CN108675782A - A kind of preparation method of superoleophobic high tenacity ceramic membrane - Google Patents

A kind of preparation method of superoleophobic high tenacity ceramic membrane Download PDF

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CN108675782A
CN108675782A CN201810593220.8A CN201810593220A CN108675782A CN 108675782 A CN108675782 A CN 108675782A CN 201810593220 A CN201810593220 A CN 201810593220A CN 108675782 A CN108675782 A CN 108675782A
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ceramic membrane
parts
superoleophobic
film
high tenacity
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胡丽春
蒋梦成
陈帅
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Foshan Mausoleum Environmental Protection Technology Co Ltd
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Foshan Mausoleum Environmental Protection Technology Co Ltd
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Abstract

The present invention relates to a kind of preparation methods of superoleophobic high tenacity ceramic membrane, belong to environmental protection technical field of membrane separation.It is that feedstock processing obtains oxide powder that the present invention will utilize graphite powder first,It is mixed with N methyl pyrrolidones,Add zirconium oxide,Yttrium oxide,Copper powder is sufficiently mixed to obtain suspension,Suspension is added in slurry tank again, performed thin film is made,It is carried out surface activation process and superoleophobic surface layer is made,Muffle furnace high temperature is finally putting into calcine up to superoleophobic high tenacity ceramic membrane,The ceramic film dynamic performance of graphite oxide enhancing,Reinforce the oleophobic property of ceramic membrane while toughness,Keep ceramic membrane internal fiber structure finer and close,And yttrium oxide and zirconium oxide chemical property are stablized,It is resistant to chemical etching,It can make ceramic membrane that there is good toughness,Copper powder is introduced into ceramic membrane,Copper surface contact angle is set to significantly increase,Surface energy reduces,As superoleophobic interlayer,Introducing hydrophilic functional group further increases oleophobic effects simultaneously,It has broad application prospects.

Description

A kind of preparation method of superoleophobic high tenacity ceramic membrane
Technical field
The present invention relates to a kind of preparation methods of superoleophobic high tenacity ceramic membrane, belong to environmental protection membrane separation technique neck Domain.
Background technology
UF membrane is to efficiently separate new technology in the present age, is widely used in environmental protection and sewage disposal, biomedicine etc. Field provides new approach for circular economy production.The film overwhelming majority that water process uses is macromolecule organic film（With Based on PVDF, PVC, PES etc.）, but organic film oxidation resistance and contamination resistance are usually poor, limit its scope of application.
Ceramic membrane is also known as inorganic ceramic membrane, be it is a kind of with ceramic material prepare have high selection permeability rise centrifugation Diaphragm.Mainly using inorganic ceramic materials such as the aluminium oxide of different size, zirconium oxide, titanium oxide and silica as supporter, It is formed through surface coating, high-temperature firing.Ceramic membrane mainly has perforated membrane, filter membrane, packaging film, battery membranes, four kinds of thermal isolation film Class.Ceramic membrane have good separative efficiency height, effect stability, chemical stability, acid and alkali-resistance, organic solvent-resistant, resistance to bacterium, high temperature resistant, The crowds such as antipollution, high mechanical strength, regenerability are good, separation process is simple, low energy consumption, simple and convenient operation and maintenance, service life length More advantages have been successfully applied to food, beverage, plant（Medicine）Numerous necks such as object depth processing, biological medicine, fermentation, fine chemistry industry Domain, separation, clarification, purifying, concentration, degerming, the desalination etc. that can be used in technical process, becomes China's high performance membrane Material Field One of kind with the fastest developing speed and most promising.
The ceramic membrane generally structure type with two layers of unlike material：Surface filtration film and supporter.Weigh a kind of film Fine or not standard is：Under the premise of ensureing filtering accuracy, film has higher filtration flux；The aperture of skin covering of the surface is sufficiently large, it is ensured that compared with High filter efficiency；The aperture of skin covering of the surface is relatively uniform, ensures effective filtering accuracy；The ceramic membrane prepared is required to have simultaneously Preferable thermal shock resistance, chemical resistance, to be easy to backwash, contamination resistance strong etc.；Ensureing the same of uniform pore diameter distribution When, film will have enough intensity.
But most of ceramic membrane is adhered to by skin covering of the surface at present（Sintering）It is prepared on to supporter.Due to the use of Material it is different, boundary strength between the two is weak, is susceptible to the phenomenon that blowback film falls off, simultaneously because aperture difference compared with Greatly, it and is susceptible to plug-hole and reduces the filtration flux of integral membrane, the difference of coefficient of thermal expansion, and thermal shock process may be caused Middle skin covering of the surface falls off.In addition, ceramic membrane, when detaching oil phase, due to existing water-oil separating ceramic membrane materials, greasy dirt is often It adheres in material surface and hole, it is difficult to remove so that the filtration flux of film is low, and the efficiency of separation declines, and equipment is caused to be thrown Provide cost and higher operating costs, it is difficult to realize the marketization, limit use scope.
Therefore, it is badly in need of inventing a kind of ceramic membrane and preparation method thereof that can be solved the above problems.
Invention content
The technical problems to be solved by the invention：For current ceramic membrane oil strain energy force difference, the insufficient defect of toughness provides A kind of preparation method of superoleophobic high tenacity ceramic membrane.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of superoleophobic high tenacity ceramic membrane, it is characterised in that specifically preparation process is：
（1）It counts in parts by weight, weighs 10~15 parts of graphite powders, 2~5 parts of potassium permanganate powders and 15~20 parts of sulfuric acid and be put into burning In cup, beaker is put into water-bath and is stirred, acid solution is obtained；
（2）The hydrogen peroxide of acid solution quality 10~15% is added into above-mentioned beaker, heat up bath temperature, is dripped after isothermal reaction Add sodium hydroxide solution to adjust pH value to neutrality, obtains dispersion liquid, filter residue is obtained by filtration in dispersion liquid and filter residue is put in temperature Modified powder is obtained for dry 2~3h in 105~110 DEG C of baking ovens；
（3）By above-mentioned powder and N-Methyl pyrrolidone in mass ratio 1:In 5 input beakers, mixed solution is obtained after being stirred And stand, it counts in parts by weight, weighs 2~5 parts of Zirconium oxide powders, 3~7 parts of yttrium oxide powders, 12~15 parts of copper powders and 20~ 25 parts of mixed solutions are stirred, and obtain suspension；
（4）Suspension is added in slurry tank, 2~3h is stood after being vacuumized to slurry tank, then straight by nitrogen is passed through in slurry tank 2.0~2.5MPa is risen to air pressure, is that 30~40mL/min is pressed into spinning head using glass rotameter coutroi velocity, spray The outer diameter of silk head is 2.5mm, internal diameter 1.0mm, squeezes out fiber and sprays into 26~28h of progress gelling solidifications in metabisulfite solution, obtains To performed thin film；
（5）It counts in parts by weight, weighs 5~7 parts of sodium hydroxides and 1~3 part of ammonium sulfate and 30~35 parts of deionized waters are put into It is mixed to get reaction solution in beaker, uses absolute ethyl alcohol, acetone and deionized water each in being cleaned by ultrasonic instrument successively performed thin film Cleaning takes out film and obtains pretreatment film with 10~12h of reaction solution dipping, pretreatment film is used and contains matter after cleaning Measure the HS that score is 10~15%（CH2）CH3With 15~20% HS（CH2）10The mixed ethanol solution of COOH impregnates 24~26h, obtains To modified film；
（6）Above-mentioned modified film is put into drying in drying box, film is put into Muffle furnace after drying, pre-heating temperature elevation is simultaneously Heat preservation, then heated up with the heating rate of 5 DEG C/min, heat preservation calcining, discharging obtains superoleophobic high tenacity ceramic membrane.
Step（1）Described in sulfuric acid mass fraction be 85~90%, bath temperature be 0~3 DEG C, stir in a water bath Incorporation time is 2~3h.
Step（2）Described in hydrogen peroxide mass fraction be 20~25%, bath temperature is adjusted to 40~45 DEG C, in water The reaction time is 40~50min in bath, and the mass fraction of sodium hydroxide solution is 20~25%.
Step（3）Described in quiescent time be 4~6h, be stirred the time be 24~26h.
Step（4）Described in the flow velocity of spinner flowmeter control be 30~40mL/min, the quality of metabisulfite solution point Number is 30~40%.
Step（5）Described in be cleaned by ultrasonic instrument in scavenging period be 15~20min.
Step（6）Described in drying box in temperature be 120~150 DEG C, drying time is 25~26h, in Muffle furnace Pre-heating temperature elevation rate be 2 DEG C/min, preheating temperature be 720~750 DEG C, preheating time be 2~3h, calcination temperature be 1350~ 1400 DEG C, calcination time is 4~6h.
The method have the benefit that：
（1）The present invention first pre-processes graphite powder with potassium permanganate and the concentrated sulfuric acid, and then carrying out oxidation with hydrogen peroxide changes Property obtains oxide powder, and oxide powder is mixed with N-Methyl pyrrolidone, zirconium oxide, yttrium oxide, copper powder are added after mixing It is sufficiently mixed to obtain suspension, then suspension is added in slurry tank, after removing bubble under vacuum conditions, carry out spinneret processing Performed thin film is made, superoleophobic surface layer then is made in performed thin film progress surface activation process, is finally putting into Muffle furnace high Temperature is calcined up to superoleophobic high tenacity ceramic membrane, and graphene oxide is introduced into ceramic membrane by the present invention, graphene oxide mechanical property Can good, good toughness, while there is a large amount of phenolic hydroxyl group, carboxyl and other epoxy groups, these functional groups are hydrophilic and oleophobic can be with Can also enhance the oleophobic property of ceramic membrane while the ceramic film dynamic performance of enhancing, toughness, group possessed by graphene oxide with Particle forms covalent bond and other molecular links resultant force in ceramic membrane, and can chelate copper ion, makes ceramic membrane internal fiber knot Structure is finer and close, and ceramic film toughness is made to be further enhanced, and yttrium oxide and zirconium oxide chemical property are stablized, mechanical strength Height, it is resistant to chemical etching, it can make ceramic membrane that there is good toughness；
（2）Copper powder is introduced into ceramic membrane by the present invention, and carrying out processing to copper powder keeps copper powder anti-with ammonium sulfate under alkaline condition Kocide SD nano wire should be generated, then by Kocide SD nano wire and HS（CH2）CH3And HS（CH2）10COOH reacts, to copper surface Molecule is modified, and copper surface contact angle is made to significantly increase, and surface energy reduces, and becomes superoleophobic interlayer, while introducing hydrophily Functional group further increases oleophobic effects, has broad application prospects.
Specific implementation mode
It counts in parts by weight, weighs 10~15 parts of graphite powders, 2~5 parts of potassium permanganate powders and 15~20 parts of mass fractions It is put into beaker for 85~90% sulfuric acid, beaker is put into the water-bath that bath temperature is 0~3 DEG C and is stirred 2~3h, Obtain acid solution；The hydrogen peroxide that the mass fraction of acid solution quality 10~15% is 20~25% is added into above-mentioned beaker, And bath temperature is warming up to 40~45 DEG C, it is that 20~25% sodium hydroxides are molten that mass fraction is added dropwise after 40~50min of isothermal reaction Liquid adjusts pH value to neutrality, obtains dispersion liquid, and it is 105~110 DEG C filter residue to be obtained by filtration and filter residue is put in temperature dispersion liquid Baking oven in dry 2~3h obtain modified powder；By above-mentioned powder and N-Methyl pyrrolidone in mass ratio 1:5 input beakers In, mixed solution is obtained after being stirred and stands 4~6h, is counted in parts by weight, is weighed 2~5 parts of Zirconium oxide powders, 3~7 parts Yttrium oxide powder, 12~15 parts of copper powders and 20~25 parts of mixed solutions are stirred 24~26h, obtain suspension；By suspension Be added in slurry tank, 2~3h stood after being vacuumized to slurry tank, then nitrogen will be passed through in slurry tank until air pressure rise to 2.0~ 2.5MPa is that 30~40mL/min is pressed into spinning head using glass rotameter coutroi velocity, and the outer diameter of spinning head is 2.5mm, internal diameter 1.0mm squeeze out fiber and spray into progress 26~28h gellings in the metabisulfite solution that mass fraction is 30~40% Solidification, obtains performed thin film；It counts in parts by weight, weighs 5~7 parts of sodium hydroxides and 1~3 part of ammonium sulfate and 30~35 parts are gone Ionized water, which is put into beaker, is mixed to get reaction solution, uses absolute ethyl alcohol, acetone and deionized water in ultrasound successively performed thin film 15~20min is respectively cleaned in cleaning device, and film is taken out after cleaning and obtains pre-processing with 10~12h of reaction solution dipping thin Film will pre-process the film HS for being 10~15% containing mass fraction（CH2）CH3With 15~20% HS（CH2）10The mixing of COOH 24~26h of alcohol solution dipping, obtains modified film；Above-mentioned modified film is put into drying box, is 120~150 in temperature Film, is put into Muffle furnace, is warming up to the heating rate of 2 DEG C/min by dry 25~26h after drying under conditions of DEG C 720~750 DEG C, 2~3h is kept the temperature, then 1350~1400 DEG C are warming up to the heating rate of 5 DEG C/min, heat preservation 4~6h of calcining goes out Material obtains superoleophobic high tenacity ceramic membrane.
It counts in parts by weight, weighs the sulfuric acid that 10 parts of graphite powders, 2 parts of potassium permanganate powders and 15 parts of mass fractions are 85% It is put into beaker, beaker is put into the water-bath that bath temperature is 0 DEG C and is stirred 2h, obtains acid solution；To above-mentioned burning The hydrogen peroxide solution of acid solution quality 10% is added in cup, and bath temperature is warming up to 40 DEG C, is dripped after isothermal reaction 40min It is that 20% sodium hydroxide solution adjusts pH value to neutrality to add mass fraction, obtains dispersion liquid, filter residue is obtained by filtration in dispersion liquid and is incited somebody to action Filter residue is put in dry 2h in the baking oven that temperature is 105 DEG C and obtains modified powder；Above-mentioned powder and N-Methyl pyrrolidone are pressed into matter Measure ratio 1:In 5 input beakers, mixed solution is obtained after being stirred and stands 4h, is counted in parts by weight, 2 parts of zirconia powders are weighed End, 3 parts of yttrium oxide powders, 12 parts of copper powders and 20 parts of mixed solutions are stirred for 24 hours, obtain suspension；Suspension is added and is starched In batch can, 2h is stood after being vacuumized to slurry tank, then will be passed through in slurry tank nitrogen until air pressure rise to 2.0MPa, utilize glass Spinner flowmeter coutroi velocity is that 30mL/min is pressed into spinning head, and the outer diameter of spinning head is 2.5mm, internal diameter 1.0mm, is squeezed out Fiber, which sprays into the metabisulfite solution that mass fraction is 30~40%, carries out 26~28h gelling solidifications, obtains performed thin film；By weight Number meter is measured, 5 parts of sodium hydroxides and 1 part of ammonium sulfate is weighed and 30 parts of deionized waters is put into beaker and is mixed to get reaction solution, Performed thin film is respectively cleaned into 15min in being cleaned by ultrasonic instrument with absolute ethyl alcohol, acetone and deionized water successively, is taken after cleaning Go out film and obtain pretreatment film with reaction solution dipping 10h, the film HS for being 10% containing mass fraction will be pre-processed（CH2） CH3With 15% HS（CH2）10The mixed ethanol solution of COOH impregnates for 24 hours, obtains modified film；Above-mentioned modified film is put into dry In dry case, film, is put into Muffle furnace, with 2 DEG C/min's by dry 25h after drying under conditions of temperature is 120 DEG C Heating rate is warming up to 720 DEG C, keeps the temperature 2h, then be warming up to 1350 DEG C, heat preservation calcining 4h with the heating rate of 5 DEG C/min, discharging Obtain superoleophobic high tenacity ceramic membrane.
It counts in parts by weight, weighs the sulfuric acid that 13 parts of graphite powders, 3 parts of potassium permanganate powders and 17 parts of mass fractions are 87% It is put into beaker, beaker is put into the water-bath that bath temperature is 2 DEG C and is stirred 2h, obtains acid solution；To above-mentioned burning The hydrogen peroxide solution of acid solution quality 13% is added in cup, and bath temperature is warming up to 43 DEG C, is dripped after isothermal reaction 45min It is that 23% sodium hydroxide solution adjusts pH value to neutrality to add mass fraction, obtains dispersion liquid, filter residue is obtained by filtration in dispersion liquid and is incited somebody to action Filter residue is put in dry 2h in the baking oven that temperature is 107 DEG C and obtains modified powder；Above-mentioned powder and N-Methyl pyrrolidone are pressed into matter Measure ratio 1:In 5 input beakers, mixed solution is obtained after being stirred and stands 5h, is counted in parts by weight, 3 parts of zirconia powders are weighed End, 7 parts of yttrium oxide powders, 13 parts of copper powders and 23 parts of mixed solutions are stirred 25h, obtain suspension；Suspension is added and is starched In batch can, 2h is stood after being vacuumized to slurry tank, then will be passed through in slurry tank nitrogen until air pressure rise to 2.3MPa, utilize glass Spinner flowmeter coutroi velocity is that 35mL/min is pressed into spinning head, and the outer diameter of spinning head is 2.5mm, internal diameter 1.0mm, is squeezed out Fiber, which sprays into the metabisulfite solution that mass fraction is 30~40%, carries out 26~28h gelling solidifications, obtains performed thin film；By weight Number meter is measured, 6 parts of sodium hydroxides and 2 parts of ammonium sulfate is weighed and 33 parts of deionized waters is put into beaker and is mixed to get reaction solution, Performed thin film is respectively cleaned into 17min in being cleaned by ultrasonic instrument with absolute ethyl alcohol, acetone and deionized water successively, is taken after cleaning Go out film and obtain pretreatment film with reaction solution dipping 11h, the film HS for being 13% containing mass fraction will be pre-processed（CH2） CH3With 17% HS（CH2）10The mixed ethanol solution of COOH impregnates 25h, obtains modified film；Above-mentioned modified film is put into dry In dry case, film, is put into Muffle furnace, with 2 DEG C/min's by dry 25h after drying under conditions of temperature is 135 DEG C Heating rate is warming up to 735 DEG C, keeps the temperature 2h, then be warming up to 1375 DEG C, heat preservation calcining 5h with the heating rate of 5 DEG C/min, discharging Obtain superoleophobic high tenacity ceramic membrane.
It counts in parts by weight, weighs the sulfuric acid that 15 parts of graphite powders, 5 parts of potassium permanganate powders and 20 parts of mass fractions are 90% It is put into beaker, beaker is put into the water-bath that bath temperature is 3 DEG C and is stirred 3h, obtains acid solution；To above-mentioned burning The hydrogen peroxide solution of acid solution quality 15% is added in cup, and bath temperature is warming up to 45 DEG C, is dripped after isothermal reaction 50min It is that 25% sodium hydroxide solution adjusts pH value to neutrality to add mass fraction, obtains dispersion liquid, filter residue is obtained by filtration in dispersion liquid and is incited somebody to action Filter residue is put in dry 3h in the baking oven that temperature is 110 DEG C and obtains modified powder；Above-mentioned powder and N-Methyl pyrrolidone are pressed into matter Measure ratio 1:In 5 input beakers, mixed solution is obtained after being stirred and stands 6h, is counted in parts by weight, 5 parts of zirconia powders are weighed End, 7 parts of yttrium oxide powders, 15 parts of copper powders and 25 parts of mixed solutions are stirred 26h, obtain suspension；Suspension is added and is starched In batch can, 3h is stood after being vacuumized to slurry tank, then will be passed through in slurry tank nitrogen until air pressure rise to 2.5MPa, utilize glass Spinner flowmeter coutroi velocity is that 40mL/min is pressed into spinning head, and the outer diameter of spinning head is 2.5mm, internal diameter 1.0mm, is squeezed out Fiber, which sprays into the metabisulfite solution that mass fraction is 30~40%, carries out 26~28h gelling solidifications, obtains performed thin film；By weight Number meter is measured, 7 parts of sodium hydroxides and 3 parts of ammonium sulfate is weighed and 35 parts of deionized waters is put into beaker and is mixed to get reaction solution, Performed thin film is respectively cleaned into 20min in being cleaned by ultrasonic instrument with absolute ethyl alcohol, acetone and deionized water successively, is taken after cleaning Go out film and obtain pretreatment film with reaction solution dipping 12h, the film HS for being 15% containing mass fraction will be pre-processed（CH2） CH3With 20% HS（CH2）10The mixed ethanol solution of COOH impregnates 26h, obtains modified film；Above-mentioned modified film is put into dry In dry case, film, is put into Muffle furnace, with 2 DEG C/min's by dry 26h after drying under conditions of temperature is 150 DEG C Heating rate is warming up to 750 DEG C, keeps the temperature 3h, then be warming up to 1400 DEG C, heat preservation calcining 6h with the heating rate of 5 DEG C/min, discharging Obtain superoleophobic high tenacity ceramic membrane.
The ceramic membrane that comparative example is produced with company of Ningbo City is as a comparison case to superoleophobic high tenacity produced by the present invention Ceramic membrane in ceramic membrane and comparative example is detected, and testing result is as shown in table 1：
Bending strength test
It is executed with reference to GB/T1964 standards.
Air permeance resistance test is tested under conditions of testing wind speed in 1m/min.
Hydrophobicity test is tested using contact angle tester.
The ceramic membrane of example 1~3 and comparative example that acid and alkali resistance test prepares the present invention temperature be 100 DEG C, it is a concentration of It is impregnated in 40% concentrated sulfuric acid for 24 hours, the sodium hydroxide solution a concentration of 20% impregnates for 24 hours, tests the mechanical strength of ceramic membrane.Power Learn loss of strength rate, mass loss rate calculation GB/T1970 according to national standards《Porous ceramics acid and alkali resistance performance test side Method》It is measured.
Pure water flux refers under certain temperature and operating pressure, the spring that the film of unit area is penetrated within the unit interval Water.Pure water flux is directly proportional to filter efficiency.
Before test, the both ends of the ceramic membrane of preparating example 1~3 of the present invention and comparative example are sealed respectively, ceramic membrane is made Component, then respectively to one end of membrane module under conditions of meter pressure is 0.1MPa（Water inlet）It is passed through pure water, measures 30min The inner membrane member other end（Water outlet）The volume V of the pure water of transmission（L）, calculate the pure water flux of ceramic membrane（PWF）.
Pure water flux=through pure water volume/（Ceramic-film tube external surface area × permeation ceramic membrane required time × operation pressure Power）
1 performance measurement result of table
According to data in table 1 it is found that superoleophobic high tenacity ceramics film dynamic performance produced by the present invention is good, oil-water separation Good, hydrophobicity is good, and resistance to chemical corrosion is strong, and filter efficiency is high, has wide prospect of the application.

Claims (7)

1. a kind of preparation method of superoleophobic high tenacity ceramic membrane, it is characterised in that specifically preparation process is：
（1）It counts in parts by weight, weighs 10~15 parts of graphite powders, 2~5 parts of potassium permanganate powders and 15~20 parts of sulfuric acid and be put into burning In cup, beaker is put into water-bath and is stirred, acid solution is obtained；
（2）The hydrogen peroxide of acid solution quality 10~15% is added into above-mentioned beaker, heat up bath temperature, is dripped after isothermal reaction Add sodium hydroxide solution to adjust pH value to neutrality, obtains dispersion liquid, filter residue is obtained by filtration in dispersion liquid and filter residue is put in temperature Modified powder is obtained for dry 2~3h in 105~110 DEG C of baking ovens；
（3）By above-mentioned powder and N-Methyl pyrrolidone in mass ratio 1:In 5 input beakers, mixed solution is obtained after being stirred And stand, it counts in parts by weight, weighs 2~5 parts of Zirconium oxide powders, 3~7 parts of yttrium oxide powders, 12~15 parts of copper powders and 20~ 25 parts of mixed solutions are stirred, and obtain suspension；
（4）Suspension is added in slurry tank, 2~3h is stood after being vacuumized to slurry tank, then straight by nitrogen is passed through in slurry tank 2.0~2.5MPa is risen to air pressure, is that 30~40mL/min is pressed into spinning head using glass rotameter coutroi velocity, spray The outer diameter of silk head is 2.5mm, internal diameter 1.0mm, squeezes out fiber and sprays into 26~28h of progress gelling solidifications in metabisulfite solution, obtains To performed thin film；
（5）It counts in parts by weight, weighs 5~7 parts of sodium hydroxides and 1~3 part of ammonium sulfate and 30~35 parts of deionized waters are put into It is mixed to get reaction solution in beaker, uses absolute ethyl alcohol, acetone and deionized water each in being cleaned by ultrasonic instrument successively performed thin film Cleaning takes out film and obtains pretreatment film with 10~12h of reaction solution dipping, pretreatment film is used and contains matter after cleaning Measure the HS that score is 10~15%（CH2）CH3With 15~20% HS（CH2）10The mixed ethanol solution of COOH impregnates 24~26h, obtains To modified film；
（6）Above-mentioned modified film is put into drying in drying box, film is put into Muffle furnace after drying, pre-heating temperature elevation is simultaneously Heat preservation, then heated up with the heating rate of 5 DEG C/min, heat preservation calcining, discharging obtains superoleophobic high tenacity ceramic membrane.
2. a kind of preparation method of superoleophobic high tenacity ceramic membrane according to claim 1, it is characterised in that：Step（1） Described in sulfuric acid mass fraction be 85~90%, bath temperature be 0~3 DEG C, be stirred in a water bath the time be 2~3h.
3. a kind of preparation method of superoleophobic high tenacity ceramic membrane according to claim 1, it is characterised in that：Step（2） Described in hydrogen peroxide mass fraction be 20~25%, bath temperature is adjusted to 40~45 DEG C, in a water bath the reaction time be 40 The mass fraction of~50min, sodium hydroxide solution are 20~25%.
4. a kind of preparation method of superoleophobic high tenacity ceramic membrane according to claim 1, it is characterised in that：Step（3） Described in quiescent time be 4~6h, be stirred the time be 24~26h.
5. a kind of preparation method of superoleophobic high tenacity ceramic membrane according to claim 1, it is characterised in that：Step（4） Described in the flow velocity of spinner flowmeter control be 30~40mL/min, the mass fraction of metabisulfite solution is 30~40%.
6. a kind of preparation method of superoleophobic high tenacity ceramic membrane according to claim 1, it is characterised in that：Step（5） Described in be cleaned by ultrasonic instrument in scavenging period be 15~20min.
7. a kind of preparation method of superoleophobic high tenacity ceramic membrane according to claim 1, it is characterised in that：Step（6） Described in drying box in temperature be 120~150 DEG C, drying time is 25~26h, and the pre-heating temperature elevation rate in Muffle furnace is 2 DEG C/min, preheating temperature is 720~750 DEG C, and preheating time is 2~3h, and calcination temperature is 1350~1400 DEG C, and calcination time is 4~6h.
CN201810593220.8A 2018-06-11 2018-06-11 A kind of preparation method of superoleophobic high tenacity ceramic membrane Withdrawn CN108675782A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109046036A (en) * 2018-10-19 2018-12-21 陈辉昌 A kind of preparation method of environment-friendly ceramic film
CN111763095A (en) * 2020-07-08 2020-10-13 山东理工大学 Zirconia whisker reinforced zirconia ceramic ultrafiltration membrane and preparation method thereof
CN111871228A (en) * 2020-07-22 2020-11-03 浙江工业大学 ZnO micro-nano composite structure ceramic membrane and preparation method and application thereof
CN113801134A (en) * 2021-10-28 2021-12-17 南京久安源环保科技有限公司 Production process for simultaneously producing ginkgolide, ginkgetin, ginkgopolysaccharide and shikimic acid

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109046036A (en) * 2018-10-19 2018-12-21 陈辉昌 A kind of preparation method of environment-friendly ceramic film
CN111763095A (en) * 2020-07-08 2020-10-13 山东理工大学 Zirconia whisker reinforced zirconia ceramic ultrafiltration membrane and preparation method thereof
CN111871228A (en) * 2020-07-22 2020-11-03 浙江工业大学 ZnO micro-nano composite structure ceramic membrane and preparation method and application thereof
CN113801134A (en) * 2021-10-28 2021-12-17 南京久安源环保科技有限公司 Production process for simultaneously producing ginkgolide, ginkgetin, ginkgopolysaccharide and shikimic acid
CN113801134B (en) * 2021-10-28 2023-10-03 南京久安源环保科技有限公司 Production process for simultaneously producing bilobalide, ginkgetin, ginkgolic polysaccharide and shikimic acid

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