separation of world patent WO 2009/058209A1
2The preparation method of composite membrane, this invention is the γ-Al about 5nm with chemical vapour deposition technique (CVD) in the aperture
2O
3Obtain unbodied SiO on the carrier
2Composite membrane.The composite membrane that this method obtains is to H
2/ CO
2The desired separated factor about 4～6.More than two pieces of disclosed SiO of world patent
2Film separation of C O
2Gas mainly is according to molecule screening mechanism, H
2/ CO
2The desired separated factor all lower, near the desired separated factor (4.7) of Knudsen diffusion.And actual industrial process such as water gas shift reaction, methane vapor reforming reaction etc. require film to industrial gasses (H
2, CO
2, O
2, N
2, CH
4, CO) in H
2(He)/CO
2Has higher separating property.
Summary of the invention:
The objective of the invention is in order to improve film H
2(He)/CO
2Separating property, solve (H in the industrial gasses
2, CO
2, O
2, N
2, CH
4, CO) in H
2(He)/CO
2High efficiency separation problem and a kind of metal-doped compound SiO of organic-inorganic that proposes
2The preparation method of film.
Technical scheme of the present invention is: the compound SiO of a kind of metal-doped organic-inorganic
2The preparation method of film, its concrete steps are:
A: the compound SiO of metal-doped organic-inorganic
2Synthesizing of colloidal sol
Siloxanes and 1: 1 by volume～1: 10 mixed of solvent are placed ice bath; To wherein adding catalyst; Again this solution being placed temperature is that first step reaction is carried out in 40～90 ℃ water bath with thermostatic control, react after 1～3 hour, and taking-up is positioned in the ice bath; To wherein adding the salting liquid that contains metal M, the mol ratio of control M: Si is 0.1～1 again; And then the adding catalyst, continue to place 40～90 ℃ water bath with thermostatic control to carry out the reaction of second step, the second step reaction 1～3 hour; Obtain the compound SiO of metal-doped organic-inorganic of appearance transparent
2Colloidal sol;
B: be coated with membrane process
Above-mentioned colloidal sol and 1: 3 by volume～1: 20 dilution proportion of solvent are mixed with preparation liquid, preparation liquid is filmed at carrier surface;
C: drying and sintering process
Carrier drying with applying preparation liquid is warming up to 200～700 ℃, cooling naturally behind insulation 1～10h under gas shield; Make the compound SiO of metal-doped organic-inorganic
2Film.
Solvent among preferred steps a and the b is absolute ethyl alcohol, methyl alcohol or butanols; Preferred siloxanes is ethyl orthosilicate (TEOS), methyl silicate (TMOS), 1,2-two (triethoxy is silica-based) ethane (BTESE) or 1,2-two (triethoxy is silica-based) methane (BTESM).The salt that preferably contains metal M is alkoxide or the nitrate that contains metal M; The salting liquid that contains metal M is the ethanolic solution that contains metal M salt; The general preferred salting liquid mass concentration that contains metal M is 10%～30%.The alkoxide that preferably contains metal M is zirconium-n-propylate (Zr (OC
3H
7)
4), tetraethyl titanate (Ti (OC
2H
5)
4) or five n-butoxy niobium (Nb (OC
4H
9)
5); The nitrate that contains metal M is Ni (NO
3)
26H
2O, Al (NO
3)
39H
2O, Mg (NO
3)
26H
2O or Co (NO
3) 6H
2O.
In step a, can obtain the compound SiO of metal-doped organic-inorganic of appearance transparent
2Can colloidal sol be to be related to finally prepare the compound SiO of metal-doped organic-inorganic
2One of key factor of film.Because the hydrolysis rate of siloxanes is widely different with salt (alkoxide or the nitrate) hydrolysis rate that contains metal M; Can't guarantee that metal M successfully mixes in the network structure that forms after the siloxanes hydrolysis, therefore control contain metal M hydrolysis rate, hydrolysis method and the addition of salt (alkoxide or nitrate) to composite S iO
2Whether the film doping vario-property successfully plays conclusive effect.The present invention has carried out a large amount of research and has explored, final success obtained the compound SiO of metal-doped organic-inorganic
2Colloidal sol.In the hydrolytic process of siloxanes, adopt the synthetic complex sol of two-step method, the mass concentration of the ethanolic solution of the general preferred salt that contains metal M is 10%～30%.Preferred catalyst is HCl, H
2SO
4Or HNO
3Its concentration is 0.4～1.5mol/l; The addition of first step catalysts is with H among the step a
+: the mol ratio of Si is 1: 10～1: 50, and the addition of the second step catalysts is with H
+: the mol ratio of M is 1: 1～1: 30.Described ice bath temperature is-20～0 ℃; The temperature of preferred water bath with thermostatic control is 50～70 ℃.
In being coated with membrane process, can the viscosity of preparation liquid to obtaining the perfect sunken compound SiO of metal-doped organic-inorganic
2The film influence is very big, and the volume ratio of preferred sols and solvent is 1: 3～1: 10.Carrier among the above-mentioned steps b is preferably γ-Al
2O
3Film, ZrO
2Film or TiO
2Film.
Protective gas among the preferred steps c is He, N
2Or Ar; Heating rate is 0.2～2 ℃/min among the step c, and firing temperature is 300～550 ℃.
Beneficial effect:
The method of modifying through colloidal sol in the hydrolytic process of siloxanes, mix contain metal M salt (alkoxide or nitrate) to SiO
2Modification is carried out on the film surface, obtains the compound SiO of organic-inorganic of metal-doped modification
2Film.SiO after this modification
2Film to and H
2(He)/CO
2Separating table reveal remarkable advantages, solved (H in the industrial gasses
2, CO
2, O
2, N
2, CH
4And CO) H
2(He)/CO
2The high efficiency separation problem.The compound SiO of metal-doped organic-inorganic of the present invention's preparation
2Film has possessed excellent H simultaneously
2(He)/CO
2Separating property and steam stability, wherein He/CO
2The desired separated factor can reach more than 200.To SiO
2Application such as water gas shift reaction and the methane vapor reforming reactions etc. of gas separation membrane in industrial process provide condition.
Description of drawings:
Fig. 1 is the gas permeability comparison diagram; Wherein
Representative is the BTESE film of presoma preparation with BTESE,
Representative is with BTESE and Nb (OC
4H
9)
5Nb-BTESE film for the presoma preparation;
Fig. 2 for the Nb-BTESE film through after the steam treatment of different time, film is to He and CO
2Permeance property and He/CO
2Desired separated factor variations figure; Wherein
Representative is He/CO in the process of steam treatment different time
2The desired separated factor variations,
Be illustrated in the permeability variation situation of He in the process of steam treatment different time,
Be illustrated in CO in the process of steam treatment different time
2The permeability variation situation.
The specific embodiment:
Embodiment 1, with BTESE and Nb (OC
4H
9)
5The compound SiO of organic-inorganic that mixes for the Nb of presoma
2The preparation of film Nb-BTESE
5ml BTESE and 30ml absolute ethyl alcohol mixed placing 0 ℃ ice bath, under stirring condition to the HCl solution that wherein adds 0.6ml, 1mol/l, after mixing; Place 60 ℃ water bath with thermostatic control; React after 1.5 hours, take out in the ice bath that is placed on 0 ℃, add 7ml Nb (OC
4H
9)
5With the absolute ethyl alcohol of 35ml, after mixing, continue to add the HCl solution of 0.6ml, 1mol/l, in 60 ℃ water bath with thermostatic control, reacted 1.5 hours then.After finishing, reaction obtains the compound SiO of organic-inorganic of the Nb doping of appearance transparent
2Colloidal sol.Being placed on-20 ℃ preserves for use down.Is that 1: 8 mixed obtains preparation liquid with colloidal sol and absolute ethyl alcohol with volume ratio, with preparation liquid at sheet γ-Al
2O
3The film surface coating, the composite S iO that the sheet Nb of process air dry mixes
2Film with the heating rate of 0.5 ℃/min at N
2Sintering under the atmosphere, reach 450 ℃ after insulation lowered the temperature naturally again in 3 hours, obtain the Nb-BTESE film.The gas permeability of this film is as shown in Figure 1.After the steam treatment of different time, the gas permeability of film and He/CO
2Separation factor change as shown in Figure 2.
Comparative Examples 1: with BTESE is the compound SiO of organic-inorganic of presoma
2The preparation of film BTESE
5ml BTESE and the mixing of 20ml absolute ethyl alcohol are placed 0 ℃ ice bath; Under stirring condition,, after mixing, place 60 ℃ water bath with thermostatic control to the HCl solution that wherein adds 0.8ml, 1mol/l; React after 2.5 hours; Taking-up is placed in 0 ℃ the ice bath, adds the HCl solution of 0.8ml, 1mol/l again, reaction 2.5 hours in 60 ℃ water bath with thermostatic control then.After finishing, reaction obtains the compound SiO of organic-inorganic of appearance transparent
2Colloidal sol.Being placed on-20 ℃ preserves for use down.Is that 1: 5 mixed obtains preparation liquid with colloidal sol and absolute ethyl alcohol with volume ratio, with preparation liquid at sheet γ-Al
2O
3The film surface coating is through the sheet SiO of air dry
2Film with the heating rate of 2 ℃/min at N
2Sintering under the atmosphere, reach 450 ℃ after insulation lowered the temperature naturally again in 5 hours, obtain the BTESE film.The gas permeability of this film is as shown in Figure 1.Fig. 1 is the gas permeability comparison diagram of Nb-BTESE and two films of BTESE.The as can be seen from Figure 1 He/CO of Nb-BTESE film
2Separation factor greatly about about 220, far above the He/CO of BTESE film
2Separation factor (4.4) explains that metal-doped modification has improved film significantly to He/CO
2Separating effect, realized He/CO
2High efficiency separation.
Embodiment 2, with ethyl orthosilicate (TEOS) and tetraethyl titanate (Ti (OC
2H
5)
4) be the compound SiO of organic-inorganic of the Ti doping of presoma
2The preparation of film Ti-TEOS
10ml TEOS and 20ml butanols mixed placing-10 ℃ ice bath, under stirring condition to the HNO3 solution that wherein adds 1.8ml, 1.5mol/l, after mixing; Place 70 ℃ water bath with thermostatic control; React after 2 hours, take out in the ice bath that is placed on-10 ℃, add 2ml Ti (OC
2H
5)
4With the ethanol of 20ml, after mixing, continue to add the HNO of 1.8ml, 1.5mol/l
3Solution reacted 2 hours in 70 ℃ water bath with thermostatic control then.The Ti that obtains appearance transparent after reaction finishes organic inorganic compounding SiO that mixes
2Colloidal sol.Being placed on-20 ℃ preserves for use down.Is to mix at 1: 10 to obtain preparation liquid with colloidal sol and butanols with volume ratio, with preparation liquid at sheet TiO
2The film surface coating is through the sheet Ti doped and compounded SiO of air dry
2Film reaches 550 ℃ after cooling naturally after being incubated 6 hours obtains the Ti-TEOS film with heating rate sintering under He atmosphere of 1 ℃/min.
Embodiment 3, with 1,2-two (triethoxy is silica-based) methane (BTESM) for presoma to wherein mixing Co (NO
3) 6H
2O prepares the compound SiO of organic-inorganic that Co mixes
2Film Co-BTESM
5ml BTESM and 45ml methanol mixed are placed-20 ℃ ice bath, under stirring condition to the H that wherein adds 6ml, 0.5mol/l
2SO
4Solution after mixing, places 55 ℃ water bath with thermostatic control, reacts after 1 hour, takes out in the ice bath that is placed on-20 ℃, adds 15.7g Co (NO
3) 6H
2The ethanol of O and 60ml after mixing, continues to add the H of 6ml, 0.5mol/l
2SO
4Solution reacted 1 hour in 55 ℃ water bath with thermostatic control then.The Co that obtains appearance transparent after reaction finishes organic inorganic compounding SiO that mixes
2Colloidal sol.Being placed on-20 ℃ preserves for use down.Is to mix at 1: 3 to obtain preparation liquid with colloidal sol and methyl alcohol with volume ratio, with preparation liquid at sheet ZrO
2The film surface coating is through the sheet Co doped and compounded SiO of air dry
2Film reaches 300 ℃ after cooling naturally after being incubated 8 hours obtains the Co-BTESM film with heating rate sintering under Ar atmosphere of 1.5 ℃/min.
Claims (7)
1. compound SiO of metal-doped organic-inorganic
2The preparation method of film, its concrete steps are:
A: the compound SiO of metal-doped organic-inorganic
2Synthesizing of colloidal sol
With ethyl orthosilicate, methyl silicate or 1; 2-two (triethoxy is silica-based) ethane and 1: 1 by volume～1: 10 mixed of solvent place ice bath, and to wherein adding catalyst, again this solution being placed temperature is that first step reaction is carried out in 40～90 ℃ water bath with thermostatic control; React after 1～3 hour; Taking-up is positioned in the ice bath, and again to the solution that wherein adds the salt that contains metal M, the mol ratio of control M: Si is 0.1～1; And then the adding catalyst, continue to place 40～90 ℃ water bath with thermostatic control to carry out the reaction of second step, the second step reaction 1～3 hour; Obtain the compound SiO of metal-doped organic-inorganic of appearance transparent
2Colloidal sol; The described salt that contains metal M is alkoxide or the nitrate that contains metal M; The salting liquid that contains metal M is the ethanolic solution that contains metal M salt; The salting liquid mass concentration that contains metal M is 10%～30%; The wherein said alkoxide that contains metal M is zirconium-n-propylate, tetraethyl titanate or five n-butoxy niobiums; The nitrate that contains metal M is Ni (NO
3)
26H
2O, Al (NO
3)
39H
2O, Mg (NO
3)
26H
2O or Co (NO
3)
26H
2O;
B: be coated with membrane process
Above-mentioned colloidal sol and 1: 3 by volume～1: 20 dilution proportion of solvent are mixed with preparation liquid, preparation liquid is filmed at carrier surface;
C: drying and sintering process
With the carrier drying that applies preparation liquid, be warming up to 200～700 ℃ the interior cooling naturally behind 1～10h under gas shield of scope; Make the compound SiO of metal-doped organic-inorganic
2Film.
2. preparation method according to claim 1 is characterized in that the ice bath temperature described in the steps A is-20～0 ℃; The temperature of first step reaction and the reaction water bath with thermostatic control of second step is 50～70 ℃; Solvent among step a and the b is absolute ethyl alcohol, methyl alcohol or butanols.
3. preparation method according to claim 1 is characterized in that described catalyst is HCl, H
2SO
4Or HNO
3, its concentration is 0.4～1.5mol/l; The addition of first step catalysts is 1: 10～1: 50 with the mol ratio of hydrogen ion and Si among the step a; The addition of the second step catalysts is 1: 1～1: 30 with the mol ratio of hydrogen ion and metal M.
4. preparation method according to claim 1 is characterized in that the volume ratio 1: 3～1: 10 of colloidal sol and solvent among the step b.
5. preparation method according to claim 1 is characterized in that the carrier among the step b is γ-Al
2O
3, ZrO
2Or TiO
2
6. preparation method according to claim 1 is characterized in that the heating rate among the step c is 0.2～2 ℃/min; Firing temperature is 300～550 ℃.
7. preparation method according to claim 1 is characterized in that the protective gas among the step c is He, N
2Or Ar.
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|---|---|---|---|
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|---|---|---|---|---|
| CN103157390A (en) * | 2013-03-22 | 2013-06-19 | 沈阳化工大学 | Silicon dioxide film for separating CH4/CO2 gas and preparation method thereof |
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| CN104797328A (en) * | 2012-11-21 | 2015-07-22 | 东洋橡胶工业株式会社 | Separation membrane for treatment of gases containing acidic gas, method for producing same, method for separating acidic gas or methane gas, and method for producing acidic gas or methane gas |
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