CN107441948A - A kind of Ni type hydrophobicity SiO2Composite membrane and preparation method thereof - Google Patents

A kind of Ni type hydrophobicity SiO2Composite membrane and preparation method thereof Download PDF

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CN107441948A
CN107441948A CN201710859624.2A CN201710859624A CN107441948A CN 107441948 A CN107441948 A CN 107441948A CN 201710859624 A CN201710859624 A CN 201710859624A CN 107441948 A CN107441948 A CN 107441948A
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sio
colloidal sol
composite membrane
ethyl alcohol
mass percent
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杨靖
贾德宝
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Xian Polytechnic University
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Xian Polytechnic University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • 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
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0048—Inorganic membrane manufacture by sol-gel transition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/38—Hydrophobic membranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

A kind of Ni type hydrophobicity SiO disclosed by the invention2Composite membrane, it is composed of the following components according to mass percent：Tetraethyl orthosilicate 14.83%~24.12%, MTES 15.23%~16.72%, absolute ethyl alcohol 41.63%~49.87%, water 15.21%~15.38%, HNO30.54%~0.63%, Ni (NO3)2·6H2O 1.68%~4.14%, the mass percent sum of above each component is 100%, solves existing common SiO2The gas permeation rate and separation factor of film are difficult the problem of improving simultaneously；The Ni type hydrophobicity SiO of the present invention2Compound membrane preparation method, improving SiO2On the basis of film water vapour stability, while increase H2Infiltration rate and H2/CO2Separation factor.

Description

A kind of Ni type hydrophobicity SiO2Composite membrane and preparation method thereof
Technical field
The invention belongs to gas separation membrane technical field, is related to a kind of Ni type hydrophobicity SiO2Composite membrane, the present invention Further relate to Ni type hydrophobicity SiO2The preparation method of composite membrane.
Background technology
It is well known that CO2It is a kind of maximum greenhouse gases of discharge capacity, is the weight that greenhouse gases are cut down and controlled Point.CO2Primary discharge source be fossil fuel use, especially burning of coal use.And H2It is a kind of great DEVELOPMENT PROSPECT Clean energy resource.At present in the world even propose by with serious pollution coal efficiently, intensively be converted into cleaning hydrogen fired Burn, i.e. hydrogen production from coal gasification, the high concentration CO that will be isolated2Transport to appointed place and stored, to reduce greenhouse gases CO2Discharge.During hydrogen production from coal gasification, the high-pressure oxygen-enriched gasification of coal is usually become into coal gas (H2+ CO), but in order to just In more isolating CO2, (H is converted it into after tending to vary with2+CO2), then by H2From CO2Middle separation.Therefore, from mixed air (H2+CO2) in isolate hydrogen be obtain high-purity hydrogen an important and key link.
Membrane separation technique is purification H2Effective ways.In recent years, for H2The research of separation inoranic membrane, SiO2Film quilt Think most to study the most extensive close to commercial Application.However, common SiO2Many shortcomings be present in film：Steam less stable, Separating effect can be reduced gradually during long-term use in wet environment.The common SiO prepared for sol-gel process2For film, Its mechanism of mass transmission is generally Knudsen diffusion, molecule screening or Knudsen diffusion+molecule screening, therefore its gas permeation rate and separation The factor is difficult to improve simultaneously.
The content of the invention
It is an object of the invention to provide a kind of Ni type hydrophobicity SiO2Composite membrane, solves common hydrophily SiO2Film The problem of hydrothermal stability difference.
It is a further object to provide a kind of Ni type hydrophobicity SiO2The preparation method of composite membrane.
The technical solution adopted in the present invention is,
A kind of Ni type hydrophobicity SiO2Composite membrane, it is composed of the following components according to mass percent：
Tetraethyl orthosilicate 14.83%~24.12%, MTES 15.23%~16.72%, absolute ethyl alcohol 41.63%~49.87%, water 15.21%~15.38%, HNO30.54%~0.63%, Ni (NO3)2·6H2O 1.68% ~4.14%, the mass percent sum of above each component is 100%.
The present invention another used technical scheme be：
A kind of Ni type hydrophobicity SiO2The preparation method of composite membrane, specifically implements according to following steps：
Step 1, weigh following component respectively according to mass percent：
Tetraethyl orthosilicate 14.83%~24.12%, MTES 15.23%~16.72%, absolute ethyl alcohol 41.63%~49.87%, water 15.21%~15.38%, HNO30.54%~0.63%, Ni (NO3)2·6H2O 1.68% ~4.14%, the mass percent sum of above each component is 100%；
Step 2, by the tetraethyl orthosilicate weighed in step 1, MTES, absolute ethyl alcohol in ice-water bath it is strong Strong stirring 40min~60min, make it well mixed, mixed solution is made；
Water, the HNO by being weighed in step 1 is added dropwise in step 3, the mixed solution obtained to step 2 while stirring3And Ni (NO3)2·6H2Homogeneous mixture solotion made from O solids, 2h~5h is stirred at reflux at 50 DEG C~70 DEG C after being added dropwise, it is natural Room temperature is cooled to, obtains original Ni/SiO2Colloidal sol；
Step 4, the original Ni/SiO for adding the mixed liquor of drying control agent and absolute ethyl alcohol in step 3 while stirring2 In colloidal sol, make original Ni/SiO2Colloidal sol dilutes 3~8 times respectively, continues to stir 40min~60min, obtains extension rate difference Ni/SiO2Colloidal sol；
Step 5, with porous α-Al2O3Ceramics are supporter, the Ni/SiO obtained from step 42It is any in colloidal sol to choose two kinds Or the Ni/SiO of two or more different extension rates2Colloidal sol, using infusion process by the Ni/SiO of the different extension rates of selection2It is molten Glue is successively coated in the supporting body surface, every layer of dip-coating 7s~10s, drying at room temperature according to the order of extension rate from small to large Roast is carried out after 3h~5h, produces Ni type hydrophobicity SiO2Composite membrane.
The features of the present invention also resides in：
Drying control agent in step 4 is N,N-dimethylformamide.
The volume of N,N-dimethylformamide is original Ni/SiO2The 30%~40% of sol volume.
In step 5, roasting is in N2、H2Or N2-H2In the non-oxidizing atmospheres such as mixed gas, first with 0.2 DEG C/min~ 0.3 DEG C/min is warming up to 110 DEG C, is then warming up to 350~400 DEG C with 0.5 DEG C/min, is calcined 2h~3h, then with 0.5 DEG C/min ~1.0 DEG C/min speed is cooled to room temperature.
The beneficial effects of the present invention are：
A kind of Ni type hydrophobicity SiO of the present invention2Composite membrane, using MTES to hydrophily SiO2Film The modification that methylates is carried out, in the SiO of hydrophobically modified2Nickel is adulterated in film, further improves SiO2The steam stability of film, is solved Existing common SiO2The problem of hydrothermal stability difference of film；Pass through Ni type hydrophobicity made from the preparation method of the present invention SiO2Composite membrane, improving SiO2On the basis of film water vapour stability, while increase H2Infiltration rate and H2/CO2Separation because Son, after being aged in water vapour environment, H2Infiltration rate is only a small amount of to be reduced, H2/CO2Separation factor increases on the contrary, hydrothermal stability Effectively improve.
Brief description of the drawings
Fig. 1 is a kind of Ni type hydrophobicity SiO of the present invention2Ni type hydrophobicity prepared by the preparation method of composite membrane SiO2Composite membrane and common SiO2Film is aged the front and rear infiltration rate comparison diagram to different-diameter gas molecule in water vapour environment；
Fig. 2 is a kind of Ni type hydrophobicity SiO of the present invention2Ni type hydrophobicity prepared by the preparation method of composite membrane SiO2Composite membrane and common SiO2Film is aged front and rear H in water vapour environment2/CO2Selective comparison diagram.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
A kind of Ni type hydrophobicity SiO of the present invention2Composite membrane, it is composed of the following components according to mass percent：Positive silicon Acetoacetic ester 14.83%~24.12%, MTES 15.23%~16.72%, absolute ethyl alcohol 41.63%~ 49.87%, water 15.21%~15.38%, HNO30.54%~0.63%, Ni (NO3)2·6H2O 1.68%~4.14%, The mass percent sum of above each component is 100%.
Above-mentioned Ni type hydrophobicity SiO2The preparation method of composite membrane, specifically implements according to following steps：
Step 1, weigh following component respectively according to mass percent：
Tetraethyl orthosilicate 14.83%~24.12%, MTES 15.23%~16.72%, absolute ethyl alcohol 41.63%~49.87%, water 15.21%~15.38%, HNO30.54%~0.63%, Ni (NO3)2·6H2O 1.68% ~4.14%, the mass percent sum of above each component is 100%.
Step 2, by the tetraethyl orthosilicate weighed in step 1, MTES, absolute ethyl alcohol in ice-water bath it is strong Strong stirring 40min~60min, make it well mixed, mixed solution is made；
Water, the HNO by being weighed in step 1 is added dropwise in step 3, the mixed solution obtained to step 2 while stirring3And Ni (NO3)2·6H2Homogeneous mixture solotion made from O solids, 2h~5h is stirred at reflux at 50 DEG C~70 DEG C after being added dropwise, it is natural Room temperature is cooled to, obtains original Ni/SiO2Colloidal sol；
Wherein, HNO3It is by dense HNO3Dilute HNO that concentration after dilution is 1mol/L3Solution.
Step 4, the original Ni/SiO for adding the mixed liquor of drying control agent and absolute ethyl alcohol in step 3 while stirring2 In colloidal sol, make original Ni/SiO2Colloidal sol dilutes 3~8 times, continues to stir 40min~60min, obtains the different Ni/ of extension rate SiO2Colloidal sol；
Drying control agent is DMF, and DMF volume accounts for original Ni/SiO2Sol Long-pending 30%~40%.
Step 5, with porous α-Al2O3Ceramics are supporter, the Ni/SiO obtained from step 42It is any in colloidal sol to choose two kinds Or the Ni/SiO of two or more different extension rates2Colloidal sol, using infusion process by the Ni/SiO of the different extension rates of selection2It is molten Glue is successively coated in the supporting body surface, every layer of dip-coating 7s~10s, drying at room temperature according to the order of extension rate from small to large Roast is carried out after 3h~5h, produces Ni type hydrophobicity SiO2Composite membrane.
Roast is in N2、H2Or N2-H2In the non-oxidizing atmospheres such as mixed gas, first with 0.2 DEG C/min~0.3 DEG C/ Min is warming up to 110 DEG C, is then warming up to 350~400 DEG C with 0.5 DEG C/min, is calcined 2h~3h, then with 0.5 DEG C/min~1.0 DEG C/min speed is cooled to room temperature.
The Ni type hydrophobicity SiO prepared by the preparation method of the present invention2Composite membrane, improving SiO2Film water vapour is steady On the basis of qualitatively, while increase H2Infiltration rate and H2/CO2Separation factor, after being aged in water vapour environment, H2Infiltration Speed is only a small amount of to be reduced, H2/CO2Separation factor increases on the contrary, and hydrothermal stability effectively improves.
A kind of Ni type hydrophobicity SiO of the present invention2The effect of each component added in the preparation method of composite membrane：Just Silester (TEOS) is used as silicon source；MTES (MTES) is used as hydrophobic modifier, instead of the positive silicic acid second in part Ester, the SiO of methyl modification is prepared by both cohydrolysis condensation reactions2Film；Absolute ethyl alcohol (EtOH) is on the one hand used as solvent, separately On the one hand it is also the product of polycondensation reaction；Deionized water (H2O reactant) is used as, participates in hydrolysis-condensation reaction；Nitric acid (HNO3) As catalyst, while adjust the pH value of solution；Nickel nitrate (Ni (NO3)2·6H2O the required nickel source of the present invention) is provided；N, Dinethylformamide (DMF) is used as drying control agent, to prevent the cracking of film.
Fig. 1 is the Ni type hydrophobicity SiO prepared by the preparation method of the present invention2Composite membrane and common SiO2Film exists The front and rear infiltration rate comparison diagram to different-diameter gas molecule is aged in water vapour environment.Common hydrophilic SiO2The positive silicon of film reaction thing Acetoacetic ester, absolute ethyl alcohol, water, the mass percent of nitric acid are 42.6%：38.2%：18.4%：0.8%, prepared by the present invention Ni type SiO2Composite membrane reactant tetraethyl orthosilicate, MTES, absolute ethyl alcohol, water, nitric acid, nickel nitrate Mass percent is 24.12%：16.72%：41.63%：15.21%：0.63%：1.68%, dip-coating 5 times.Can from Fig. 1 Go out, before being aged in water vapour environment, common SiO2Film is to H2、CO2、O2、N2、CH4Infiltration rate difference 6.03 × 10-6、1.22 ×10-6、1.08×10-6、1.05×10-6、1.1×10-6mol·m-2·Pa-1·s-1, the Ni type SiO of the invention prepared2 Composite membrane is to H2、CO2、O2、N2、CH4Infiltration rate then be respectively 7.86 × 10-6、1.50×10-6、1.10×10-6、1.19× 10-6、1.36×10-6mol·m-2·Pa-1·s-1.The load of nickel makes H2Infiltration rate improve 1.31 times.75%RH's In water vapour environment it is aging for one week after, common SiO2Film is to H2、CO2、O2、N2、CH4Infiltration rate be respectively 2.95 × 10-6、5.81 ×10-7、5.18×10-7、5.01×10-7、4.88×10-7mol·m-2·Pa-1·s-1, the metal Ni of the invention prepared Type SiO2Composite membrane is to H2、CO2、O2、N2、CH4Infiltration rate then be respectively 7.32 × 10-6、1.34×10-6、9.64×10-7、 1.04×10-6、1.17×10-6mol·m-2·Pa-1·s-1.Common SiO after steam ageing2Film is to H2Infiltration rate reduce 51.08%, and Ni type SiO prepared by the present invention2Composite membrane is to H2Infiltration rate reduced by only 6.88%.
Fig. 2 is Ni type hydrophobicity SiO prepared by the present invention2Composite membrane and common SiO2Film is aged in water vapour environment Front and rear H2/CO2Selective comparison diagram.Before being aged in water vapour environment, common SiO2Film is to H2/CO2Gas selectivity be 4.95, metallic nickel support type SiO prepared by the present invention2Composite membrane is then 5.24.The load of nickel makes H2/CO2Separation factor improves 5.86%.In 75%RH water vapour environment it is aging for one week after, common SiO2Film is to H2/CO2Gas selectivity be 5.08, metallic nickel support type SiO prepared by the present invention2Composite membrane is then 5.48.Common SiO after steam ageing2Film is to H2/CO2 Separation factor add 2.63%, Ni type SiO prepared by the present invention2Composite membrane then adds 4.58%.
Embodiment 1
Step 1, weigh following component respectively according to mass percent：
Tetraethyl orthosilicate 24.12%, MTES 16.72%, absolute ethyl alcohol 41.63%, water 15.21%, HNO30.63%, Ni (NO3)2·6H2O 1.68%, the mass percent sum of above each component is 100%；
Step 2, by the tetraethyl orthosilicate weighed in step 1, MTES, absolute ethyl alcohol in ice-water bath it is strong Strong stirring 45min, make it well mixed, mixed solution is made；
Water, the dilute HNO by being weighed in step 1 is added dropwise in step 3, the mixed solution obtained to step 2 while stirring3And Ni (NO3)2·6H2Homogeneous mixture solotion made from O solids, 5h is stirred at reflux at 50 DEG C after being added dropwise, naturally cools to room Temperature, obtain original Ni/SiO2Colloidal sol；
Step 4, the original Ni/SiO for adding the mixed liquor of drying control agent and absolute ethyl alcohol in step 3 while stirring2 In colloidal sol, make original Ni/SiO2Colloidal sol dilutes 3 times and 4 times respectively, continues to stir 40min, obtains the different Ni/ of extension rate SiO2Colloidal sol；
Drying control agent is DMF, and DMF accounts for original Ni/SiO2Sol volume 30%.
Step 5, with porous α-Al2O3Ceramics are supporter (porous α-Al2O3Ceramics thick 5mm, average pore size 100nm, Transition zone is by Al thereon2O3、Y2O3And ZrO2Material cladding forms, and 5 μm of transition thickness, porosity is about 35%, and average pore size is 4nm, surface is smooth, non-microcracked), 3 times and 4 times of Ni/SiO for being obtained step 4 using infusion process2Colloidal sol according to The order of extension rate from small to large is successively coated in the supporting body surface, in H after dip-coating 7s, drying at room temperature 3h2In atmosphere, 110 DEG C are warming up to 0.2 DEG C/min first, is then warming up to 350 DEG C with 0.5 DEG C/min, is calcined 3h, then with 0.5 DEG C/min's Speed is cooled to room temperature.
Embodiment 2
Step 1, weigh following component respectively according to mass percent：
Tetraethyl orthosilicate 22.41%, MTES 16.30%, absolute ethyl alcohol 42.69%, water 15.49%, HNO30.61%, Ni (NO3)2·6H2O 2.50%, the mass percent sum of above each component is 100%；
Step 2, by the tetraethyl orthosilicate weighed in step 1, MTES, absolute ethyl alcohol in ice-water bath it is strong Strong stirring 45min, make it well mixed, mixed solution is made；
Water, the dilute HNO by being weighed in step 1 is added dropwise in step 3, the mixed solution obtained to step 2 while stirring3And Ni (NO3)2·6H2Homogeneous mixture solotion made from O solids, 3h is stirred at reflux at 60 DEG C after being added dropwise, naturally cools to room Temperature, obtain original Ni/SiO2Colloidal sol；
Step 4, the original Ni/SiO for adding the mixed liquor of drying control agent and absolute ethyl alcohol in step 3 while stirring2 In colloidal sol, make original Ni/SiO2Colloidal sol dilutes 3 times, 4 times and 5 times respectively, continues to stir 45min, it is different to obtain extension rate Ni/SiO2Colloidal sol；
Drying control agent is DMF, and DMF accounts for original Ni/SiO2Sol volume 32%.
Step 5, with porous α-Al2O3Ceramics are supporter (porous α-Al2O3Ceramics thick 5mm, average pore size 100nm, Transition zone is by Al thereon2O3、Y2O3And ZrO2Material cladding forms, and 5 μm of transition thickness, porosity is about 35%, and average pore size is 4nm, surface is smooth, non-microcracked), the Ni/SiO for three kinds of concentration for respectively being obtained step 4 using infusion process2Colloidal sol is pressed The supporting body surface is successively coated according to the order of extension rate from small to large, after dip-coating 8s, drying at room temperature 3.5h, in N2Gas It is to be warming up to 110 DEG C with 0.25 DEG C/min first in atmosphere, is then warming up to 360 DEG C with 0.5 DEG C/min, is calcined 2.5h, then with 0.5 DEG C/min speed is cooled to room temperature, produces Ni type hydrophobicity SiO2Composite membrane.
Embodiment 3
Step 1, weigh following component respectively according to mass percent：
Tetraethyl orthosilicate 20.64%, MTES 15.90%, absolute ethyl alcohol 43.95%, water 16.05%, HNO30.59%, Ni (NO3)2·6H2O 2.88%, the mass percent sum of above each component is 100%；
Step 2, by the tetraethyl orthosilicate weighed in step 1, MTES, absolute ethyl alcohol in ice-water bath it is strong Strong stirring 50min, make it well mixed, mixed solution is made；
Water, the dilute HNO by being weighed in step 1 is added dropwise in step 3, the mixed solution obtained to step 2 while stirring3And Ni (NO3)2·6H2Homogeneous mixture solotion made from O solids, 2.5h is stirred at reflux at 65 DEG C after being added dropwise, naturally cools to room Temperature, obtain original Ni/SiO2Colloidal sol；
Step 4, the original Ni/SiO for adding the mixed liquor of drying control agent and absolute ethyl alcohol in step 3 while stirring2 In colloidal sol, make original Ni/SiO2Colloidal sol dilutes 3 times, 4 times, 5 times and 6 times respectively, continues to stir 50min, obtains extension rate not Same Ni/SiO2Colloidal sol；
Drying control agent is DMF, and DMF accounts for original Ni/SiO2Sol volume 34%.
Step 5, with porous α-Al2O3Ceramics are supporter (porous α-Al2O3Ceramics thick 5mm, average pore size 100nm, Transition zone is by Al thereon2O3、Y2O3And ZrO2Material cladding forms, and 5 μm of transition thickness, porosity is about 35%, and average pore size is 4nm, surface is smooth, non-microcracked), the Ni/SiO for four kinds of various concentrations for respectively being obtained step 4 using infusion process2It is molten Glue is successively coated in the supporting body surface according to the order of extension rate from small to large, after dip-coating 9s, drying at room temperature 4h, in H2 It is to be warming up to 110 DEG C with 0.28 DEG C/min first in atmosphere, is then warming up to 370 DEG C with 0.5 DEG C/min, is calcined 2.3h, then with 0.8 DEG C/min speed is cooled to room temperature, produces Ni type hydrophobicity SiO2Composite membrane.
Embodiment 4
Step 1, weigh following component respectively according to mass percent：
Tetraethyl orthosilicate 18.06%, MTES 15.46%, absolute ethyl alcohol 46.55%, water 15.60%, HNO30.55%, Ni (NO3)2·6H2O 3.78%, the mass percent sum of above each component is 100%；
Step 2, by the tetraethyl orthosilicate weighed in step 1, MTES, absolute ethyl alcohol in ice-water bath it is strong Strong stirring 55min, make it well mixed, mixed solution is made；
Water, the dilute HNO by being weighed in step 1 is added dropwise in step 3, the mixed solution obtained to step 2 while stirring3And Ni (NO3)2·6H2Homogeneous mixture solotion made from O solids, 2.5h is stirred at reflux at 68 DEG C after being added dropwise, naturally cools to room Temperature, obtain original Ni/SiO2Colloidal sol；
Step 4, the original Ni/SiO for adding the mixed liquor of drying control agent and absolute ethyl alcohol in step 3 while stirring2 In colloidal sol, make original Ni/SiO2Colloidal sol dilutes 3 times, 4 times, 5 times, 6 times and 7 times respectively, continues to stir 55min, obtains dilution times The different Ni/SiO of number2Colloidal sol；
Drying control agent is DMF, and DMF accounts for original Ni/SiO2Sol volume 36%.
Step 5, with porous α-Al2O3Ceramics are supporter (porous α-Al2O3Ceramics thick 5mm, average pore size 100nm, Transition zone is by Al thereon2O3、Y2O3And ZrO2Material cladding forms, and 5 μm of transition thickness, porosity is about 35%, and average pore size is 4nm, surface is smooth, non-microcracked), the Ni/SiO for five kinds of various concentrations for respectively being obtained step 4 using infusion process2It is molten Glue is successively coated in the supporting body surface according to the order of extension rate from small to large, after dip-coating 9s, drying at room temperature 4.5h, H2It is to be warming up to 110 DEG C with 0.3 DEG C/min first in atmosphere, is then warming up to 380 DEG C with 0.5 DEG C/min, is calcined 2.2h, then Room temperature is cooled to 0.8 DEG C/min speed, produces Ni type hydrophobicity SiO2Composite membrane.
Embodiment 5
Step 1, weigh following component respectively according to mass percent：
Tetraethyl orthosilicate 14.83%, MTES 15.23%, absolute ethyl alcohol 49.87%, water 15.38%, HNO30.54%, Ni (NO3)2·6H2O 4.14%, the mass percent sum of above each component is 100%；
Step 2, by the tetraethyl orthosilicate weighed in step 1, MTES, absolute ethyl alcohol in ice-water bath it is strong Strong stirring 60min, make it well mixed, mixed solution is made；
Water, the dilute HNO by being weighed in step 1 is added dropwise in step 3, the mixed solution obtained to step 2 while stirring3And Ni (NO3)2·6H2Homogeneous mixture solotion made from O solids, 2h is stirred at reflux at 70 DEG C after being added dropwise, naturally cools to room Temperature, obtain original Ni/SiO2Colloidal sol；
Step 4, the original Ni/SiO for adding the mixed liquor of drying control agent and absolute ethyl alcohol in step 3 while stirring2 In colloidal sol, make original Ni/SiO2Colloidal sol dilutes 3 times, 4 times, 5 times, 6 times, 7 times and 8 times respectively, continues to stir 60min, obtains Ni/SiO2Colloidal sol；
Drying control agent is DMF, and DMF accounts for original Ni/SiO2Sol volume 40%.
Step 5, with porous α-Al2O3Ceramics are supporter (porous α-Al2O3Ceramics thick 5mm, average pore size 100nm, Transition zone is by Al thereon2O3、Y2O3And ZrO2Material cladding forms, and 5 μm of transition thickness, porosity is about 35%, and average pore size is 4nm, surface is smooth, non-microcracked), the Ni/SiO for six kinds of various concentrations for respectively being obtained step 4 using infusion process2It is molten Glue is successively coated in the supporting body surface according to the order of extension rate from small to large, after dip-coating 10s, drying at room temperature 5h, N2-H2It is to be warming up to 110 DEG C with 0.3 DEG C/min first in mixed-gas atmosphere, is then warming up to 400 DEG C with 0.5 DEG C/min, roasting 2h is burnt, then room temperature is cooled to 1.0 DEG C/min speed, produces Ni type hydrophobicity SiO2Composite membrane.

Claims (5)

  1. A kind of 1. Ni type hydrophobicity SiO2Composite membrane, it is characterised in that composed of the following components according to mass percent：Just Silester 14.83%~24.12%, MTES 15.23%~16.72%, absolute ethyl alcohol 41.63%~ 49.87%, water 15.21%~15.38%, HNO30.54%~0.63%, Ni (NO3)2·6H2O 1.68%~4.14%, The mass percent sum of above each component is 100%.
  2. A kind of 2. Ni type hydrophobicity SiO2The preparation method of composite membrane, it is characterised in that specifically implement according to following steps：
    Step 1, weigh following component respectively according to mass percent：
    Tetraethyl orthosilicate 14.83%~24.12%, MTES 15.23%~16.72%, absolute ethyl alcohol 41.63%~49.87%, water 15.21%~15.38%, HNO30.54%~0.63%, Ni (NO3)2·6H2O 1.68% ~4.14%, the mass percent sum of above each component is 100%；
    Step 2, the tetraethyl orthosilicate weighed in step 1, MTES, absolute ethyl alcohol stirred strongly in ice-water bath 45min~60min is mixed, makes it well mixed, mixed solution is made；
    Water, the HNO by being weighed in step 1 is added dropwise in step 3, the mixed solution obtained to step 2 while stirring3And Ni (NO3)2·6H2Homogeneous mixture solotion made from O solids, 2h~5h is stirred at reflux at 50 DEG C~75 DEG C after being added dropwise, it is natural Room temperature is cooled to, obtains original Ni/SiO2Colloidal sol；
    Step 4, the original Ni/SiO for adding the mixed liquor of drying control agent and absolute ethyl alcohol in step 3 while stirring2Colloidal sol In, make original Ni/SiO2Colloidal sol dilutes 3~8 times, continues to stir 40min~60min, obtains the different Ni/SiO of extension rate2 Colloidal sol；
    Step 5, with porous α-Al2O3Ceramics are supporter, the Ni/SiO obtained from step 42It is any in colloidal sol to choose two kinds or two The Ni/SiO of different extension rates more than kind2Colloidal sol, using infusion process by the Ni/SiO of the different extension rates of selection2Colloidal sol is pressed The supporting body surface is successively coated according to the order of extension rate from small to large, every layer of dip-coating 7s~10s, drying at room temperature 3h~ Roast is carried out after 5h, produces Ni type hydrophobicity SiO2Composite membrane.
  3. A kind of 3. Ni type hydrophobicity SiO as claimed in claim 22The preparation method of composite membrane, it is characterised in that described Drying control agent in step 4 is N,N-dimethylformamide.
  4. A kind of 4. Ni type hydrophobicity SiO as claimed in claim 32The preparation method of composite membrane, it is characterised in that described N,N-dimethylformamide accounts for original Ni/SiO2The 30%~40% of sol volume.
  5. A kind of 5. Ni type hydrophobicity SiO as claimed in claim 22The preparation method of composite membrane, it is characterised in that described In step 5, roast is in N2、H2Or N2-H2In the non-oxidizing atmospheres such as mixed gas, first with 0.2 DEG C/min~0.3 DEG C/ Min is warming up to 110 DEG C, is then warming up to 350~400 DEG C with 0.5 DEG C/min, is calcined 2h~3h, then with 0.5 DEG C/min~1.0 DEG C/min speed is cooled to room temperature.
CN201710859624.2A 2017-09-21 2017-09-21 A kind of Ni type hydrophobicity SiO2Composite membrane and preparation method thereof Pending CN107441948A (en)

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CN109331838A (en) * 2018-10-09 2019-02-15 华侨大学 A kind of preparation method of the super-hydrophobic catalytic film of noble metal@silicic acid nickel
CN110052181A (en) * 2019-04-30 2019-07-26 西安工程大学 A kind of preparation method of zirconia-supported hydrophobic silica composite membrane
CN110124530A (en) * 2019-04-30 2019-08-16 西安工程大学 Enhanced ZrO2Load hydrophobicity SiO2The preparation method of composite membrane
CN110201553A (en) * 2019-05-31 2019-09-06 西安工程大学 A kind of preparation method of titania oxide supported hydrophobic silica composite membrane
CN111389241A (en) * 2020-03-20 2020-07-10 西安工程大学 Niobium-doped hydrophobic SiO2Method for preparing composite membrane
CN111773928A (en) * 2020-07-02 2020-10-16 中国科学院城市环境研究所 Aerogel composite membrane and preparation method and application thereof

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CN101856595A (en) * 2010-06-10 2010-10-13 南京工业大学 Preparation method of metal doped organic-inorganic composite SiO2 film
WO2014105246A2 (en) * 2012-10-05 2014-07-03 Massachusetts Institute Of Technology Nanofluidic sorting system for gene synthesis and pcr reaction products
CN105498551A (en) * 2015-12-16 2016-04-20 西安工程大学 Preparation method of metal palladium loaded type SiO2 composite membrane

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CN101856595A (en) * 2010-06-10 2010-10-13 南京工业大学 Preparation method of metal doped organic-inorganic composite SiO2 film
WO2014105246A2 (en) * 2012-10-05 2014-07-03 Massachusetts Institute Of Technology Nanofluidic sorting system for gene synthesis and pcr reaction products
CN105498551A (en) * 2015-12-16 2016-04-20 西安工程大学 Preparation method of metal palladium loaded type SiO2 composite membrane

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109331838A (en) * 2018-10-09 2019-02-15 华侨大学 A kind of preparation method of the super-hydrophobic catalytic film of noble metal@silicic acid nickel
CN109331838B (en) * 2018-10-09 2021-04-30 华侨大学 Preparation method of noble metal @ nickel silicate super-hydrophobic catalytic film
CN110052181A (en) * 2019-04-30 2019-07-26 西安工程大学 A kind of preparation method of zirconia-supported hydrophobic silica composite membrane
CN110124530A (en) * 2019-04-30 2019-08-16 西安工程大学 Enhanced ZrO2Load hydrophobicity SiO2The preparation method of composite membrane
CN110201553A (en) * 2019-05-31 2019-09-06 西安工程大学 A kind of preparation method of titania oxide supported hydrophobic silica composite membrane
CN111389241A (en) * 2020-03-20 2020-07-10 西安工程大学 Niobium-doped hydrophobic SiO2Method for preparing composite membrane
CN111773928A (en) * 2020-07-02 2020-10-16 中国科学院城市环境研究所 Aerogel composite membrane and preparation method and application thereof

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Application publication date: 20171208