CN105198476B - The preparation method of inorganic porous ceramic film - Google Patents
The preparation method of inorganic porous ceramic film Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of inorganic porous ceramic film, comprise the following steps：Weigh：Raw material, pore creating material, sintering aid are weighed according to certain ratio, and mixed；Wet-milling and dry grinding；It is granulated；Compression molding；Sintering.It is obtained ceramics have flux is big, compression strength is high, recyclability is good, ceramic membrane porosity is uniform；Inorganic ceramic membrane has the characteristics that high temperature resistant, acid-alkali-corrosive-resisting performance is good, compression strength is high, reproducible utilization rate is high, non-secondary pollution.It is respectively 82.3%, 85.3% and 89.6% to COD in water body, oil content, suspended solids content clearance, can reach preferable deoiling effect；Modified ceramic film carries out backwash regeneration under 0.05MPa washing conditions, and its clear water flux can recover to 94.7%.
Description
Technical field
The invention belongs to environmental protection technical field, and in particular to a kind of preparation method of inorganic porous ceramic film.
Background technology
In water treatment technology, ceramic membrane has good separative efficiency height, effect stability, chemical stability, acid and alkali-resistance, resistance to had
Solvent, resistance to bacterium, high temperature resistant, antipollution, high mechanical strength, film regenerability is good, separation process is simple, energy consumption is low, operation dimension
The many merits such as shield is easy, film service life length, are largely favored, are had been widely used in water treatment applications；
(1) oily waste water is handled：Heterogeneity, different content can be all produced in industries such as oil, machinery and food food and drink
Oily waste water, what processing oily waste water utilized is microcellular structure inside ceramic membrane, and oil droplet is separated from water.In cold rolling wastewater
In processing, inorganic ceramic membrane and organic film are contrasted, it is found that both treatment effects are suitable, but ceramic membrane is in running cost
Use the advantage for showing that its is absolute.
(2) petrochemical wastewater is handled：Some would generally be produced in chemical industry and petroleum chemical industry has strong acid, highly basic
Or the waste water containing particle of severe corrosive, organic film are often difficult to be competent at, and inoranic membrane is due to its excellent chemical stability,
With certain advantage when handling these waste water.
(3) reverse osmosis seawater desalting pre-processes：In seawater desalinization pretreatment system, ceramic membrane technology is introduced, profit
With the micro-filtration performance of ceramic membrane, new method is provided for the pretreatment of desalinization.
(4) drink water purifying：The processing of surface water is carried out using microporous membrane.The advantages of its is main has and can ensured
More preferable and more reliable water quality, does not add chemical substance.Especially suitable for high value added product.
(5) handle in dyeing waste water and heavy metal wastewater thereby：The a large amount of pollutants of oil-containing, mainly have in dyeing waste water：Suspension,
BOD, COD, bleaching agent, heavy metal (such as lead, chromium) and colourity etc., intractability is relatively large.Ceramic membrane dynamic filtration
Technology and flocculation technique combine, and are then applied to be handled in waste water from dyestuff and bleaching and dyeing wastewater, and discovery can so fill
Divide the advantages of showing dynamic filtration and ceramic membrane and advantage, treatment effect quite notable.
The preparation of conventional ceramic membrane mainly has following：(1) Polymeric sponge method；Schwartzwalder in 1963 et al.
Organic foam plastic infused ceramic slurry is used earliest, is burnt up organic foam after drying, has been prepared into porous ceramics.Tsing-Hua University
It is 70~80% to be prepared for the porosity using this method, and its average pore size is about in 200~300 μm of porous hydroxyapatite；
Xi'an Communications University is using biological glass powder and hydroxylapatite powder mixing as ceramic slurry, using Ludox as solvent with gluing
Agent is tied, hydroxymethyl cellulose has prepared aperture between 450~500 μm with this method and hole communicates as rheological agent
Multiporous biological active ceramic.This method relies on the three-dimensional netted skeleton structure of special drilling type possessed by organic foam, passes through
Ceramic slurry is uniformly coated on organic reticulate body, obtains the porous ceramics material with mesh-type open pore after the sintering
Material.The porous ceramics being prepared with this method, the porosity may be up to 70~90%.The preparation-obtained stomata shape of this method
Almost identical with the structure of organic foam presoma used, size also depends primarily on the hole chi of the organic foam of use
It is very little and relevant with the drying of coating thickness and slurry on parent and sintering shrinkage.
(2) sol-gal process；Sol-gal process (sol-gel), which is primarily adapted for use in, prepares the tiny microporous membrane in aperture,
Particularly nano level ceramic membrane, has high regularity by product made from this method.Its basic preparation process is as follows：
The alkoxide of metal is dissolved among lower alcohol, water droplet is gradually dropped so that reaction is hydrolyzed, then obtains corresponding metal oxygen
The colloidal sol of compound；PH value size is further adjusted, organic matter is produced polymerisation, is flocked together between oxide particle,
The gel of amorphous network structure is formed, is dried, organic matter is excluded, porous ceramic film is just obtained after sintering.Use collosol and gel
The aperture that method obtains, aperture is be about nano level, by adjusting the acid-base value of solution come the size of control hole and surface
Product etc., it can improve the control of porous ceramic film pore-size distribution, phase transformation and microstructure, but because organic matter is amorphous
Polymerisation, cause the shape of product to be not easy to be controlled.
(3) granulation mass area method；Ceramic membrane granule is usually have a geometry polyhedron of different shapes, and its heap can be with
Form porous structure.Can be added in ceramic membrane aggregate same composition ceramic fine particle or add binding agent so as to
Aggregate is connected.Because fine particle is easily sintered together, so at a certain temperature can be by bulky grain aggregate
Sintering gets up.Wu road political affairs et al. are by using SiO2-Al2O3-R2O-RO (R refers to organic group) is used as binding agent, by it in height
Liquid phase caused by temperature is lower, so as to the α-Al of certain particle size2O3Aggregate mutually is bonded, and its research is drawn：For isometrical spheroid
Accumulation, the porosity is unrelated with granular size, and relevant with the mode of accumulation, and aggregate particles are distributed narrower, obtained porosity value
It is bigger, and aperture is also more uniform, and its sintering temperature should be selected in the temperature that particle sintering but is below higher than binding agent melting temperature
In degree.
(4) pore creating material method is added；By adding pore creating material, in sintering process, due to pore creating material volatilization carbonization and inside
Portion forms the hole largely to communicate with each other, so as to which larger molecular organicses be separated from water.This method is by ceramic batch
Middle addition volatility or flammable pore-creating material, are volatilized or burnt at a certain temperature using these materials, Jin Er
Hole is left in ceramic body.Porous materials complex-shaped and that pore structure is different can be made using this method, its key exists
In type, size and the dosage of selection pore creating material.
(5) solid particles sintering process；Solid particles sintering process is to be well mixed inorganic particle with medium, forms stabilization
Green compact are made through technique in suspension, then suspension turned into uniform mixed powder through PROCESS FOR TREATMENT, powder, then through drying, finally
Thermal sintering at high temperature.Solid particles sintering process is exactly briquet to be placed on thermally equivalent in appropriate environment, and process is a series of
Physical and chemical changes, the viscosity between powder granule changes, continues to rise with temperature, due to the contraction of briquet
Mechanical strength and density is caused to increase, and the incorporation of pore creating material make it that system gross energy is reduced in sintering process in briquet.
In sintering process, under number of mechanisms collective effect, briquet changes to stable state.In order that particle has changed to stable state in itself
Entirely, it is necessary to be heated to certain temperature.In sintering process, the mechanical strength and performance of finished product and the heating rate of sintering, burning
Junction temperature, soaking time and cooldown rate have much relations.Due to ceramic film support intensity and porosity, pore size
And itself, there is restrictive function, so suitable sintering method can only be selected, is so just avoided that between shrinkage factor etc.
Product defects, and obtain support body material of good performance.
In summary, using previous methods prepare pottery membrane flux it is small, compression strength is low, to COD in water body, oil-containing
Amount, suspended solids content clearance are also than relatively low.
The content of the invention
The technical problem to be solved in the present invention is：Overcome the deficiencies in the prior art, there is provided a kind of inorganic porous ceramic film
Preparation method, solves the defects of ceramic membrane oil removal rate that prepared in the past is low.
The technical solution adopted for the present invention to solve the technical problems is：A kind of preparation method of inorganic porous ceramic film,
Comprise the following steps：
1., weigh：Raw material, pore creating material, sintering aid are weighed according to certain ratio, and mixed；The raw material is selected
Diatomite, the pore creating material include sawdust, graphene and CaCO3, described sintering aid is TiO2；
2., wet-milling：Ball mill is chosen, load weighted material, agate bead and distilled water are together loaded in ball mill, thing
The ratio of material, agate bead and distilled water is 2:1:1, the material includes raw material, pore creating material, sintering aid, is filled through ball mill
Divide and rotate, make material grinding uniform；
3., dry grinding：Liquid in ball mill is filtered through screen cloth, material liquid is obtained, material liquid is then put into baking
Case is dried, and material liquid drying is put into ball mill after completing together with agate bead, and the ratio between agate bead and material is 2:
1, material is regrind by ball mill uniform；
4., be granulated：Agate bead is screened out through screen cloth, material powders is taken out and is fitted into beaker, add appropriate distilled water, Bian Jia
Form block while stirring to powder to darken and have；Then it is granulated in the sieve of 60 mesh, is pressurizeed by using hand and extrude powder
60 mesh sieve are crossed, the powder after extruding is placed in culture dish and is aged；
5., compression molding：From electro-hydraulic servo universal press, the material for measuring ageing is placed in mould, electro-hydraulic servo
Universal press works, and makes compact formation, needs to ensure full pressure 3min after each malleation and back-pressure；
6., sintering：After ceramic membrane compacting, film base is put into the moisture dried in baking oven in 24h to film base and all volatilized；
The TiO2Content is the 1% of material total amount, and the pore creating material is the 35% of material total amount；Sawed in the pore creating material
End：Graphene：The component ratio of calcium carbonate is 2：2：1.
Further, the step 6. in sintering include four-stage, preceding three phases are carbonization volatilization period, the 4th
Stage is the sinter molding stage；
First stage：340 DEG C are warming up to, and is incubated 0.5h；Second stage：600 DEG C are warming up to, and is incubated 1h, the 3rd rank
Section：780 DEG C are warming up to, and is incubated 0.5h；Fourth stage：1100 DEG C are warming up to, and is incubated 0.5h.
Further, the step 2. in, rotating speed is 220r/min during ball milling, using 50min as a ball milling cycle, every
The individual cycle has rotating forward to grind and invert grinding two parts, respectively each 20min, can suspend 10min after 40min operatings, then hand
The dynamic grinding for starting next cycle, milling time carry out 4 cycles.
Further, the step 3. in, the rotating speed of dry grinding is 220r/min, and 50min is a ball milling cycle, Mei Gezhou
Phase has rotating forward to grind and invert each 20min of grinding, suspends 10min after 40min operatings, then starts next cycle manually
Grinding, dry grinding 2 cycles of grinding.
Further, the step 5. in, positive pressure pressure 11kN, back-pressure pressure is 13kN.
The beneficial effects of the invention are as follows：Obtained ceramics are with flux is big, compression strength is high, recyclability is good, ceramic membrane
Porosity is uniform；Inorganic ceramic membrane has high temperature resistant, acid-alkali-corrosive-resisting performance is good, compression strength is high, reproducible utilization rate is high, nothing
The features such as secondary pollution.It is respectively 82.3%, 85.3% and to COD in water body, oil content, suspended solids content clearance
89.6%, it can reach preferable deoiling effect；Modified ceramic film carries out backwash regeneration under 0.05MPa washing conditions, and its is clear
Water flux can recover to 94.7%.
Inorganic modified ceramic membrane performance evaluation and sign display, the ceramic membrane have aperture narrow, are evenly distributed, separation effect
The features such as rate is high.Belong to microfiltration membranes, can effectively remove the polluter such as oils in water body, the processing applied to oily waste water is can
Capable.
Brief description of the drawings
The present invention is further described below in conjunction with the accompanying drawings.
The schematic diagram of the influence of sawdust and graphene content to porosity in Fig. 1 ceramic membranes；
Sawdust and CaCO in Fig. 2 ceramic membranes3The schematic diagram of influence of the content to porosity；
Graphene and CaCO in Fig. 3 ceramic membranes3The schematic diagram of influence of the content to porosity
Embodiment
Presently in connection with specific embodiment, the present invention is further illustrated.These accompanying drawings be simplified schematic diagram only with
Illustration illustrates the basic structure of the present invention, therefore it only shows the composition relevant with the present invention.
A kind of preparation method of inorganic porous ceramic film, comprises the following steps：
1., weigh：Raw material, pore creating material, sintering aid are weighed according to certain ratio, and mixed；The raw material is selected
Diatomite, the pore creating material include sawdust, graphene and CaCO3, sintering aid TiO2；
2., wet-milling：Ball mill is chosen, load weighted material, agate bead and distilled water are together loaded in ball mill, thing
The ratio of material, agate bead and distilled water is 2:1:1, material includes raw material, pore creating material, sintering aid, fully turns through ball mill
It is dynamic, make material grinding uniform；
Rotating speed is 220r/min during ball milling, using 50min as a ball milling cycle, has rotating forward to grind and invert in each cycle
Two parts are ground, respectively each 20min, can suspend 10min after 40min operatings, then start the grinding of next cycle manually,
Milling time carries out 4 cycles.
3., dry grinding：Liquid in ball mill is filtered through screen cloth, material liquid is obtained, material liquid is then put into baking
Case is dried, and material liquid drying is put into ball mill after completing together with agate bead, and the ratio between agate bead and material is 2:
1, material is regrind by ball mill uniform；
The rotating speed of dry grinding is 220r/min, and 50min is a ball milling cycle, and each cycle has rotating forward to grind and invert grinding
Each 20min, suspend 10min after 40min operatings, then start the grinding of next cycle, dry grinding 2 cycles of grinding manually.
4., be granulated：Agate bead is screened out through screen cloth, material powders is taken out and is fitted into beaker, add appropriate distilled water, Bian Jia
Form block while stirring to powder to darken and have；Then it is granulated in the sieve of 60 mesh, is pressurizeed by using hand and extrude powder
60 mesh sieve are crossed, the powder after extruding is placed in culture dish and is aged.
5., compression molding：From electro-hydraulic servo universal press, the material for measuring ageing is placed in mould, electro-hydraulic servo
Universal press works, and makes compact formation, needs to ensure full pressure 3min after each malleation and back-pressure；Positive pressure pressure is 11kN,
Back-pressure pressure is 13kN.
6., sintering：After ceramic membrane compacting, film base is put into the moisture dried in baking oven in 24h to film base and all volatilized.
Sintering includes four-stage, and preceding three phases are carbonization volatilization period, and fourth stage is the sinter molding stage；First
Stage：340 DEG C are warming up to, and is incubated 0.5h；Second stage：600 DEG C are warming up to, and is incubated 1h, the phase III：It is warming up to 780
DEG C, and it is incubated 0.5h；Fourth stage：1100 DEG C are warming up to, and is incubated 0.5h.
Graphene absorbs heat volatilization comparatively fast at 600 DEG C, therefore need to be incubated 1h.After sintering terminates, baking oven power supply is closed, is allowed
Temperature is slowly fallen in baking oven, at this moment can't otherwise be likely to result in out baking to take the method for directly opening fire door to cool
Case moment body is damaged and with air contact meeting and the too fast division for causing ceramic membrane that cools.Because ceramic membrane sinters
Temperature when reaching 1200 DEG C, ceramic membrane shrinkage factor can become big, occur deforming and bond phenomenon, be easier to fracture and
Color is deeper, and section is in smooth stone planar, has very bright gloss, it is because the fracture of crystal grain in itself that expression, which fractures, illustrates crystalline substance
The defects of grain itself is existing a lot, the hole of inside configuration is fully sintered extremely, is not used to handle water.So draw experiment choosing
It is sintered with 1100 DEG C.
TiO2Content is the 1% of material total amount, and pore creating material is the 35% of material total amount；Sawdust in pore creating material：Graphene：Carbon
The component ratio of sour calcium is 2：2：1.
Porosity, refer to the volume of sample mesopore and the percentage of sample cumulative volume.As shown in figure 1, in carbonic acid
When calcium content is 10%, with the increase of sawdust content, porosity is initially what is reduced, however as the increase of sawdust content,
Situation is changed, and porosity increases therewith；This is due to that pore creating material sawdust main chemical compositions are made up of C, H, works as matter
When measuring fraction and being less than 7.5%, space that pore creating material occupies is less than the hole that base substrate particle accumulates formation at random in itself, therefore pore creating material
The increase of sawdust is little to Porosity Rate Influence, conversely now due to the rising of temperature, the contraction change of base substrate is more than hole
Formed, therefore the porosity when mass fraction is less than 7.5% reduces；When sawdust mass fraction is more than 7.5%, base substrate particle
Between the hole accumulated be not enough to accommodate the space needed for pore creating material, the distribution serialization transition of pore creating material, thus porosity
Dramatically increase, the hole now formed is significantly greater than the contraction change of base substrate.With the increase of graphene content, porosity is originally
And reduce, but with the increase of graphene content, porosity starts to increase.Wherein, porosity maximum is 46.5%,
Sawdust content at this point is 15%, and graphene content is 10%.
As shown in Fig. 2 when graphene content is 10%, with the increase of sawdust content, originally porosity reduces, with
Sawdust content continues to increase, and porosity is in increase tendency.With the increase of calcium carbonate content, originally porosity increases therewith,
When reaching 10% Deng calcium carbonate content, porosity reaches maximum, then as the increase of calcium carbonate content, porosity subtract on the contrary
It is small.Volatile carbon is melted into calcium oxide and carbon dioxide to calcium carbonate at high temperature.Porosity maximum can be obtained from figure is
46.5%, now sawdust content 15%, calcium carbonate content 10%.
As shown in figure 3, when sawdust content is 10%, with the increase of graphene content, originally porosity reduces, still
Continue to increase with sawdust content, porosity is in increase tendency；This is due to that pore creating material graphene main chemical compositions are C,
When mass fraction is less than 6%, space that pore creating material occupies is less than the hole that base substrate particle accumulates formation at random in itself, therefore pore-creating
The increase of agent graphene is little to Porosity Rate Influence, conversely now hole is more than due to the rising of temperature, the contraction change of base substrate
The formation of gap, therefore the porosity when mass fraction is less than 6% reduces；When sawdust mass fraction is more than 6%, base substrate particle
Between the hole accumulated be not enough to accommodate the space needed for pore creating material, the distribution serialization transition of pore creating material, thus porosity
Dramatically increase, the hole now formed is significantly greater than the contraction change of base substrate.And with the increase of calcium carbonate content, originally hole
Rate increases therewith, and when waiting the calcium carbonate content to reach 10%, porosity reaches maximum, then with the increase of calcium carbonate content, hole
Gap rate reduces on the contrary.As can be seen from the figure porosity maximum is 39.5%, and now graphene content is 15%, and calcium carbonate contains
Measure as 10%.Optimized using Design-Expert softwares, obtain optimum condition：Sawdust content 20%, graphene content
20%th, calcium carbonate content 11.21%, porosity are up to 56.9%.
In optimum condition sawdust content：Graphene content：Calcium carbonate content=20%：20%：11.21% ≈ 2:2:1, system
Standby ceramic membrane sample, prepare according to the method described above ceramic membrane pore creating material sawdust, graphene and calcium carbonate content be followed successively by 14%,
14%th, 7%.
Therefore, using sawdust in pore creating material：Graphene：The component ratio of calcium carbonate is 2：2：When 1, ceramic membrane cloth hole is equal
It is even, and surface is very smooth.Ceramic membrane porosity is uniform.
It is complete by above-mentioned description, relevant staff using the above-mentioned desirable embodiment according to the present invention as enlightenment
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property scope is not limited to the content on specification, it is necessary to determines its technical scope according to right.
Claims (4)
1. a kind of preparation method of inorganic porous ceramic film, it is characterized in that, comprise the following steps：
1., weigh：Raw material, pore creating material, sintering aid are weighed according to certain ratio, and mixed；The raw material selects diatom
Soil, the pore creating material include sawdust, graphene and CaCO3, described sintering aid is TiO2；
2., wet-milling：Ball mill is chosen, load weighted material, agate bead and distilled water are together loaded in ball mill, material,
The ratio of agate bead and distilled water is 2:1:1, the material includes raw material, pore creating material, sintering aid, fully turns through ball mill
It is dynamic, make material grinding uniform；
3., dry grinding：Liquid in ball mill is filtered through screen cloth, obtains material liquid, material liquid then is put into baking oven dries
Dry, material liquid drying is put into ball mill after completing together with agate bead, and the ratio between agate bead and material is 2:1, according to
Material is regrind by ball mill uniform；
4., be granulated：Agate bead is screened out through screen cloth, material powders is taken out and is fitted into beaker, add appropriate distilled water, side edged stirs
Mix to powder to darken and have and form block；Then it is granulated in the sieve of 60 mesh, is pressurizeed by using hand and powder was extruded 60
Mesh sieve, the powder after extruding is placed in culture dish and is aged；
5., compression molding：From electro-hydraulic servo universal press, the material for measuring ageing is placed in mould, and electro-hydraulic servo is omnipotent
Forcing press works, and makes compact formation, needs to ensure full pressure 3min after each malleation and back-pressure；
6., sintering：After ceramic membrane compacting, film base is put into the moisture dried in baking oven in 24h to film base and all volatilized；
The TiO2Content is the 1% of material total amount, and the pore creating material is the 35% of material total amount；Sawdust in the pore creating material：Stone
Black alkene：The component ratio of calcium carbonate is 2：2：1；
The step 6. in sintering include four-stage, preceding three phases are carbonization volatilization period, and fourth stage is sinters into
The type stage；
First stage：340 DEG C are warming up to, and is incubated 0.5h；Second stage：600 DEG C are warming up to, and is incubated 1h, the phase III：
780 DEG C are warming up to, and is incubated 0.5h；Fourth stage：1100 DEG C are warming up to, and is incubated 0.5h.
2. the preparation method of inorganic porous ceramic film according to claim 1, it is characterized in that, the step 2. in, ball milling
When rotating speed be 220r/min, using 50min as a ball milling cycle, have in each cycle rotating forward grind and reversion grinding two parts,
Each 20min respectively, it can suspend 10min after 40min operatings, then start the grinding of next cycle manually, milling time is entered
4 cycles of row.
3. the preparation method of inorganic porous ceramic film according to claim 1, it is characterized in that, the step 3. in, dry grinding
Rotating speed be 220r/min, 50min is a ball milling cycle, there is that rotating forward is ground and each 20min is ground in reversion each cycle,
Suspend 10min after 40min operatings, then start the grinding of next cycle, dry grinding 2 cycles of grinding manually.
4. the preparation method of inorganic porous ceramic film according to claim 1, it is characterized in that, the step 5. in, malleation
Pressure is 11kN, and back-pressure pressure is 13kN.
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| CN106007778A (en) * | 2016-05-13 | 2016-10-12 | 黄贺明 | Inorganic lightweight porous plate and preparation method thereof |
| CN105854632A (en) * | 2016-05-15 | 2016-08-17 | 东北电力大学 | Method for preparing diatomite hollow fiber ceramic membrane |
| CN107051407A (en) * | 2017-06-01 | 2017-08-18 | 浙江永续环境工程有限公司 | Industrial reuse method for treating water |
| CN108484209B (en) * | 2018-04-09 | 2020-11-03 | 四川兴凯歌建设工程有限公司 | Flat ceramic membrane and preparation process thereof |
| CN108706685A (en) * | 2018-05-29 | 2018-10-26 | 佛山市盟发净水科技有限公司 | A kind of ceramic film water purifier |
| CN108610085A (en) * | 2018-05-30 | 2018-10-02 | 佛山市航祥千安科技有限公司 | A kind of preparation method of the ceramic membrane based on natural polymer |
| CN108840703A (en) * | 2018-08-16 | 2018-11-20 | 北京工业大学 | A method of desalination hydrophobic porous cordierite ceramic film is prepared by raw material low cost of high silicon industrial solid castoff |
| CN112545066B (en) * | 2020-12-25 | 2024-03-29 | 海宁新纳陶科技有限公司 | Graphene porous ceramic capable of heating, atomization core and preparation method thereof |
| CN113336537B (en) * | 2021-05-12 | 2022-08-09 | 四川凯歌微纳科技有限公司 | Tubular ceramic membrane for industrial sewage treatment and preparation process |
| CN114368961B (en) * | 2022-01-27 | 2023-01-20 | 中钢集团马鞍山矿山研究总院股份有限公司 | Preparation method and new application of iron tailing ceramic filter material |
| CN115321948A (en) * | 2022-08-25 | 2022-11-11 | 山西工程技术学院 | Method for preparing ceramic filtering membrane by using wulan thea-crystal stone |
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| CN102391011B (en) * | 2011-08-10 | 2013-08-28 | 华南理工大学 | Preparation method of diatomite-based porous ceramic microspheres |
| CN103011893A (en) * | 2012-12-18 | 2013-04-03 | 常州大学 | Diatomite substrate-shaped ceramic membrane, and preparation method and application thereof |
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