CN106823843B - A kind of regulation method and its application of silica membrane aperture - Google Patents
A kind of regulation method and its application of silica membrane aperture Download PDFInfo
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- CN106823843B CN106823843B CN201710028138.6A CN201710028138A CN106823843B CN 106823843 B CN106823843 B CN 106823843B CN 201710028138 A CN201710028138 A CN 201710028138A CN 106823843 B CN106823843 B CN 106823843B
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- membrane aperture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention relates to a kind of regulation method and its application of silica membrane aperture, regulate and control method comprising steps of alkoxy silane, water and HCl hydrolytic-polymeric reaction, prepare silsesquioxane colloidal sol；It will be with SiO2‑ZrO2The silica glass granule of colloidal sol mixing is coated on porous glass tube, and calcining obtains the transition zone of film under hot conditions；By the erasing of silsesquioxane colloidal sol on transition zone, calcining obtains silicon dioxide film after being painted with；Silicon dioxide film is placed in ammonia atmosphere and carries out reaction in-situ, obtains modified silicon dioxide film.The beneficial effects of the present invention are: the reaction in-situ in ammonia, forms Si-NH in silicon dioxide structure2And/or Si-NH group, so that the network structure of film is become finer and close, leads to H2Permeability ratio initial value reduce about 40%, but other gases such as CO2、N2、CH3Deng permeability ratio H2What is reduced is more, so that modified SiO2Film is to H2Selectivity with higher, the film show excellent selectivity in Hydrogen Separation system to hydrogen.
Description
Technical field
The invention belongs to inorganic material film preparation field, it is related to a kind of regulation method of silica membrane aperture and its answers
With.
Background technique
It is concerned recently as environmental problems such as global air temperature warmings, the small research and development of environmental pollution is more next
More it is taken seriously.Hydrogen is a kind of new energy, and it is can be recycled and pollution-free to have many advantages, such as, is industrially had in chemical industry etc.
Broad application prospect.The acquisition channel of hydrogen is very various, and extracting the hydrogen in industry byproduct is the efficient, honest and clean of acquisition hydrogen
One of valence, recyclable effective way.
Membrane separation technique is to obtain one of most effective approach of high-purity hydrogen source at present, and the membrane material for Hydrogen Separation mainly has
Carbon Molecular Sieve Membrane, zeolite membrane, Pd metal film and silicon dioxide film etc..Silicon dioxide film is in gas separation not by Knudsen diffusion
Limitation, can be realized molecule screening, it is considered to be one of current most promising hydrogen permeation membrane material.But since tradition is amorphous
The average pore size of silicon dioxide film is still larger for hydrogen screening separation in 0.4nm or so, therefore not to the selectivity of hydrogen
Enough ideals, limit its large-scale application in Hydrogen Separation.
Summary of the invention
The technical problem to be solved by the present invention is based on the above issues, the present invention provides a kind of silica membrane aperture
Regulate and control method and its application.
The present invention solves a technical solution used by its technical problem: a kind of regulation side of silica membrane aperture
Method, comprising the following steps:
(1) in isopropanol, by the hydrolytic-polymeric reaction of alkoxy silane, water and HCl, it is molten to prepare silsesquioxane
Glue；
It (2) will be with SiO2-ZrO2The silica glass granule of colloidal sol mixing is coated on porous glass tube, hot conditions
Lower calcining obtains the transition zone of film；
(3) silsesquioxane colloidal sol obtained in step (1) is rubbed on the transition zone obtained in step (2), is painted with
Calcining obtains silicon dioxide film afterwards；
(4) silicon dioxide film obtained in step (3) is placed in the ammonia atmosphere of high temperature and pressure and carries out reaction in-situ, obtained
To modified silicon dioxide film.
Further, alkoxy silane is one of trimethoxy silane, triethoxysilane or two in step (1)
Kind.
Further, the molar ratio of the alkoxy silane in step (1), water and HCl are 1:240:0.1.
Further, in step (1) alkoxy silane mass fraction be 2.0%, hydrolytic-polymeric reaction temperature be 25~
45 DEG C, the hydrolytic-polymeric reaction time is 1~2h.
Further, the aperture of porous glass tube is 500nm, porosity 64% in step (2).
Further, silica glass granule diameter is 300nm in step (2), and calcination temperature is 550 DEG C, calcines gas
Atmosphere is air, calcination time 30min.
Further, calcination temperature is 400~650 DEG C in step (3), and calcination atmosphere is nitrogen, and calcination time is
30min。
Further, temperature is 550~650 DEG C, pressure 200kPa in step (4), the concentration of ammonia is 10~
100mol%, the carrier gas of ammonia are helium.
A kind of application of the regulation method of silica membrane aperture, the regulation method of silica membrane aperture are suitable for containing
The silicon fiml of Si -- H bond.
The beneficial effects of the present invention are: due to having Si-O-Si network structure inside silicon dioxide film obtained, it is basic herein
Upper addition NH3With SiO2Reaction in-situ occurs for the Si -- H inside film, and Si-NH is formed in silicon dioxide structure2And/or Si-
NH group makes the network structure of film become finer and close, leads to H2Permeability ratio initial value reduce about 40%, but other
Gas such as CO2、N2、CH3Deng permeability ratio H2What is reduced is more, so that modified SiO2Film is to H2Selection with higher
Property, which shows excellent selectivity in Hydrogen Separation system to hydrogen.
Detailed description of the invention
The following further describes the present invention with reference to the drawings.
Fig. 1 is SiO2The mechanism schematic diagram of film progress reaction in-situ；
Fig. 2 is in 400~650 DEG C of N2The SiO calcined under atmosphere2The FTIR of film schemes and and NH3After carrying out reaction in-situ
FTIR figure, wherein (a) is and NH3Before carrying out reaction in-situ, (b) it is and NH3After progress reaction in-situ；
Fig. 3 is the relational graph and the SiO at 550 DEG C of gas permeability and molecular size at 400 DEG C2Film and NH3It carries out former
The relational graph of gas permeability and molecular size after the reaction of position；
Fig. 4 is H2/N2,H2/CH4,H2/CO2Selectivity and NH3The performance map in (550 DEG C, 10mol%) reaction time.
Specific embodiment
Presently in connection with specific embodiment, the invention will be further described, following embodiment be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment 1
(1) in isopropanol, pass through TRIES, water and HCl (molar ratio TRIES:H at 25 DEG C2O:HCl=1:240:
0.1) hydrolysis and polymerization reaction 1h prepares silsesquioxane (SQ) colloidal sol；
It (2) will be with SiO2-ZrO2The silica glass granule (particle diameter 300nm) of colloidal sol mixing is coated in average hole
On the porous glass tube that diameter is 500nm and porosity is 64%, calcining obtains average hole under 550 DEG C of hot conditions of air atmosphere
Diameter is the transition zone of the film of 1~2nm；
(3) polymerization colloidal sol obtained in step (1) is rubbed on the transition zone obtained in step (2), in N after being painted with2
30min is calcined under 550 DEG C of high temperature of atmosphere, obtains silicon dioxide film；
(4) at 200kPa, film obtained in step (3) is placed in the NH that temperature is 550 DEG C and concentration is 10mol%3
Reaction in-situ is carried out in (carrier gas: He), and Si-NH is formed in silicon dioxide structure2And/or Si-NH group.
Embodiment 2
(1) in isopropanol, pass through TRIES, water and HCl (molar ratio TRIES:H at 45 DEG C2O:HCl=1:240:
0.1) hydrolysis and polymerization reaction 2h prepares silsesquioxane (SQ) colloidal sol；
It (2) will be with SiO2-ZrO2The silica glass granule (particle diameter 300nm) of colloidal sol mixing is coated in average hole
On the porous glass tube that diameter is 500nm and porosity is 64%, calcining obtains average hole under 550 DEG C of hot conditions of air atmosphere
Diameter is the transition zone of the film of 1~2nm；
(3) polymerization colloidal sol obtained in step (1) is rubbed on the transition zone obtained in step (2), in N after being painted with2
30min is calcined under 650 DEG C of high temperature of atmosphere, obtains silicon dioxide film；
(4) at 200kPa, film obtained in step (3) is placed in the NH that temperature is 650 DEG C and concentration is 10mol%3
Reaction in-situ is carried out in (carrier gas: He), and Si-NH is formed in silicon dioxide structure2And/or Si-NH group.
If Fig. 2 shows, (a) figure is the infrared spectrogram of the silicon dioxide film under 400~650 DEG C of nitrogen atmospheres, Cong Tuzhong
It can be seen that having Si-O-Si network structure and Si -- H bond；Si -- H bond does not change under high temperature inert atmosphere；(b) figure is to be modified
The infrared spectrogram of silicon dioxide film afterwards, as can be seen from the figure Si -- H bond disappears at 550~650 DEG C, Si-NH2Key and
Si-NH key occur, illustrate the Si -- H bond in silicon dioxide film at 550~650 DEG C with NH3It is reacted.
If Fig. 3 shows, by NH3Modification after most gas permeabilities have decline, but H2Permeability decrease
Amplitude is compared with CO2、N2And CH4Equal gases are less, illustrate the film after being modified to H2With better choice.
If Fig. 4 shows, with NH in situ3The extension in reaction time, in H2/CH4、H2/N2Or H2/CO2In separation system, film pair
H2Selectivity stepping up.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (8)
1. a kind of regulation method of silica membrane aperture, it is characterized in that: the following steps are included:
(1) in isopropanol, by the hydrolytic-polymeric reaction of alkoxy silane, water and HCl, silsesquioxane colloidal sol is prepared；
It (2) will be with SiO2-ZrO2The silica glass granule of colloidal sol mixing is coated on porous glass tube, is forged under hot conditions
Burning obtains the transition zone of film；
(3) silsesquioxane colloidal sol obtained in step (1) is rubbed on the transition zone obtained in step (2), is forged after being painted with
Burning obtains silicon dioxide film；
(4) silicon dioxide film obtained in step (3) is placed in the ammonia atmosphere of high temperature and pressure and carries out reaction in-situ, changed
Silicon dioxide film after property；
Temperature is 550~650 DEG C, pressure 200kPa in the step (4), and the concentration of ammonia is 10~100mol%, ammonia
The carrier gas of gas is helium.
2. the regulation method of a kind of silica membrane aperture according to claim 1, it is characterized in that: the step (1)
Middle alkoxy silane is one or both of trimethoxy silane, triethoxysilane.
3. the regulation method of a kind of silica membrane aperture according to claim 1, it is characterized in that: the step (1)
In alkoxy silane, water and HCl molar ratio be 1:240:0.1.
4. the regulation method of a kind of silica membrane aperture according to claim 1, it is characterized in that: the step (1)
The mass fraction of middle alkoxy silane is 2.0%, and hydrolytic-polymeric reaction temperature is 25~45 DEG C, and the hydrolytic-polymeric reaction time is 1
~2h.
5. the regulation method of a kind of silica membrane aperture according to claim 1, it is characterized in that: the step (2)
The aperture of middle porous glass tube is 500nm, porosity 64%.
6. the regulation method of a kind of silica membrane aperture according to claim 1, it is characterized in that: the step (2)
Middle silica glass granule diameter is 300nm, and calcination temperature is 550 DEG C, and calcination atmosphere is air, calcination time 30min.
7. the regulation method of a kind of silica membrane aperture according to claim 1, it is characterized in that: the step (3)
Middle calcination temperature is 400~650 DEG C, and calcination atmosphere is nitrogen, calcination time 30min.
8. the application of the regulation method of a kind of silica membrane aperture described in claim 1, it is characterized in that: the titanium dioxide
The regulation method in silicon fiml aperture is suitable for the silicon fiml containing Si -- H bond.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107952374A (en) * | 2017-11-24 | 2018-04-24 | 常州大学 | A kind of preparation method and application of micropore fluosilicic hybridized film |
| CN108479413B (en) * | 2018-04-10 | 2020-10-09 | 常州大学 | Preparation method of separation membrane for small molecule polypeptide |
| CN115090130B (en) * | 2021-09-13 | 2023-04-25 | 浙江美易膜科技有限公司 | Nanofiltration membrane containing silica gel nanoparticle intermediate layer and preparation method thereof |
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| US4656300A (en) * | 1985-06-26 | 1987-04-07 | Rhone Poulenc Specialites Chimiques | Process for a thermal treatment of a polysilazane containing .tbd.SiH groups and .tbd.Si--NH-- groups |
| CN1390223A (en) * | 1999-11-12 | 2003-01-08 | 基昂公司 | Novel silizane and/or polysilazane compounds and methods of making |
| CN1562450A (en) * | 2004-03-25 | 2005-01-12 | 复旦大学 | New type nano SiO2 separation membrane and preparation method |
| CN101233200A (en) * | 2005-07-26 | 2008-07-30 | 克拉里安特国际有限公司 | Method for the production of a thin glassy coating on substrates in order to reduce gas permeation |
| CN102171796A (en) * | 2008-10-01 | 2011-08-31 | 应用材料股份有限公司 | Methods for forming silicon nitride based film or silicon carbon based film |
| CN102886211A (en) * | 2012-09-28 | 2013-01-23 | 天津大学 | Solvent-free preparation method of aperture controllable porous film |
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2017
- 2017-01-13 CN CN201710028138.6A patent/CN106823843B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4656300A (en) * | 1985-06-26 | 1987-04-07 | Rhone Poulenc Specialites Chimiques | Process for a thermal treatment of a polysilazane containing .tbd.SiH groups and .tbd.Si--NH-- groups |
| CN1390223A (en) * | 1999-11-12 | 2003-01-08 | 基昂公司 | Novel silizane and/or polysilazane compounds and methods of making |
| CN1562450A (en) * | 2004-03-25 | 2005-01-12 | 复旦大学 | New type nano SiO2 separation membrane and preparation method |
| CN101233200A (en) * | 2005-07-26 | 2008-07-30 | 克拉里安特国际有限公司 | Method for the production of a thin glassy coating on substrates in order to reduce gas permeation |
| CN102171796A (en) * | 2008-10-01 | 2011-08-31 | 应用材料股份有限公司 | Methods for forming silicon nitride based film or silicon carbon based film |
| CN102886211A (en) * | 2012-09-28 | 2013-01-23 | 天津大学 | Solvent-free preparation method of aperture controllable porous film |
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