CN110002893A - A kind of preparation method of ceramic super-filtering film - Google Patents
A kind of preparation method of ceramic super-filtering film Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of ceramic super-filtering film, belong to filtration art.The present invention makes the heavy metal ion in zircon sand form citrate by citric acid complex by raw materials mixing and ball millings such as zircon sand, citric acid, acetic acid, and being formed by nanofiber sponge medium-length fibre has uniform pores, the relatively narrow ceramic super-filtering film of pore-size distribution；Temperature is 400~450 DEG C after heating up for the first time in sintering process in the present invention, at this moment liquid phase is silica solution, amorphous silicon di-oxide has very high activity, with the variation of saturated vapor pressure after temperature continues to increase, adjustable non-uniform hole, the mechanical strength and consistency for improving ceramic super-filtering film form the amorphous Si O of high activity on surface2Oxide layer forms more hydrophilic silicone hydroxyls under the negative oxygen ion effect that nanofiber sponge and peach gum pyrolysis generate, and the long hole of connection and hydrophilic silicone hydroxyl synergistic effect improve the flux of ceramic super-filtering film, have broad application prospects.
Description
Technical field
The invention discloses a kind of preparation methods of ceramic super-filtering film, belong to filtration art.
Background technique
The growth requirement in epoch has been complied in the appearance of Ceramic excessive filtration membrane technology, it belongs to a kind of inorganic separating film, accounts at present
The 80% of this field, sales volume is also held a safe lead, it is seen that the importance of its status, ceramic super-filtering film can carry out essence to substance
Close to be separated by filtration, so receiving the favor of people, now with the continuous promotion of membrane technology, the development of accurate seperation film is
Become an independent development trend.So application trend of the Ceramic excessive filtration membrane technology in substance separation is still continuous
Promotion in.
The maximum feature of ceramic super-filtering film is exactly that aperture is atomic small, can filter and retain extremely small organic matter, its energy
Enough to be separated in the case where room temperature, the energy consumption of utilization is lower, and the utilization rate of water is high.In lactic acid process purification engineering, pottery
The advantage of porcelain device for ultrafiltration membrane is just more prominent, its antifouling property is stronger, and penetrating fluid is best in quality, can substitute precipitating
Process, this just makes lactic acid purification process more facilitation, improves production efficiency.Since lactic acid is using relatively broad, institute
Also to have different requirements in purity of the different fields to lactic acid, the selection on purifying technique is had to using reasonable
Mode, can reduce the production cost of lactic acid, while promoting productivity, guarantee the quality of production.In ceramic super-filtering film
It is certain it is noted that carry out the maintenance of science to it in use process, and regularly cleaned, guarantee the normal operation of equipment, guarantor
The quality for demonstrate,proving product, extends the service life of equipment.
The distinctive micropore of ultrafiltration membrane can effectively detention bacterium, most of viruses, colloid and mud, reach separation, classification,
The purpose of purifying, concentration.Nowadays it has been widely applied in industry and sphere of life, for separating, being concentrated, purifying biological system
Product.
Ceramic super-filtering film particles sintering method multi-purpose greatly prepares basement membrane at present, and prepares conversion zone with sol-gel method, is making
Porous supporter will be used as carrier during standby ceramic super-filtering film, and the shape of carrier is all unified fixation, no
Can arbitrarily it change with needs of production, complicated planform can not also form, to limit making for ceramic super-filtering film
Use range.A kind of preparation method of zirconia ceramic ultrafiltration film of patent disclosure, the present invention prepare oxalic acid by chemical coprecipitation
The Zirconium powder easily dispersed is prepared using low temperature calcination method for zirconium colloidal sol, then carries out grinding distribution, then be added at
Film auxiliary agent, drying control agent, defoaming agent be made coating liquid, which is applied on porous ceramic film support, by drying,
Sintering obtains zirconia ceramic ultrafiltration film film layer, reduces energy consumption, improves the cost performance of ultrafiltration membrane.Patent disclosure is a kind of non-right
Claim structural ceramics ultrafiltration membrane and preparation method thereof, the present invention disperses one dimension fibre shape material in colloidal sol, is sufficiently mixed, and is added
Dispersing agent, thickener, defoaming agent are configured to preparation liquid, and the film on porous supporting body forms transition zone, in transition after drying
Layer surface coating colloidal sol preparation liquid, wet film is dried, is dried, roasting, and Temperature fall, should up to unsymmetric structure ceramic super-filtering film
Ceramic super-filtering film has the advantages that water flux significantly.A kind of preparation method of ceramic micro filter film of patent disclosure, this method is by nanoscale
Oxide is scattered in by being formed uniformly coating liquid, then add in dispersing agent, thickener, defoaming agent and preservative mixed aqueous solution
Template, with obtained coating liquid on porous metals or porous ceramic support film, and dry in wet film, dry
Afterwards, processing removing polymer template agent, finally carries out roasting molding, obtains ceramic microfiltration membrane.
Above-mentioned patent is all the preparation method of ceramic super-filtering film, using different formula and preparation method, being made property
The excellent ceramic super-filtering film of energy, but carrier of the porous supporting body as film is all employed, so that the ultrafiltration membrane of preparation has shape
Defect single, molding cycle is long, ultrafiltration membrane forming method falls behind, is unfavorable for the need of ceramic super-filtering film in the actual production process
It wants.There is also pore size control it is difficult, the lower defect of the flux of membrane aperture wider distribution and film.
Therefore, inventing the ceramic super-filtering film that a kind of aperture is controllable and membrane flux is high is necessary to filtration art
's.
Summary of the invention
Present invention mainly solves the technical issues of, it is difficult for the pore size control of ceramic super-filtering film film, membrane aperture distribution compared with
The lower defect of the flux of width and film, provides a kind of preparation method of ceramic super-filtering film.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of ceramic super-filtering film the preparation method comprises the following steps:
(1) silica solution that dry gel powder and mass fraction are 35% is mixed to get Bibulous Silica Gel, will having a size of 60mm × 60mm ×
The nanofiber sponge of 80mm is immersed in the sodium hydroxide solution that mass fraction is 15%, is heated to 40~45 DEG C, hydrolysis 40
~45min, is put into clear water after taking-up and washes by rubbing with the hands, is put into 4~5h of dipping in Bibulous Silica Gel after natural drying, and taking-up is put into silicon carbide
40~45min of impregnation in ceramic slurry is obtained to fired porous ceramic film support；
(2) it will be put into fired porous ceramic film support equipped in the reaction kettle in spare zirconium acetate colloidal sol, under oxygen atmosphere
70~80 DEG C are heated to, takes out and is placed in high temperature resistance furnace after 30~40min of isothermal holding, heating sintering, natural cooling
Demoulding obtains ceramic super-filtering film after to room temperature；
Dry gel powder the preparation method comprises the following steps:
30~40g peach gum is placed in three-necked flask, blender is started, is stirred with the revolving speed of 250~300r/min, is dripped with constant pressure
The inclined silicon of nine water that 200~300mL mass fraction is 40% is added dropwise with the drop rate of 2~3mL/min into three-necked flask for liquid funnel
Acid sodium solution is stirred to react 2~3h, and cooled to room temperature is filtered after discharging with vacuum filtration machine, and removal filtrate is filtered
Slag is placed in the baking oven that set temperature is 45~50 DEG C with petroleum ether, and dry 3~4h is ground up, sieved to obtain xerogel
Powder；
Silicon carbide ceramics slurry preparation method are as follows:
(1) carborundum powder, schmigel, kaolin powder are put into 4~5min of mixing in batch mixer, obtain mixed powder, to mixing
Silica solution, the deionized water that mass fraction is 40% are added in powder, the hydroxide that mass fraction is 40% is added after being dispersed with stirring
Sodium solution, adjusting pH is 10.0~10.5, stands 2~3h, obtains mixed slurry；
(2) above-mentioned mixed slurry is placed in ball mill, rotational speed of ball-mill is 400~500r/min, after 1~2h of ball milling, to ball milling
The n-butanol that mixed slurry weight 2% is added in machine stands 40~50min of defoaming, obtains silicon carbide ceramics slurry；
Zirconium acetate colloidal sol the preparation method comprises the following steps:
Zircon sand, citric acid, acetic acid, deionized water is taken to be put into ball mill, after 4~5h of ball milling, filtering removal filter residue obtains ball
Ball milling slurries are placed in reaction kettle, heating water bath by grinding slurry, and 30~40min of concentration obtains zirconium acetate colloidal sol.
The silica solution mixing mass ratio that dry gel powder and mass fraction are 35% is 1 ︰ 10.
Heat up sintering process in high temperature resistance furnace are as follows: is warming up to 400~450 DEG C with the rate program of 5~10 DEG C/min, perseverance
Temperature 45~55min of processing, is continuously heating to 1300~1350 DEG C, 3~4h of Isothermal sinter.
The be sieved specification of dry gel powder is limited to 200 mesh in the preparation method of dry gel powder.
Mixed slurry each component raw material in silicon carbide ceramics slurry preparation method, according to parts by weight, including carborundum powder
60~65 parts, 30~35 parts of schmigel, 10~15 parts of kaolin powder, silica solution 8~10 part, deionization of the mass fraction for 40%
80~100 parts of water.
Controlling ball material mass ratio in silicon carbide ceramics slurry preparation method when mixed slurry ball milling is 10 ︰ 1.
Zirconium acetate colloidal sol each component raw material in zirconium acetate colloidal sol preparation method, according to parts by weight, including zircon sand 70~
80 parts, 20~25 parts of citric acid, 40~45 parts of acetic acid, 100~120 parts of deionized water.
Temperature when ball milling slurries are concentrated in zirconium acetate colloidal sol preparation method, further control is 70~75 DEG C.
The beneficial effects of the present invention are:
(1) present invention prepares dry gel powder using peach gum and non-hydrate sodium metasilicate solution as raw material, by carborundum powder, schmigel, height
Soil powder mixing in ridge is put into silica solution, silicon carbide ceramics slurry is obtained through dilution, alkalization, ball milling, defoaming, by nanofiber sponge
It is put into the paraffin silica gel that dry gel powder and silica solution mix and impregnates, is dried to obtain to fired porous ceramic film support, it will
It is put into zirconium acetate colloidal sol to fired porous ceramic film support, heating is carried on zirconium acetate to fired porous ceramic film support
In micropore surface, it is sintered to obtain ceramic super-filtering film through secondary temperature elevation, the present invention is mixed by raw materials such as zircon sand, citric acid, acetic acid
Ball milling is closed, so that the heavy metal ion in zircon sand is formed citrate by citric acid complex, to extract zirconia ceramics film
Presoma zirconium acetate colloidal sol, after sintering to fired porous ceramic film support, nanofiber sponge pyrolysis ceramic membrane support
Uniform porous structure is formed in body, peach gum has lubricant effect that can be formed uniformly in first time high temperature sintering in Bibulous Silica Gel
Connection pore structure, zirconium acetate form zirconia ceramics film during the sintering process, are formed and are had by nanofiber sponge medium-length fibre
The ceramic super-filtering film for having uniform pores, pore-size distribution relatively narrow；
(2) temperature is 400~450 DEG C after heating up for the first time in sintering process in the present invention, and at this moment liquid phase is silica solution, silica solution
In amorphous silica gel is dehydrated and occurs particle agglomeration first in temperature-rise period, on the one hand become Si-OH key
Si-O bond is closed, and generates preliminary densification, while the pyrolysis of nanofiber sponge generates the long hole of uniform connection, makes green body
Some strength and shape are kept in middle low temperature, on the other hand, amorphous silicon di-oxide has very high activity, continues in temperature
With the variation of saturated vapor pressure after raising, a variety of crystalline state and variant can be formed, thermodynamically stable phase is generated, works as saturated vapor pressure
When reaching certain value, these stable solid phases can be changed into liquid phase, to promote the flowing of powder, diffusion, firing, when high temperature may be used also
It is reacted with other oxides in matrix, generates low melting point eutectic, to play the work for making up big gap, promoting densification
With adjustable non-uniform hole improves the mechanical strength and consistency of ceramic super-filtering film, and silicon carbide fills in the base
Work as skeleton, sintering forms the densification of the second phase product under middle cryogenic conditions, and the power of ceramic super-filtering film can be improved
Performance is learned, silicon carbide aoxidizes under second of high temperature, forms the amorphous Si O of high activity on surface2Oxide layer, both can be with matrix
Interior impurity reaction generates low melting point phase acceleration of sintering, and can form mullite with oxidation reactive aluminum, improves porous ceramic film branch
The intensity of support body, and amorphous Si O2Oxide layer nanofiber sponge and peach gum pyrolysis generate negative oxygen ion effect under,
More hydrophilic silicone hydroxyls are formed, the long hole of connection and hydrophilic silicone hydroxyl synergistic effect improve the flux of ceramic super-filtering film,
It has broad application prospects.
Specific embodiment
According to parts by weight, 60~65 parts of carborundum powders, 30~35 parts of schmigels, 10~15 parts of kaolin powder are put into mixed
4~5min of mixing, obtains mixed powder in material machine, be added into mixed powder silica solution that 8~10 parts of mass fractions are 40%,
80~100 parts of deionized waters, after being dispersed with stirring be added mass fraction be 40% sodium hydroxide solution, adjust pH be 10.0~
10.5,2~3h is stood, mixed slurry is obtained；Above-mentioned mixed slurry is placed in ball mill, control ball material mass ratio is 10 ︰ 1,
Rotational speed of ball-mill is 400~500r/min, and after 1~2h of ball milling, the n-butanol that mixed slurry weight 2% is added into ball mill is stood
40~50min is defoamed, silicon carbide ceramics slurry is obtained；According to parts by weight, take 70~80 parts of zircon sands, 20~25 portions of lemons,
40~45 parts of acetic acid, 100~120 parts of deionized waters are put into ball mill, and after 4~5h of ball milling, filtering removal filter residue obtains ball milling
Ball milling slurries are placed in reaction kettle by slurries, and heating water bath is warming up to 70~75 DEG C, and it is molten that 30~40min of concentration obtains zirconium acetate
Glue, it is spare；30~40g peach gum is placed in three-necked flask, blender is started, is stirred with the revolving speed of 250~300r/min, with perseverance
Nine water that 200~300mL mass fraction is 40% are added dropwise with the drop rate of 2~3mL/min into three-necked flask for pressure dropping funel
Solution of sodium metasilicate through is stirred to react 2~3h, and cooled to room temperature is filtered after discharging with vacuum filtration machine, and removal filtrate obtains
Filter residue is placed in the baking oven that set temperature is 45~50 DEG C with petroleum ether, and dry 3~4h, ground 200 mesh obtains
Dry gel powder；It is in mass ratio that 1 ︰ 10 is mixed to get Bibulous Silica Gel by the silica solution that above-mentioned dry gel powder and mass fraction are 35%,
It will be immersed having a size of 60mm × 60mm × 80mm nanofiber sponge in the sodium hydroxide solution that mass fraction is 15%, heating
40~45 DEG C are warming up to, 40~45min is hydrolyzed, is put into clear water and washes by rubbing with the hands after taking-up, be put into Bibulous Silica Gel soak after natural drying
4~5h of stain, taking-up are put into 40~45min of impregnation in silicon carbide ceramics slurry, obtain to fired porous ceramic film support；It will
It is put into fired porous ceramic film support equipped in the reaction kettle in spare zirconium acetate colloidal sol, is heated under oxygen atmosphere
It 70~80 DEG C, takes out after 30~40min of isothermal holding and is impregnated in high temperature resistance furnace, with the rate program liter of 5~10 DEG C/min
For temperature to 400~450 DEG C, constant temperature handles 45~55min, is continuously heating to 1300~1350 DEG C, Isothermal sinter 3~4h, naturally cold
But ceramic super-filtering film is obtained to demoulding after room temperature.
The preparation of silicon carbide ceramics slurry: according to parts by weight, by 60 parts of carborundum powders, 30 parts of schmigels, 10 parts of kaolinites
Native powder is put into mixing 4min in batch mixer, obtains mixed powder, and it is molten that the silicon that 8 parts of mass fractions are 40% is added into mixed powder
The sodium hydroxide solution that mass fraction is 40% is added in glue, 80 parts of deionized waters after being dispersed with stirring, adjusting pH is 10.0, stands
2h obtains mixed slurry；
Above-mentioned mixed slurry is placed in ball mill, control ball material mass ratio is 10 ︰ 1, rotational speed of ball-mill 400r/min, ball milling 1h
Afterwards, the n-butanol that mixed slurry weight 2% is added into ball mill stands defoaming 40min, obtains silicon carbide ceramics slurry.
The preparation of zirconium acetate colloidal sol: according to parts by weight, take 70 parts of zircon sands, 20 portions of lemons, 40 parts of acetic acid, 100 parts go
Ionized water is put into ball mill, and after ball milling 4h, filtering removal filter residue obtains ball milling slurries, ball milling slurries are placed in reaction kettle,
Heating water bath is warming up to 70 DEG C, and concentration 30min obtains zirconium acetate colloidal sol.
The preparation of dry gel powder: 30g peach gum is placed in three-necked flask, is started blender, is stirred with the revolving speed of 250r/min
It mixes, nine water that 200mL mass fraction is 40% is added dropwise into three-necked flask with the drop rate of 2mL/min with constant pressure funnel
Solution of sodium metasilicate through is stirred to react 2h, and cooled to room temperature is filtered after discharging with vacuum filtration machine, and removal filtrate is filtered
Slag is placed in the baking oven that set temperature is 45 DEG C with petroleum ether, and dry 3h, ground 200 mesh obtains dry gel powder.
The preparation of ceramic super-filtering film: being 1 ︰ 10 by the silica solution that above-mentioned dry gel powder and mass fraction are 35% in mass ratio
It is mixed to get Bibulous Silica Gel, the hydrogen that mass fraction is 15% will be immersed having a size of 60mm × 60mm × 80mm nanofiber sponge
In sodium hydroxide solution, 40 DEG C are heated to, 40min is hydrolyzed, is put into clear water and washes by rubbing with the hands after taking-up, be put into water suction after natural drying
4h is impregnated in silica gel, taking-up is put into impregnation 40min in silicon carbide ceramics slurry, obtains to fired porous ceramic film support；
It will be put into fired porous ceramic film support equipped in the reaction kettle in spare zirconium acetate colloidal sol, heated under oxygen atmosphere
70 DEG C are warming up to, takes out and is impregnated in high temperature resistance furnace after isothermal holding 30min, is warming up to 400 with the rate program of 5 DEG C/min
DEG C, constant temperature handles 45min, is continuously heating to 1300 DEG C, Isothermal sinter 3h, and demoulding obtains Ceramic excessive filtration after cooled to room temperature
Film.
The preparation of silicon carbide ceramics slurry: according to parts by weight, by 62 parts of carborundum powders, 32 parts of schmigels, 12 parts of kaolinites
Native powder is put into mixing 4min in batch mixer, obtains mixed powder, and it is molten that the silicon that 9 parts of mass fractions are 40% is added into mixed powder
The sodium hydroxide solution that mass fraction is 40% is added in glue, 90 parts of deionized waters after being dispersed with stirring, adjusting pH is 10.2, stands
2.5h obtains mixed slurry；
Above-mentioned mixed slurry is placed in ball mill, control ball material mass ratio is 10 ︰ 1, rotational speed of ball-mill 450r/min, ball milling
After 1.5h, the n-butanol that mixed slurry weight 2% is added into ball mill stands defoaming 45min, obtains silicon carbide ceramics slurry.
The preparation of zirconium acetate colloidal sol: according to parts by weight, take 75 parts of zircon sands, 22 portions of lemons, 42 parts of acetic acid, 110 parts go
Ionized water is put into ball mill, and after ball milling 4.5h, filtering removal filter residue obtains ball milling slurries, ball milling slurries are placed in reaction kettle
In, heating water bath is warming up to 72 DEG C, and concentration 35min obtains zirconium acetate colloidal sol.
The preparation of dry gel powder: 35g peach gum is placed in three-necked flask, is started blender, is stirred with the revolving speed of 270r/min
It mixes, nine water that 250mL mass fraction is 40% is added dropwise into three-necked flask with the drop rate of 2mL/min with constant pressure funnel
Solution of sodium metasilicate through is stirred to react 2.5h, and cooled to room temperature is filtered after discharging with vacuum filtration machine, and removal filtrate obtains
Filter residue is placed in the baking oven that set temperature is 47 DEG C with petroleum ether, and dry 3.5h, ground 200 mesh obtains dry solidifying
Rubber powder.
The preparation of ceramic super-filtering film: being 1 ︰ 10 by the silica solution that above-mentioned dry gel powder and mass fraction are 35% in mass ratio
It is mixed to get Bibulous Silica Gel, the hydrogen that mass fraction is 15% will be immersed having a size of 60mm × 60mm × 80mm nanofiber sponge
In sodium hydroxide solution, 42 DEG C are heated to, 42min is hydrolyzed, is put into clear water and washes by rubbing with the hands after taking-up, be put into water suction after natural drying
4.5h is impregnated in silica gel, taking-up is put into impregnation 42min in silicon carbide ceramics slurry, obtains supporting to fired porous ceramic membrane
Body；
It will be put into fired porous ceramic film support equipped in the reaction kettle in spare zirconium acetate colloidal sol, heated under oxygen atmosphere
75 DEG C are warming up to, takes out and is impregnated in high temperature resistance furnace after isothermal holding 35min, is warming up to 420 with the rate program of 7 DEG C/min
DEG C, constant temperature handles 50min, is continuously heating to 1320 DEG C, Isothermal sinter 3.5h, it is super to obtain ceramics for demoulding after cooled to room temperature
Filter membrane.
The preparation of silicon carbide ceramics slurry: according to parts by weight, by 65 parts of carborundum powders, 35 parts of schmigels, 15 parts of kaolinites
Native powder is put into mixing 5min in batch mixer, obtains mixed powder, and it is molten that the silicon that 10 parts of mass fractions are 40% is added into mixed powder
The sodium hydroxide solution that mass fraction is 40% is added in glue, 100 parts of deionized waters after being dispersed with stirring, adjusting pH is 10.5, stands
3h obtains mixed slurry；
Above-mentioned mixed slurry is placed in ball mill, control ball material mass ratio is 10 ︰ 1, rotational speed of ball-mill 500r/min, ball milling 2h
Afterwards, the n-butanol that mixed slurry weight 2% is added into ball mill stands defoaming 50min, obtains silicon carbide ceramics slurry.
The preparation of zirconium acetate colloidal sol: according to parts by weight, take 80 parts of zircon sands, 25 portions of lemons, 45 parts of acetic acid, 120 parts go
Ionized water is put into ball mill, and after ball milling 5h, filtering removal filter residue obtains ball milling slurries, ball milling slurries are placed in reaction kettle,
Heating water bath is warming up to 75 DEG C, and concentration 40min obtains zirconium acetate colloidal sol.
The preparation of dry gel powder: 40g peach gum is placed in three-necked flask, is started blender, is stirred with the revolving speed of 300r/min
It mixes, nine water that 300mL mass fraction is 40% is added dropwise into three-necked flask with the drop rate of 3mL/min with constant pressure funnel
Solution of sodium metasilicate through is stirred to react 3h, and cooled to room temperature is filtered after discharging with vacuum filtration machine, and removal filtrate is filtered
Slag is placed in the baking oven that set temperature is 50 DEG C with petroleum ether, and dry 4h, ground 200 mesh obtains dry gel powder.
The preparation of ceramic super-filtering film: being 1 ︰ 10 by the silica solution that above-mentioned dry gel powder and mass fraction are 35% in mass ratio
It is mixed to get Bibulous Silica Gel, the hydrogen that mass fraction is 15% will be immersed having a size of 60mm × 60mm × 80mm nanofiber sponge
In sodium hydroxide solution, 45 DEG C are heated to, 45min is hydrolyzed, is put into clear water and washes by rubbing with the hands after taking-up, be put into water suction after natural drying
5h is impregnated in silica gel, taking-up is put into impregnation 45min in silicon carbide ceramics slurry, obtains to fired porous ceramic film support；
It will be put into fired porous ceramic film support equipped in the reaction kettle in spare zirconium acetate colloidal sol, heated under oxygen atmosphere
80 DEG C are warming up to, takes out and is impregnated in high temperature resistance furnace after isothermal holding 40min, is warming up to the rate program of 10 DEG C/min
450 DEG C, constant temperature handles 55min, is continuously heating to 1350 DEG C, Isothermal sinter 4h, and demoulding obtains ceramics after cooled to room temperature
Ultrafiltration membrane.
Comparative example 1: it is essentially identical with the preparation method of example 2, it has only the difference is that lacking zirconium acetate colloidal sol.
Comparative example 2: it is essentially identical with the preparation method of example 2, it has only the difference is that lacking dry gel powder.
Comparative example 3: the ceramic super-filtering film of Shandong company production.
Membrane flux test: with 80 DEG C of water inlet, oil content 18.70mg/L, the test of iron content 345.53ug/L condensed water in high temperature
Ceramic super-filtering film measures experiment effluent flux, oil content, iron content.
Pore-size distribution test obtains electromicroscopic photograph using the surface scan of PAN ultrafiltration membrane, by electromicroscopic photograph come peep hole
Diameter distribution situation.
1 ceramic super-filtering film performance measurement result of table
| Test item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Water flux (m3/ m2H) | 1.7 | 1.7 | 1.8 | 1.3 | 1.0 | 1.1 |
| Oil content (mg/L) | 0.10 | 0.09 | 0.09 | 0.22 | 0.30 | 0.25 |
| Iron content (μ g/L) | 12.5 | 12.4 | 12.3 | 17.1 | 18.3 | 16.8 |
| Pore-size distribution | Membrane granule is uniform, Pore-size distribution is narrow | Membrane granule is uniform, Pore-size distribution is narrow | Membrane granule is uniform, Pore-size distribution is narrow | Aperture point Cloth is wide | Membrane granule is more equal It is even, pore-size distribution compared with It is narrow | Membrane granule is more equal It is even, pore-size distribution compared with It is narrow |
According to above-mentioned detection data, Ceramic excessive filtration membrane flux of the invention is big, and water yield is higher than 1.7m3/m2H, aperture are easy
Control, membrane granule is uniform, and pore-size distribution is narrow, has broad application prospects.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of ceramic super-filtering film, it is characterised in that specific preparation step are as follows:
(1) silica solution that dry gel powder and mass fraction are 35% is mixed to get Bibulous Silica Gel, will having a size of 60mm × 60mm ×
The nanofiber sponge of 80mm is immersed in the sodium hydroxide solution that mass fraction is 15%, is heated to 40~45 DEG C, hydrolysis 40
~45min, is put into clear water after taking-up and washes by rubbing with the hands, is put into 4~5h of dipping in Bibulous Silica Gel after natural drying, and taking-up is put into silicon carbide
40~45min of impregnation in ceramic slurry is obtained to fired porous ceramic film support；
(2) it will be put into fired porous ceramic film support equipped in the reaction kettle in spare zirconium acetate colloidal sol, under oxygen atmosphere
70~80 DEG C are heated to, takes out and is placed in high temperature resistance furnace after 30~40min of isothermal holding, heating sintering, natural cooling
Demoulding obtains ceramic super-filtering film after to room temperature；
The specific preparation step of the dry gel powder are as follows:
30~40g peach gum is placed in three-necked flask, blender is started, is stirred with the revolving speed of 250~300r/min, is dripped with constant pressure
The inclined silicon of nine water that 200~300mL mass fraction is 40% is added dropwise with the drop rate of 2~3mL/min into three-necked flask for liquid funnel
Acid sodium solution is stirred to react 2~3h, and cooled to room temperature is filtered after discharging with vacuum filtration machine, and removal filtrate is filtered
Slag is placed in the baking oven that set temperature is 45~50 DEG C with petroleum ether, and dry 3~4h is ground up, sieved to obtain xerogel
Powder；
The specific preparation step of silicon carbide ceramics slurry are as follows:
(1) carborundum powder, schmigel, kaolin powder are put into 4~5min of mixing in batch mixer, obtain mixed powder, to mixing
Silica solution, the deionized water that mass fraction is 40% are added in powder, the hydroxide that mass fraction is 40% is added after being dispersed with stirring
Sodium solution, adjusting pH is 10.0~10.5, stands 2~3h, obtains mixed slurry；
(2) above-mentioned mixed slurry is placed in ball mill, rotational speed of ball-mill is 400~500r/min, after 1~2h of ball milling, to ball milling
The n-butanol that mixed slurry weight 2% is added in machine stands 40~50min of defoaming, obtains silicon carbide ceramics slurry；
The specific preparation step of zirconium acetate colloidal sol are as follows:
Zircon sand, citric acid, acetic acid, deionized water is taken to be put into ball mill, after 4~5h of ball milling, filtering removal filter residue obtains ball
Ball milling slurries are placed in reaction kettle, heating water bath by grinding slurry, and 30~40min of concentration obtains zirconium acetate colloidal sol.
2. a kind of preparation method of ceramic super-filtering film according to claim 1, it is characterised in that: the dry gel powder with
The silica solution mixing mass ratio that mass fraction is 35% is 1 ︰ 10.
3. a kind of preparation method of ceramic super-filtering film according to claim 1, it is characterised in that: heat up in high temperature resistance furnace
It is sintered detailed process are as follows: be warming up to 400~450 DEG C with the rate program of 5~10 DEG C/min, constant temperature handles 45~55min, continues
1300~1350 DEG C are warming up to, 3~4h of Isothermal sinter.
4. a kind of preparation method of ceramic super-filtering film according to claim 1, it is characterised in that: the dry gel powder
The be sieved specification of dry gel powder is limited to 200 mesh in specific preparation step.
5. a kind of preparation method of ceramic super-filtering film according to claim 1, it is characterised in that: the silicon carbide ceramics
Mixed slurry each component raw material in the specific preparation step of slurry (1), according to parts by weight, including 60~65 parts of carborundum powder, just
30~35 parts of beautiful powder, 10~15 parts of kaolin powder, mass fraction be 40% 8~10 parts of silica solution, 80~100 parts of deionized water.
6. a kind of preparation method of ceramic super-filtering film according to claim 1, it is characterised in that: the silicon carbide ceramics
Controlling ball material mass ratio in the specific preparation step of slurry (2) when mixed slurry ball milling is 10 ︰ 1.
7. a kind of preparation method of ceramic super-filtering film according to claim 1, it is characterised in that: the zirconium acetate colloidal sol
Zirconium acetate colloidal sol each component raw material in specific preparation step, according to parts by weight, including 70~80 parts of zircon sand, citric acid 20~
25 parts, 40~45 parts of acetic acid, 100~120 parts of deionized water.
8. a kind of preparation method of ceramic super-filtering film according to claim 1, it is characterised in that: the zirconium acetate colloidal sol
The temperature when concentration of ball milling slurries in specific preparation step, further control is 70~75 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299871A (en) * | 2020-11-16 | 2021-02-02 | 哈尔滨科友半导体产业装备与技术研究院有限公司 | Preparation method of porous ceramic containing silicon carbide film |
| CN113800939A (en) * | 2021-08-30 | 2021-12-17 | 华中科技大学 | Nano fiber SiO2Porous ceramic material and preparation method thereof |
| CN114002125A (en) * | 2021-11-03 | 2022-02-01 | 中南大学 | Method for rapidly testing resistance coefficient of sintered material layer |
| CN114773090A (en) * | 2021-11-09 | 2022-07-22 | 广东佛山市陶瓷研究所控股集团股份有限公司 | Method for enhancing strength of ceramic membrane support |
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2019
- 2019-02-20 CN CN201910126870.6A patent/CN110002893A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299871A (en) * | 2020-11-16 | 2021-02-02 | 哈尔滨科友半导体产业装备与技术研究院有限公司 | Preparation method of porous ceramic containing silicon carbide film |
| CN113800939A (en) * | 2021-08-30 | 2021-12-17 | 华中科技大学 | Nano fiber SiO2Porous ceramic material and preparation method thereof |
| CN113800939B (en) * | 2021-08-30 | 2023-02-28 | 华中科技大学 | Nano fiber SiO 2 Porous ceramic material and preparation method thereof |
| CN114002125A (en) * | 2021-11-03 | 2022-02-01 | 中南大学 | Method for rapidly testing resistance coefficient of sintered material layer |
| CN114002125B (en) * | 2021-11-03 | 2023-10-13 | 中南大学 | Rapid testing method for resistance coefficient of sinter bed |
| CN114773090A (en) * | 2021-11-09 | 2022-07-22 | 广东佛山市陶瓷研究所控股集团股份有限公司 | Method for enhancing strength of ceramic membrane support |
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