CN101069819A - Method for preparing composite ceramic super-filtering film on porous stainless steel substrate - Google Patents

Method for preparing composite ceramic super-filtering film on porous stainless steel substrate Download PDF

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CN101069819A
CN101069819A CN 200710017580 CN200710017580A CN101069819A CN 101069819 A CN101069819 A CN 101069819A CN 200710017580 CN200710017580 CN 200710017580 CN 200710017580 A CN200710017580 A CN 200710017580A CN 101069819 A CN101069819 A CN 101069819A
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film
composite ceramic
colloidal sol
counterdie
flask
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CN100478057C (en
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李忠宏
杨公明
仇农学
杨祖培
杨继红
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Northwest A&F University
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Northwest A&F University
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Abstract

The present invention discloses a method for preparing composite ceramic ultrafiltration membrane on porous stainless steel basal body. Its technical scheme includes the following steps: respectively preparing TiO2 sol, SiO2 sol, Al2O3 sol and ZrO2 sol; preparing Al2O3 bottom membrane; respectively preparing SiO2 composite ceramic membrane, ZrO2 composite ceramic membrane and TiO2 composite ceramic membrane on the bottom membrane, According to the above-mentioned technical scheme three types of composite ceramic ultrafiltration membrane can be prepared on the porous stainless steel basal body whose pore size is 1 micrometer. Said composite ceramic membrane can be further made into the ultrafiltration membrane component.

Description

A kind of method that on porous stainless steel base, prepares composite ceramic super-filtering film
Technical field
The present invention relates to a kind of membrane separation technique, specifically is a kind of method for preparing composite ceramic super-filtering film on porous stainless steel base, belongs to the metallurgical chemistry field.
Background technology
Membrane separation technique is novel, efficient, the accurate isolation technics of succeeding in developing in 20th century, is widely used in fields such as electronics, food, environmental protection, and the film that uses in the industrial production comprises organic film, ceramic membrane and metal film with regard to its material at present.Organic film is to be that matrix, high-molecular organic material are a kind of asymmetric membrane that film material is prepared from the high-molecular organic material, and the shortcoming of macromolecular material is that heat endurance and corrosion resistance are poor, not easy cleaning, intensity is low, the life-span is short; Ceramic membrane is to be that matrix, pottery of the same race or not of the same race are a kind of asymmetric membrane that film material is prepared from the pottery, although its heat endurance and corrosion resistance are better than organic film, but the fragility of ceramic membrane is too big, takes place easily in the use to damage suddenly to cause separation function to be lost.All there be defective and the deficiency on the performance in employed membrane material in the membrane separation plant, so utilize ceramic super-filtering film that on porous metals matrix preparation has a separation function that the development of membrane separation technique is had important practical significance.
Summary of the invention
The present invention seeks to disclose a kind of method that on porous stainless steel base, prepares composite ceramic super-filtering film, the new membrane material that provides a kind of intensity to be higher than ceramic membrane for membrane separation technique.
The present invention takes following technical scheme:
Prepare TiO respectively 2Colloidal sol, SiO 2Colloidal sol, Al 2O 3Colloidal sol and ZrO 2Colloidal sol → preparation Al 2O 3Counterdie → on counterdie, prepare respectively SiO 2Composite ceramic film, ZrO 2Composite ceramic film and TiO 2Composite ceramic film → porous stainless steel base composite ceramic milipore filter.
Can prepare three types composite ceramic super-filtering film according to technique scheme on the porous stainless steel base of aperture 1 μ m, its pore size distribution range is 0.08～0.3 μ m.This composite ceramic film can and then be made hyperfiltration membrane assembly, replace the organic or ceramic super-filtering film of use at present, can be widely used in electronics, food, environmental protection, chemical industry, metallurgy, medicine, biology, the energy, oil, field such as bionical, have wide market application prospect.
The specific embodiment
The present invention specifically can be undertaken by following technical scheme:
A. prepare TiO 2Colloidal sol
A.1 mol ratio: Ti (OBu) 4: H 2O: HNO 3: EtOH=1: 300: 1.2: 2
A.2 remove ionized water and place flask
A.3 get Ti (OBu) 4In beaker
A.4 pipette the ethanol adding and fill Ti (OBu) 4Beaker in, stir
A.5 under the vigorous stirring, with Ti (OBu) 4Ethanolic solution dropwise be added drop-wise in the flask
A.6 in flask, drip HNO 3Solution
A.7 60 ℃～65 ℃ are back to transparent
A.8 make TiO 2Colloidal sol;
B. prepare SiO 2Colloidal sol
B.1 mol ratio: TEOS: H 2O: EtOH: NH 4OH=1: 52.6: 38.2: 2.1
B.2 pipette absolute ethyl alcohol and place flask
B.3 add TEOS again and become mixed liquor
B.4 on flask, assemble reflux, mixed liquor is heated to 5O ℃
B.5 pipette deionized water and ammoniacal liquor in beaker, mix
B.6 the ethanolic solution temperature for the treatment of TEOS begins dropwise dropping ammonia solution when reaching 50 ℃
B.7 drip the back in 50 ℃～60 ℃ following colloidal sol 12～14h
B.8 make SiO 2Colloidal sol;
C. prepare Al 2O 3Colloidal sol
C.1 mol ratio: Al (C 3HO) 3: H 2O: HNO 3=1: 300: 0.22
C.2 remove ionized water and place flask
C.3 on flask, assemble reflux, add hot deionized water to 85 ℃
C.4 weigh Al (C 3HO) 3, add flask behind the porphyrize
C.5 drip HNO 3
C.6 85 ℃～90 ℃ following peptization 12～14h
C.7 make Al 2O 3Colloidal sol;
D. prepare ZrO 2Colloidal sol
D.1 the ZrOCl of volume ratio: 0.5mol/L 28H 2The oxalic acid of O: 0.25mol/L=1: 0.5
D.2 pipette ZrOCl 28H 2O solution adds conical flask
D.3 heated solution to 85 ℃ stirs
D.4 pipette oxalic acid solution, dropwise drip
D.5 continue to stir 30～35 minutes
D.6 make ZrO 2Colloidal sol;
E. prepare Al 2O 3Counterdie
E.1 with Al 2O 3Colloidal sol is diluted to 0.032mol/L with deionized water
E.2 add 1% polyvinyl alcohol (PVA)
E.3 15 ℃～20 ℃ following ageing 12～14h
E.4 film with dip coating
E.5 wet film obtains the xerogel film in 15 ℃～20 ℃ air drying
E.6 with the heat treatment of xerogel film
E.6.1 temperature is 1200 ℃～1300 ℃
E.6.2 time 3～4h
E.7 make Al 2O 3Counterdie;
F. on counterdie, prepare SiO 2The type ceramic membrane
F.1 be 0.047mol/L with deionized water dilution collosol concentration
F.2 add 1% polyvinyl alcohol (PVA)
F.3 15 ℃～20 ℃ following ageing 12～14h
F.4 film with dip coating
F.5 wet film obtains the xerogel film in 15 ℃～20 ℃ air drying
F.6 heat treatment
F.6.1 temperature is 800 ℃～900 ℃
F.6.2 time 3～4h
F.7 obtain SiO 2The type composite ceramic super-filtering film;
G. on counterdie, prepare ZrO 2The type ceramic membrane
G.1 be 0.47mol/L with deionized water dilution collosol concentration
G.2 add 1% polyvinyl alcohol (PVA)
G.3 15 ℃～20 ℃ following ageing 12～14h
G.4 film with dip coating
G.5 wet film obtains the xerogel film in 15 ℃～20 ℃ air drying
G.6 heat treatment
G.6.1 temperature is 800 ℃～900 ℃
G.6.2 time 3～4h;
G.7 obtain ZrO 2The type composite ceramic super-filtering film;
H. on counterdie, prepare TiO 2The type ceramic membrane
H.1 be 0.0036mol/L with deionized water dilution collosol concentration
H.2 add 1% polyvinyl alcohol (PVA)
H.3 15 ℃～20 ℃ following ageing 12～14h
H.4 film with dip coating
H.5 wet film obtains the xerogel film in 15 ℃～20 ℃ air drying
H.6 heat treatment
H.6.1 temperature is 800 ℃～900 ℃
H.6.2 time 3～4h
H.7 obtain TiO 2The type composite ceramic super-filtering film.
Make three types porous stainless steel base composite ceramic milipore filter, from Al 2O 3Counterdie is to its aperture of teleblem distribution gradient successively, and the aperture minimum of outermost tunic, its pore size distribution range are 0.08～0.3 μ m.
Embodiment:
1. at first dilute Al 2O 3Colloidal sol to concentration is 0.032mol/L, adds 1% PVA binder, stirs, and places ageing 12～14h down for 15 ℃～20 ℃;
2. the stirring preparation liquid immerses abundant absorption preparation liquid in the preparation liquid with stainless steel base, lifts out stainless steel base afterwards, and gets rid of the too much preparation liquid in surface, forms the wet dissolved glue film of one deck on stainless steel base;
3. wet film is placed on air drying, promptly becomes the xerogel film;
4. the xerogel film is heat-treated under 1200 ℃～1300 ℃, 3～4 hours time, then can on porous stainless steel base, form one deck Al 2O 3The pottery counterdie;
5. dilute TiO respectively 2, SiO 2, ZrO 2Three kinds of colloidal sols are to 0.036mol/L, 0.047mol/L and 0.47mol/L;
6. in above-mentioned three kinds of colloidal sols, add 1% PVA respectively and prepare preparation liquid;
7. carry out filming the second time with dip coating, obtain SiO 2, ZrO 2, TiO 2Three types wet film;
8. three types wet film all in 15 ℃～20 ℃ air drying, promptly becomes the xerogel film;
With the xerogel film in 800 ℃～900 ℃ following heat treatment 3～4h, can be in the aperture porous stainless steel surface of 1 μ m obtain three types multi-layer ceramics composite hyperfiltration membrane, the pore size distribution range of its rete is 0.08～0.3 μ m.

Claims (3)

1. a method for preparing composite ceramic super-filtering film on porous stainless steel base is characterized in that taking following technical scheme: prepare TiO respectively 2Colloidal sol, SiO 2Colloidal sol, Al 2O 3Colloidal sol and ZrO 2Colloidal sol → preparation Al 2O 3Counterdie → on counterdie, prepare respectively SiO 2Composite ceramic film, ZrO 2Composite ceramic film and TiO 2Composite ceramic film → porous stainless steel base composite ceramic milipore filter.
2. a kind of method for preparing composite ceramic super-filtering film on porous stainless steel base according to claim 1 is characterized in that specifically can being undertaken by following technical scheme:
2.a preparation TiO 2Colloidal sol
2.a.1 mol ratio: Ti (OBu) 4: H 2O: HNO 3: EtOH=1: 300: 1.2: 2
Place flask 2.a.2 remove ionized water
2.a.3 get Ti (OBu) 4In beaker
Fill Ti (OBu) 2.a.4 pipette the ethanol adding 4Beaker in, stir
2.a.5 under the vigorous stirring, with Ti (OBu) 4Ethanolic solution dropwise be added drop-wise in the flask
2.a.6 in flask, drip HNO 3Solution
2.a.7 60 ℃～65 ℃ are back to transparent
2.a.8 make TiO 2Colloidal sol;
2.b preparation SiO 2Colloidal sol
2.b.1 mol ratio: TEOS: H 2O: EtOH: NH 4OH=1: 52.6: 38.2: 2.1
Place flask 2.b.2 pipette absolute ethyl alcohol
Become mixed liquor 2.b.3 add TEOS again
2.b.4 on flask, assemble reflux, mixed liquor be heated to 50 ℃
2.b.5 pipette deionized water and ammoniacal liquor in beaker, mix
Begin dropwise dropping ammonia solution when reaching 50 ℃ 2.b.6 treat the ethanolic solution temperature of TEOS
2.b.7 drip the back in 50 ℃～60 ℃ following colloidal sol 12～14h
2.b.8 make SiO 2Colloidal sol;
2.c preparation Al 2O 3Colloidal sol
2.c.1 mol ratio: Al (C 3HO) 3: H 2O: HNO 3=1: 300: 0.22
Place flask 2.c.2 remove ionized water, the assembling reflux
2.c.3 on flask, assemble reflux, add hot deionized water to 85 ℃
2.c.4 weigh Al (C 3HO) 3, add flask behind the porphyrize
2.c.5 drip HNO 3
2.c.6 85 ℃～90 ℃ following peptization 12～14h
2.c.7 make Al 2O 3Colloidal sol;
2.d preparation ZrO 2Colloidal sol
The ZrOCl of 2.d.1 volume ratio: 0.5mol/L 28H 2The oxalic acid of O: 0.25mol/L=1: 0.5
2.d.2 pipette ZrOCl 28H 2O solution adds conical flask
2.d.3 heated solution to 85 ℃ stirs
2.d.4 pipette oxalic acid solution, dropwise drip
2.d.5 continue to stir 30～35 minutes
2.d.6 make ZrO 2Colloidal sol;
2.e preparation Al 2O 3Counterdie
2.e.1 with Al 2O 3Colloidal sol is diluted to 0.032mol/L with deionized water
2.e.2 add 1% polyvinyl alcohol (PVA)
2.e.3 15 ℃～20 ℃ following ageing 12～14h
2.e.4 film with dip coating
2.e.5 wet film obtains the xerogel film in 15 ℃～20 ℃ air drying
2.e.6 with the heat treatment of xerogel film
2.e.6.1 1200 ℃～1300 ℃ of temperature
2.e.6.2 time 3～4h
2.e.7 make Al 2O 3Counterdie;
2.f on counterdie, prepare SiO 2The type ceramic membrane
2.f.1 with deionized water dilution collosol concentration is 0.047mol/L
2.f.2 add 1% polyvinyl alcohol (PVA)
2.f.3 15 ℃～20 ℃ following ageing 12～14h
2.f.4 film with dip coating
2.f.5 wet film obtains the xerogel film in 15 ℃～20 ℃ air drying
2.f.6 heat treatment
2.f.6.1 800 ℃～900 ℃ of temperature
2.f.6.2 time 3～4h
2.f.7 obtain SiO 2The type composite ceramic super-filtering film;
2.g on counterdie, prepare ZrO 2The type ceramic membrane
2.g.1 with deionized water dilution collosol concentration is 0.47mol/L
2.g.2 add 1% polyvinyl alcohol (PVA)
2.g.3 15 ℃～20 ℃ following ageing 12～14h
2.g.4 film with dip coating
2.g.5 wet film obtains the xerogel film in 15 ℃～20 ℃ air drying
2.g.6 heat treatment
2.g.6.1 800 ℃～900 ℃ of temperature
2.g.6.2 time 3～4h;
2.g.7 obtain ZrO 2The type composite ceramic super-filtering film;
2.h on counterdie, prepare TiO 2The type ceramic membrane
2.h.1 with deionized water dilution collosol concentration is 0.0036mol/L
2.h.2 add 1% polyvinyl alcohol (PVA)
2.h.3 15 ℃～20 ℃ following ageing 12～14h
2.h.4 film with dip coating
2.h.5 wet film obtains the xerogel film in 15 ℃～20 ℃ air drying
2.h.6 heat treatment
2.h.6.1 800 ℃～900 ℃ of temperature
2.h.6.2 time 3～4h
2.h.7 obtain TiO 2The type composite ceramic super-filtering film.
3. a kind of method for preparing composite ceramic super-filtering film on porous stainless steel base according to claim 1 is characterized in that making three types porous stainless steel base composite ceramic milipore filter, from Al 2O 3Counterdie is to its aperture of teleblem distribution gradient successively, and the aperture minimum of outermost tunic, its pore size distribution range are 0.08～0.3 μ m.
CNB2007100175805A 2007-03-29 2007-03-29 Method for preparing composite ceramic super-filtering film on porous stainless steel substrate Expired - Fee Related CN100478057C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101265123B (en) * 2008-04-18 2010-12-01 南京工业大学 Method for preparing small aperture ceramic film
CN103100309A (en) * 2013-01-28 2013-05-15 西北农林科技大学 Method for preparing porous stainless steel iron oxide film for removing heavy metal ion Cr (VI) in aqueous solution
CN104741007A (en) * 2015-04-16 2015-07-01 柳州豪祥特科技有限公司 Preparation method of membrane separation layer for water treatment
CN105749763A (en) * 2014-12-18 2016-07-13 华东理工大学 Preparation method of ceramic hollow-fiber solvent-resistant composite nanofiltration membrane
CN108602037A (en) * 2016-02-02 2018-09-28 华盛顿大学 Ceramic selective membrane
CN111304652A (en) * 2020-03-22 2020-06-19 浙江宇达新材料有限公司 Process method for replacing phosphorization by coating ceramic membrane
CN111495209A (en) * 2020-04-03 2020-08-07 南京钛净流体技术有限公司 Ceramic membrane and preparation method thereof
CN112159208A (en) * 2020-09-28 2021-01-01 上海应用技术大学 Preparation method of alumina-silica composite ceramic membrane

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101265123B (en) * 2008-04-18 2010-12-01 南京工业大学 Method for preparing small aperture ceramic film
CN103100309A (en) * 2013-01-28 2013-05-15 西北农林科技大学 Method for preparing porous stainless steel iron oxide film for removing heavy metal ion Cr (VI) in aqueous solution
CN103100309B (en) * 2013-01-28 2015-06-17 西北农林科技大学 Method for preparing porous stainless steel iron oxide film for removing heavy metal ion Cr (VI) in aqueous solution
CN105749763A (en) * 2014-12-18 2016-07-13 华东理工大学 Preparation method of ceramic hollow-fiber solvent-resistant composite nanofiltration membrane
CN105749763B (en) * 2014-12-18 2018-07-10 华东理工大学 A kind of preparation method of Ceramic Hollow Fiber solvent-resistant compound nanofiltration membrane
CN104741007A (en) * 2015-04-16 2015-07-01 柳州豪祥特科技有限公司 Preparation method of membrane separation layer for water treatment
CN108602037A (en) * 2016-02-02 2018-09-28 华盛顿大学 Ceramic selective membrane
CN111304652A (en) * 2020-03-22 2020-06-19 浙江宇达新材料有限公司 Process method for replacing phosphorization by coating ceramic membrane
CN111495209A (en) * 2020-04-03 2020-08-07 南京钛净流体技术有限公司 Ceramic membrane and preparation method thereof
CN112159208A (en) * 2020-09-28 2021-01-01 上海应用技术大学 Preparation method of alumina-silica composite ceramic membrane

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