CN103011186A - Mica and preparation method thereof - Google Patents
Mica and preparation method thereof Download PDFInfo
- Publication number
- CN103011186A CN103011186A CN2012105498921A CN201210549892A CN103011186A CN 103011186 A CN103011186 A CN 103011186A CN 2012105498921 A CN2012105498921 A CN 2012105498921A CN 201210549892 A CN201210549892 A CN 201210549892A CN 103011186 A CN103011186 A CN 103011186A
- Authority
- CN
- China
- Prior art keywords
- mica
- multilevel hierarchy
- alkali metal
- kaolin
- metal compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to mica. The mica is multilevel structural mica prepared by arranging nano mica sheets in a three-dimensional direction. The mica has a multilevel structure of nano mica sheet, monthly rose and macropaticle, is high in specific surface area, and can be applied to the fields of composite materials, absorbent materials, sound-insulating materials, catalysts and the like; and a preparation method is simple in process, easy to operate, low in requirements on reaction equipment, easy to implement and free of environment pollution.
Description
Technical field
The present invention relates to a kind of mica and preparation method thereof, relate in particular to a kind of multilevel hierarchy mica and preparation method thereof, belong to the non-metallic material preparation field.
Background technology
Mica is a kind of rockforming mineral, usually is tabular, sheet, the column crystalline form of false six sides or rhombus.The characteristic of mica is that insulation, high temperature resistant, glossy, physical and chemical performance are stable, has good thermal insulation, elasticity and toughness.The mica powder that is processed to form also has preferably sliding and stronger sticking power.
Industrial with the most use be white mica, be phlogopite secondly.It is widely used in the chemical engineering industries such as building material industry, fire protection sector, fire-fighting medium, welding electrode, plastics, electrical isolation, papermaking, pitch paper, rubber, pearly pigment.Ultrafine mica powder can also can improve its physical strength as the functional stuffing of plastics, coating, paint, rubber etc., increases toughness, sticking power, anti-aging, resistance to corrosion etc.Because mica has insulation, heat-resisting, antiacid, alkali resistant, is widely used as the insulating material of electric installation and electrical material.
CN 102659129A(was on 09 12nd, 2012 in open day) a kind of preparation method of ultra-thin synthetic mica crystal powder is disclosed, with SiO
2, Al
2O
3, MgO, CaO, F by a certain percentage in the electric capacity smelting furnace melting prepare fluorine mica, pulverize through waterpower again and obtain ultra-thin mica ultra thin wafer, can see that from its SEM figure the mica wafer thickness is about 400 ~ 500nm.
CN 1034521A(was on 08 09th, 1989 in open day) a kind of preparation method of fluorine mica is disclosed, will contain the mixture heating up to 700 of alkalize silicofluoride, alkalization fluoride and talcum powder ~ 900 ℃ and obtain fluorine mica.
CN 1903721A(was on 01 31st, 2007 in open day) take quartz sand, magnesium oxide, aluminum oxide, potassium silicofluoride and salt of wormwood as raw material, prepare fluorine mica through the electrically heated melting.
CN 101037208A(was on 09 19th, 2007 in open day) take kaolin as raw material, with the mixture heating up to 850 of kaolin and Sodium Silicofluoride, magnesium compound ~ 900 ℃ of fluorine micas that prepare swelling.
In the aforesaid method, all need and will contain the raw material Hybrid Heating melting of fluorochemical, expensive raw material price, the heating and melting energy consumption is high.
Micro/nano material with special appearance, size and level has great importance in basic scientific research and practical application, has been subject to people and has paid close attention to widely.The material of multilevel hierarchy is as primary structure units, by the aggregation structure of certain order assembling formation by the nano materials such as nano particle, nanometer rod or pipe, nano wire and nanometer sheet of hanging down dimension.The material of multilevel hierarchy is except the characteristic of low-dimension nano material, again owing to have simultaneously different patterns, different particle diameter or special structure, give coupling effect that material structure unit self-assembly produces and systemic effect etc., so that certain or several effect are more outstanding, has certain special property, having broad application prospects, is a kind of popular thinking of current design and development novel material.
Hu Hanmei etc. are with CuCl
22H
2O, SnCl
2With thiocarbamide be raw material, under the ethylene glycol solvent heat condition, make the flower-shaped Cu of the Chinese rose with multilevel hierarchy
3SnS
4Microballoon.Prepared microballoon by certain thickness sheet petal from same nucleation centre to around radiation growth assemble, petal then is (the Cu of the synthetic multilevel hierarchy of solvent thermal that is stacked up by Van der Waals force by the nano flake with single crystal structure
3SnS
4The flower-shaped microballoon of Chinese rose, Hu Hanmei, Chinese Journal of Inorganic Chemistry, in July, 2010, the 7th phase of the 26th volume: 1189-1194).The multilevel hierarchy micro/nano material that design and preparation have special appearance, size, and the structure and properties of research material relation is one of direction of multilevel structure material research.
Although mica is widely used industrial, have mica and the synthetic report that also there is not yet thereof of multilevel hierarchy.The at present preparation of mica mineral focuses mostly in the preparation of fluorine mica, for the multilevel hierarchy mica, and rare report.Therefore, there is a kind of demand with mica of multilevel hierarchy of exploitation this area.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention is to provide a kind of mica with multilevel hierarchy.Described multilevel hierarchy mica is arranged at three-dimensional by the nano mica sheet and is formed.
As optimal technical scheme, the three-dimensional structure of described mica mainly is made of by any a kind or 2 kinds in face-face connection, face-end connection or the end-end mode of connection the nano mica sheet at least.
Further preferably, the primary structure of described multilevel hierarchy mica is the nano mica sheet, the Chinese rose flower-like structure of secondary structure for being consisted of from same center to external irradiation by the nano mica sheet, and tertiary structure is by the stacking macroscopic particles of Chinese rose flower-like structure.
Preferably, the thickness of described nano mica sheet is 5-50nm, such as 6nm, 12nm, 18nm, 24nm, 29nm, 33nm, 37nm, 41nm, 46nm, 49nm etc., preferred 20-50nm.
Preferably, the specific surface area of multilevel hierarchy mica of the present invention is 15-300m
2/ g, for example 15.2m
2/ g, 15.9m
2/ g, 18m
2/ g, 32m
2/ g, 47m
2/ g, 65m
2/ g, 88m
2/ g, 115m
2/ g, 138m
2/ g, 157m
2/ g, 175m
2/ g, 194m
2/ g, 234m
2/ g, 278m
2/ g, 199m
2/ g etc., preferred 100-200m
2/ g.
Preferably, the pore volume of multilevel hierarchy mica of the present invention is 0.2-20m
3/ g, for example 0.3m
3/ g, 0.8m
3/ g, 1.4m
3/ g, 3.5m
3/ g, 5.6m
3/ g, 7.8m
3/ g, 9.5m
3/ g, 12.3m
3/ g, 14.5m
3/ g, 16.8m
3/ g, 18.4m
3/ g, 19.6m
3/ g etc., preferred 0.5-1.5m
3/ g.
Preferably, multilevel hierarchy mica of the present invention has acidity, with H
+Meter, its acidity is 0.01 ~ 0.8mmol/g, such as 0.02mmol/g, 0.05mmol/g, 0.09mmol/g, 0.12mmol/g, 0.16mmol/g, 0.23mmol/g, 0.29mmol/g, 0.42mmol/g, 0.56mmol/g, 0.73mmol/g, 0.76mmol/g, 0.78mmol/g etc.
Two of purpose of the present invention is to provide a kind of preparation method of the mica such as the described multilevel hierarchy of one of purpose, described method is: after the kaolin powder activation, mix with alkali metal compound and water, hydrothermal treatment consists is carried out in heating, and solid product is the multilevel hierarchy mica.
Preferably, described alkali metal compound is the compound of basic metal potassium, the combination of any a kind or at least 2 kinds in preferred potassium hydroxide, Repone K, salt of wormwood or the vitriolate of tartar, described combination such as potassium hydroxide/Repone K, vitriolate of tartar/salt of wormwood, salt of wormwood/potassium hydroxide/Repone K etc., further preferred potassium hydroxide.
Fig. 1 is the process flow sheet of preparation multilevel hierarchy mica provided by the invention.
As optimal technical scheme, the preparation method of multilevel hierarchy mica of the present invention comprises the steps:
(1) kaolin powder is activated, get the activation kaolin powder;
(2) the activation kaolin powder that step (1) is obtained mixes with alkali metal compound, water, gets slurry;
(3) with the heating of step (2) gained slurry, carry out hydrothermal treatment consists;
(4) with the product solid-liquid separation after step (3) hydrothermal treatment consists, the solid product that obtains is the multilevel hierarchy mica.
" kaolin " word derives from that Jiangxi, China Jing Dezhen Gao Lingcun produces a kind of can porcelain making white clay and gain the name.Kaolin ore is that kaolinite subtribe clay mineral reaches clay or the tonstein that can utilize content.Mainly by forming less than kaolinite bunch mineral (kaolinite, dickite, nacrite, halloysite etc.) such as the small sheet of 2 microns, tubulose, lamination shapes, desirable chemical formula is Al to kaolin
2O
32SiO
22H
2O.
Kaolinic mineralogical composition is comprised of clay mineral and non-clay mineral, and clay mineral mainly comprises kaolinite, dickite, nakrite, metakaolin (1.0nm and 0.7nm halloysite), hydromica and montmorillonite; Non-clay mineral mainly is the detrital minerals such as quartz, feldspar, mica, and a small amount of heavy mineral and the mineral that some are spontaneous and secondary are such as magnetite, rutile, limonite, alunite, gibbsite, diaspore and boehmite etc.
Preferably, the described kaolin of step of the present invention (1) is selected from the mineral of combination that main phase comprises any a kind or at least 2 kinds of kaolinite, halloysite, nakrite, dickite, described combination such as kaolinite/halloysite, nakrite/dickite, halloysite/pearl potter's clay, kaolinite/halloysite/nakrite, kaolinite/halloysite/nakrite/dickite etc.
Kaolinite is the product of feldspar and the natural alteration of other silicate mineralss, is a kind of moisture aluminosilicate.
Halloysite, nakrite, dickite are kaolinic multi-form, and wherein halloysite claims again halloysite, halloysite; Nakrite is the most stable a kind of of crystalline structure in the kaolinite family, forms an Institutional Layer by 6 kaolinite synthems; Dickite is clay mineral, is kaolinic a kind of variant.
Kaolinic typical but non-limiting example of the present invention has any a kind in kaolin mineral, halloysite mineral, nakrite mineral, the dickite mineral, preferred kaolin mineral, further preferred Coaseries kaolin mineral.Coaseries kaolin is again coal gangue, is hard kaoline raw material a kind of and the common association of coal.
The kaolin main component is kaolinite, and in reactivation process, great changes will take place for the kaolinite physicochemical property.Preferably, the described activation method of step (1) comprises calcination process, mechanochemistry processing, adds any a kind in the alkali metal compound melting treatment.
Preferably, described calcination process is for to carry out roasting with kaolin powder, the temperature of described roasting is 500 ℃-1000 ℃, such as 510 ℃, 534 ℃, 570 ℃, 630 ℃, 750 ℃, 885 ℃, 934 ℃, 965 ℃, 980 ℃ etc., roasting time 〉=0.1h, such as 0.2h, 1.4h, 3.8h, 6h, 18h, 26h, 48h, 120h, 300h, 1000h etc., preferred 2-4h.
Kaolinite through the calcining after, alumina octahedral sheet generation dehydroxylation, the ligancy of aluminium atom changes, the ratio of four-coordination and pentacoordinate aluminium atom increases gradually.Lytic activity and the reactive behavior of kaolin in alkaline environment after calcining all strengthens, and is conducive under thermal and hydric environment and the alkalimetal ion effect, changes to mica fast.
Preferably, described mechanochemistry is treated in dry ball milling, wet ball grinding, high-energy ball milling and the airflow milling any a kind.
The mechanochemistry processing is the different modes of action by the high-energy mechanical force, such as shearing, friction, compression and impact etc., the physicochemical property of stressed object (solid, liquids and gases) are changed, thereby change (the application of mechanochemistry in resource and chemical engineering of materials and environmental protection of its reactive behavior, Li Ximing, Chen Jiayong, chemical industry metallurgical, in October, 2010, the 4th phase of the 21st volume: 443-448).
Kaolin is carried out mechanochemistry to be processed, can change the surface properties of kaolin particle, increase kaolin particle surface imperfection, scission of link, free ion and electronics, increase surface energy, thereby the reactive behavior of kaolin particle is greatly strengthened, promote it to the transformation of mica.
Preferably, described alkali-melting is treated to kaolin powder is mixed with alkali metal compound, then carries out the melting activation; The blending ratio of described kaolin powder and alkali metal compound is by amount of substance, be preferably 1:(0.01-0.6), such as 1:0.02,1:0.05,1:0.08,1:0.11,1:0.14,1:0.17,1:0.24,1:0.30,1:0.37,1:0.42,1:0.47,1:0.53,1:0.58 etc.; The temperature of described melting activation is 200-1000 ℃, such as 510 ℃, 534 ℃, 570 ℃, 630 ℃, 750 ℃, 885 ℃, 934 ℃, 965 ℃, 980 ℃ etc.
Preferably, described alkali metal compound is the compound of basic metal potassium, the combination of any a kind or at least 2 kinds in preferred potassium hydroxide, Repone K, salt of wormwood or the vitriolate of tartar, further preferred potassium hydroxide.
The kaolin alkali-melting is processed, be conducive to alkalimetal ion and kaolinic reaction, can make that the co-ordination state of silicon and aluminium atom changes in the kaolinite, improve its reactive behavior, promote simultaneously contacting of kaolinite and alkalimetal ion, be conducive to the carrying out of next step hydro-thermal reaction.
Preferably, the described ratio that is mixed into according to the amount of substance of kaolin, alkali metal compound, water of step (2) is 1:(0.01-0.6): (10-300) mix, wherein, kaolinic amount is in the amount of substance of element silicon.
Amount of substance with element silicon of the present invention calculates kaolinic blending ratio, and described kaolin is Al by chemical formula
2O
32SiO
22H
2O calculates, and namely kaolinic molecular weight is by 258.16, and the molecular weight of silicon is 21.76.For example when kaolinic quality be that the amount of substance of 25.816g(Si is 0.2mol), the quality of potassium hydroxide is 0.561g(0.01mol), the quality of water is 36g(2mol) time, the ratio of the amount of substance of kaolin, alkali metal compound, water is 1:0.05:10; When kaolinic quality is that the amount of substance of 12.908g(Si is 0.1mol), the quality of potassium hydroxide is 2.805g(0.05mol), the quality of water is 180g(10mol) time, the ratio of the amount of substance of kaolin, alkali metal compound, water is 1:0.5:100.
The ratio of the amount of substance of the described kaolin of step (2), alkali metal compound, water can be 1:0.02:13,1:0.06:285,1:0.09:25,1:0.1:35,1:0.15:70,1:0.19:250,1:0.23:158,1:0.26:174,1:0.31:265,1:0.35:248,1:0.38:223,1:0.42:95,1:0.48:274,1:0.53:56,1:0.58:42 etc.
Basic metal (alkali metal) refers to all metallic elements in the periodic table of elements IA family element, amount at present six kinds of lithiums (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), francium (Fr), the first five kind is present in nature, and francium can only be produced by nuclear reaction.The example of alkali metal compound of the present invention has sodium hydroxide, potassium hydroxide, lithium hydroxide, Repone K, salt of wormwood, yellow soda ash, sodium-chlor, vitriolate of tartar, lithium chloride etc., specifically selects which kind of alkali metal compound, and the present invention is not specifically limited.
Preferably, alkali metal compound of the present invention is the compound of basic metal potassium, the combination of any a kind or at least 2 kinds in preferred potassium hydroxide, Repone K, salt of wormwood or the vitriolate of tartar, further preferred potassium hydroxide.
Preferably, the temperature of the described hydrothermal treatment consists of step (3) is 50-500 ℃, such as 52 ℃, 57 ℃, 63 ℃, 74 ℃, 88 ℃, 102 ℃, 125 ℃, 178 ℃, 200 ℃, 235 ℃, 256 ℃, 287 ℃, 294 ℃, 298 ℃ etc., hydrothermal treatment consists time 〉=0.1h, such as 0.2h, 1.4h, 3.8h, 6h, 18h, 26h, 48h, 120h, 300h, 1000h etc., the preferably water heat treatment time is 3-72h.The temperature of the described hydrothermal treatment consists of step of the present invention (3) is more than 50 ℃, and this is because the rising temperature can significantly improve the speed of reaction of hydrothermal crystallizing.
Preferably, the method for the described solid-liquid separation of step (4) is selected from the combination of any a kind or at least 2 kinds in normal pressure filtration, suction filtration, centrifugation, the gravity settling separation, preferred suction filtration.The mode that can solid-liquid separation obtains solid product that any those skilled in the art can be known all can be used for the present invention.
Preferably, carry out step (5) after the solid-liquid separation of step (4): the solid product that solid-liquid separation is obtained is through washing, and then oven dry obtains the multilevel hierarchy mica;
Preferably, described bake out temperature is 105-130 ℃, and such as 106 ℃, 108 ℃, 115 ℃, 121 ℃, 129 ℃ etc., drying time is 3-6h, such as 3.2h, 3.9h, 4.6h, 5.3h, 5.8h etc.; Preferred bake out temperature is 115-125 ℃, and drying time is 4-6h; Most preferably bake out temperature is 120 ℃, and drying time is 5h.
Three of purpose of the present invention provides a kind of purposes such as the described mica of one of the object of the invention, and described mica can be used for matrix material, sorbing material, catalytic field, lagging material, soundproof material.
The mica of multilevel hierarchy provided by the invention is as sorbing material, the anionic sites in number that produces owing to isomorphous substitution can be used for adsorbing in the Industrial processes such as mining and metallurgy, machinofacture, chemical industry, electronics, instrument and produces contents of many kinds of heavy metal ion, such as chromium, cadmium, copper, mercury, nickel, zinc etc.
(acidity is 0.01 ~ 0.8mmol/g) to the mica of multilevel hierarchy provided by the invention owing to have certain acidity, simultaneously the various active component can be on its branch shape structure the formation of deposits avtive spot, available and catalytic field is such as can be used as FCC catalytic cracking catalyst carrier, homogeneous complex support of the catalyst etc.
Compared with prior art, the present invention has following beneficial effect:
(1) the invention provides a kind of mica with multilevel hierarchy;
The multilevel hierarchy of (2) multilevel hierarchy mica provided by the invention has nano mica sheet-Chinese rose flower-shaped-macroscopic particles shape, the specific surface area height can be up to 130m
2More than/the g, the specific surface area of common mica only has 30-50m
2Therefore/g is used for the present invention the fields such as matrix material, sorbing material, soundproof material, and effect is very good;
(3) multilevel hierarchy mica provided by the invention has acidity, and acidity is 0.01 ~ 0.8mmol/g, and common mica does not show relevant nature, and therefore mica provided by the invention can be used for corresponding catalyst field;
(4) preparation technology of multilevel hierarchy mica provided by the invention is simple, and is easy to operate, less demanding and be easy to realize environmentally safe to conversion unit.
Description of drawings
Fig. 1 is the process flow sheet that the present invention prepares the multilevel hierarchy mica;
Fig. 2 is the XRD spectra of the multilevel hierarchy mica for preparing of one embodiment of the present invention;
Fig. 3 is scanning electronic microscope (SEM) figure of the multilevel hierarchy mica for preparing of one embodiment of the present invention, and enlargement ratio is 10,000;
Fig. 4 is scanning electronic microscope (SEM) figure of the multilevel hierarchy mica for preparing of one embodiment of the present invention, and enlargement ratio is 50,000;
Fig. 5 is the isothermal adsorption curve of the multilevel hierarchy mica that makes of one embodiment of the present invention;
Fig. 6 is the pore size distribution curve of the multilevel hierarchy mica that makes of one embodiment of the present invention.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand that described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
A kind of preparation method of mica comprises the steps:
(1) granularity is placed retort furnace less than the Coaseries kaolin of 20 μ m, make the activation kaolin powder at 650 ℃ of lower calcining 4h;
(2) take by weighing activation kaolin powder 20g, potassium hydroxide 3.36g, the 100mL water that step (1) makes, it is joined the ball grinder of 500mL, add simultaneously the zirconium oxide balls of 210g, ball milling 4h makes slurry;
(3) take by weighing the stainless steel self-pressure reactor that slurry 60g that step (2) makes joins 100mL, under 280 ℃, carry out hydro-thermal reaction crystallization 3h;
(4) after hydro-thermal reaction is finished, with hydro-thermal reaction slurry cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains namely obtains the multilevel hierarchy mica at 120 ℃ of lower oven dry 5h.
Shown in Fig. 2 (Fig. 2 is the XRD spectra of the multilevel hierarchy mica that makes of present embodiment), products therefrom is mica;
(Fig. 3 is the scanning electron microscope diagram of the multilevel hierarchy mica that makes of present embodiment for the pattern of products therefrom such as Fig. 3, enlargement ratio is 10,000), (Fig. 4 is the scanning electron microscope diagram of the multilevel hierarchy mica that makes of present embodiment to Fig. 4, enlargement ratio is 50,000) as seen, it is to be arranged at three-dimensional by the mica nano flake to form the about 20nm of mica nano flake thickness;
At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 146m
2/ g, pore volume is about 0.94cm
3/ g.Fig. 5 is the isothermal adsorption graphic representation of the multilevel hierarchy mica that makes of present embodiment; Fig. 6 is the pore size distribution curve of the multilevel hierarchy mica that makes of present embodiment; Described mica acidity is 0.5mmol/g.
Embodiment 2
A kind of preparation method of mica comprises the steps:
(1) with the Coaseries kaolin of granularity less than 20 μ m, places in the retort furnace and make the activation kaolin powder at 800 ℃ of lower calcining 2h;
(2) take by weighing activation kaolin powder 10g, potassium hydroxide 1.68g, the 100mL water that step (1) makes, it is joined in the ball grinder of 500mL, add simultaneously the 210g zirconium oxide balls, ball milling 4h makes slurry;
(3) take by weighing the slurry 60g that step (2) makes, join the stainless steel self-pressure reactor of 100mL, under 300 ℃, carry out hydro-thermal reaction crystallization 3h;
(4) after hydro-thermal reaction is finished, with reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains is dried 5h and is namely obtained the multilevel hierarchy mica in 120 ℃ baking oven.
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 20nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 153m
2/ g, pore volume is about 0.99cm
3/ g; Described mica acidity is 0.3mmol/g.
Embodiment 3
A kind of preparation method of mica comprises the steps:
(1) with the Coaseries kaolin of granularity less than 20 μ m, place retort furnace to make the activation kaolin powder at 650 ℃ of lower calcining 2h;
(2) take by weighing activation kaolin powder 20g, potassium hydroxide 3.36g, the 100mL water that step (1) makes, it is joined the ball grinder of 500mL, add simultaneously the 210g zirconium oxide balls, ball milling 4h makes slurry;
(3) take by weighing the slurry 60g that step (2) makes, join the stainless steel self-pressure reactor of 100mL, under 250 ℃, carry out hydro-thermal reaction crystallization 24h;
(4) after hydro-thermal reaction is finished, with reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains is dried 5h and is namely obtained the multilevel hierarchy mica in 120 ℃ baking oven.
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 20nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 141m
2/ g, pore volume is about 0.92cm
3/ g; Described mica acidity is 0.75mmol/g.
Embodiment 4
A kind of preparation method of mica comprises the steps:
(1) with the Coaseries kaolin of granularity less than 20 μ m, place retort furnace to make the activation kaolin powder at 650 ℃ of lower calcining 2h,
(2) take by weighing activation kaolin powder 40g, potassium hydroxide 6.73g, the 100mL water that step (1) makes, it is joined the ball grinder of 500mL, add simultaneously the 210g zirconium oxide balls, ball milling 10h makes slurry;
(3) take by weighing the slurry 60g that step (2) makes, join the stainless steel self-pressure reactor of 100mL, under 250 ℃, carry out hydro-thermal reaction crystallization 24h;
(4) after hydro-thermal reaction is finished, with reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains is dried 5h and is namely obtained the multilevel hierarchy mica in 120 ℃ baking oven.
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 30nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 139m
2/ g, pore volume is about 0.87cm
3/ g; Described mica acidity is 0.8mmol/g.
Embodiment 5
A kind of preparation method of mica comprises the steps:
(1) with the Coaseries kaolin of granularity less than 20 μ m, place retort furnace to make the activation kaolin powder at 650 ℃ of lower calcining 2h;
(2) take by weighing activation kaolin powder 20g, potassium hydroxide 3.36g, the 100mL water that step (1) makes, it is joined the ball grinder of 500mL, add simultaneously the 210g zirconium oxide balls, ball milling 2h makes slurry;
(3) take by weighing the slurry 60g that step (2) makes, join the stainless steel self-pressure reactor of 100ml, under 200 ℃, 72h, carry out the hydro-thermal reaction crystallization;
(4) after hydro-thermal reaction is finished, with reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains is dried 5h and is namely obtained the multilevel hierarchy mica in 120 ℃ baking oven.
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 20nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 171m
2/ g, pore volume is about 1.03cm
3/ g; Described mica acidity is 0.03mmol/g.
Embodiment 6
A kind of preparation method of mica comprises the steps:
(1) with the Coaseries kaolin of granularity less than 20 μ m, place retort furnace to make the activation kaolin powder at 1000 ℃ of lower calcining 0.1h;
(2) take by weighing activation kaolin powder 20g, potassium hydroxide 3.36g, the 100mL water that step (1) makes, it is joined in the ball grinder of 500mL, add simultaneously the 210g zirconium oxide balls, ball milling 4h makes slurry;
(3) take by weighing the stainless steel self-pressure reactor that slurry 60g that step (2) makes joins 100mL, under 280 ℃, 3h, carry out the hydro-thermal reaction crystallization;
(4) after hydro-thermal reaction is finished, with reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains namely obtains the multilevel hierarchy mica at 120 ℃ of lower oven dry 5h.
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 25nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 140m
2/ g, pore volume is about 0.90cm
3/ g; Described mica acidity is 0.05mmol/g.
Embodiment 7
A kind of preparation method of mica comprises the steps:
(1) with the Coaseries kaolin of granularity less than 20 μ m, places in the retort furnace and make the activation kaolin powder at 500 ℃ of lower calcining 1000h;
(2) take by weighing activation kaolin powder 10g, potassium hydroxide 1.68g, the 100mL water that step (1) makes, it is joined in the ball grinder of 500mL, add simultaneously the 210g zirconium oxide balls, ball milling 4h makes slurry;
(3) take by weighing the above-mentioned slurry 60g that makes, join the stainless steel self-pressure reactor of 100mL, under 300 ℃, 3h, carry out the hydro-thermal reaction crystallization;
(4) after hydro-thermal reaction is finished, with reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains is dried 5h and is namely obtained the multilevel hierarchy mica in 120 ℃ baking oven.
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 25nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 148m
2/ g, pore volume is about 0.95cm
3/ g; Described mica acidity is 0.01mmol/g.
Embodiment 8
A kind of preparation method of mica comprises the steps:
(1) with the Coaseries kaolin of granularity less than 20 μ m, dry ball milling makes the activation kaolin powder;
(2) take by weighing activation kaolin powder 43g, potassium hydroxide 0.187g, the 60mL water that step (1) makes, it is joined in the ball grinder of 500mL, add simultaneously the 210g zirconium oxide balls, ball milling 4h makes slurry, and the mol ratio that wherein activates kaolin powder (take the molar ratio computing of Si), hydroxide agent and water is 1:0.01:10;
(3) take by weighing the above-mentioned slurry 60g that makes, join the stainless steel self-pressure reactor of 100mL, under 500 ℃, 0.1h, carry out the hydro-thermal reaction crystallization;
(4) after hydro-thermal reaction is finished, with reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains is dried 6h and is namely obtained the multilevel hierarchy mica in 105 ℃ baking oven.
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 26nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 300m
2/ g, pore volume is about 20cm
3/ g; Described mica acidity is 0.01mmol/g.
Embodiment 9
A kind of preparation method of mica comprises the steps:
(1) with the Coaseries kaolin of granularity less than 20 μ m, alkali-melting is processed and is made the activation kaolin powder; Kaolin powder is mixed by amount of substance 1:0.01 with potassium hydroxide, then under 1000 ℃, carry out the melting activation;
(2) take by weighing activation kaolin powder 4.3g, potassium hydroxide 0.112g, the 180mL water that step (1) makes, it is joined in the ball grinder of 500mL, add simultaneously the 210g zirconium oxide balls, ball milling 4h makes slurry, and the mol ratio that wherein activates kaolin powder (take the molar ratio computing of Si), hydroxide agent and water is 1:0.6:300;
(3) take by weighing the above-mentioned slurry 60g that makes, join the stainless steel self-pressure reactor of 1000mL, under 1000 ℃, 240h, carry out the hydro-thermal reaction crystallization;
(4) after hydro-thermal reaction is finished, with reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains is dried 3h and is namely obtained the multilevel hierarchy mica in 130 ℃ baking oven.
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 45nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 15
2/ g, pore volume is about 0.2cm
3/ g; Described mica acidity is 0.07mmol/g.
A kind of preparation method of mica compares with embodiment 9, and only the alkali-melting treatment condition of step (1) are different, and all the other are all identical, and step (1) is: with the Coaseries kaolin of granularity less than 20 μ m, alkali-melting is processed and is made the activation kaolin powder; Kaolin powder is mixed by amount of substance 1:0.6 with potassium hydroxide, then under 200 ℃, carry out the melting activation;
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 23nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 80
2/ g, pore volume is about 1.2cm
3/ g.
Embodiment 11
A kind of preparation method of mica comprises the steps:
(1) with the Coaseries kaolin of granularity less than 20 μ m, place retort furnace to make the activation kaolin powder at 650 ℃ of lower calcining 2h;
(2) take by weighing activation kaolin powder 20g, Repone K 5.10g, the 100mL water that step (1) makes, it is joined the ball grinder of 500mL, add simultaneously the 210g zirconium oxide balls, ball milling 2h makes slurry;
(3) take by weighing the slurry 60g that step (2) makes, join the stainless steel self-pressure reactor of 100ml, under .300 ℃, 72h, carry out the hydro-thermal reaction crystallization;
(4) after hydro-thermal reaction is finished, with reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains is dried 5h and is namely obtained the multilevel hierarchy mica in 120 ℃ baking oven.
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 25nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 169m
2/ g, pore volume is about 0.93cm
3/ g.
Embodiment 12
A kind of preparation method of mica comprises the steps:
(1) with the Coaseries kaolin of granularity less than 20 μ m, place retort furnace to make the activation kaolin powder at 650 ℃ of lower calcining 2h;
(2) take by weighing activation kaolin powder 20g, salt of wormwood 14.90g, the 100mL water that step (1) makes, it is joined the ball grinder of 500mL, add simultaneously the 210g zirconium oxide balls, ball milling 2h makes slurry;
(3) take by weighing the slurry 60g that step (2) makes, join the stainless steel self-pressure reactor of 100ml, under .300 ℃, 80h, carry out the hydro-thermal reaction crystallization;
(4) after hydro-thermal reaction is finished, with reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains is dried 5h and is namely obtained the multilevel hierarchy mica in 120 ℃ baking oven.
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 27nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 163m
2/ g, pore volume is about 0.90cm
3/ g.
Embodiment 13
A kind of preparation method of mica comprises the steps:
(1) with the Coaseries kaolin of granularity less than 20 μ m, place retort furnace to make the activation kaolin powder at 650 ℃ of lower calcining 2h;
(2) take by weighing activation kaolin powder 20g, lithium hydroxide 2.52g, the 100mL water that step (1) makes, it is joined the ball grinder of 500mL, add simultaneously the 210g zirconium oxide balls, ball milling 2h makes slurry;
(3) take by weighing the slurry 60g that step (2) makes, join the stainless steel self-pressure reactor of 100ml, under .300 ℃, 80h, carry out the hydro-thermal reaction crystallization;
(4) after hydro-thermal reaction is finished, with reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product that obtains is dried 5h and is namely obtained the multilevel hierarchy mica in 120 ℃ baking oven.
Gained multilevel hierarchy mica is to be arranged at three-dimensional by the mica nano flake to form the about 27nm of mica nano flake thickness; At 300 ℃ of lower degassed 3h, nitrogen suction-attached desorption records its specific surface area and is about 163m
2/ g, pore volume is about 0.90cm
3/ g.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. a mica is characterized in that, described mica is for arranging the multilevel hierarchy mica that forms by the nano mica sheet at three-dimensional.
2. mica as claimed in claim 1 is characterized in that, the three-dimensional structure of described mica mainly is made of by any a kind or 2 kinds in face-face connection, face-end connection or the end-end mode of connection the nano mica sheet at least;
Preferably, the primary structure of described multilevel hierarchy mica is the nano mica sheet, the Chinese rose flower-like structure of secondary structure for being consisted of from same center to external irradiation by the nano mica sheet, and tertiary structure is by the stacking macroscopic particles of Chinese rose flower-like structure;
Preferably, the thickness of described nano mica sheet is 5-50nm, preferred 20-50nm;
Preferably, the specific surface area of described mica is 15-300m
2/ g, preferred 100-200m
2/ g;
Preferably, the pore volume of described mica is 0.2-20m
3/ g, preferred 0.5-1.0m
3/ g;
Preferably, described mica is acid, and its acidity is 0.01 ~ 0.8mmol/g.
3. the preparation method of a mica as claimed in claim 1 or 2 is characterized in that, described method is: after the kaolin powder activation, mix with alkali metal compound and water, hydrothermal treatment consists is carried out in heating, and solid product is the multilevel hierarchy mica;
Preferably, described alkali metal compound is the compound of basic metal potassium, the combination of any a kind or at least 2 kinds in preferred potassium hydroxide, Repone K, salt of wormwood or the vitriolate of tartar, further preferred potassium hydroxide.
4. method as claimed in claim 3 is characterized in that, described method comprises the steps:
(1) kaolin powder is activated, get the activation kaolin powder;
(2) the activation kaolin powder that step (1) is obtained mixes with alkali metal compound, water, gets slurry;
(3) with the heating of step (2) gained slurry, carry out hydrothermal treatment consists;
(4) with the product solid-liquid separation after step (3) hydrothermal treatment consists, the solid product that obtains is the multilevel hierarchy mica.
5. method as claimed in claim 4 is characterized in that, the described kaolin of step (1) is selected from the mineral of combination that main phase comprises any a kind or at least 2 kinds of kaolinite, halloysite, nakrite, dickite;
Preferably, the described activation method of step (1) comprises calcination process, mechanochemistry processing, adds any a kind in the alkali metal compound melting treatment;
Preferably, described calcination process is for to carry out roasting with kaolin powder, and the temperature of described roasting is 500 ℃-1000 ℃, roasting time 〉=0.1h, preferred 2-4h;
Preferably, described mechanochemistry is treated in dry ball milling, wet ball grinding, high-energy ball milling and the airflow milling any a kind;
Preferably, described alkali-melting is treated to kaolin powder is mixed with alkali metal compound, then carries out the melting activation; The blending ratio of described kaolin powder and alkali metal compound is preferably 1:(0.01-0.6 by amount of substance); The temperature of described melting activation is 200-1000 ℃;
Preferably, described alkali metal compound is the compound of basic metal potassium, the combination of any a kind or at least 2 kinds in preferred potassium hydroxide, Repone K, salt of wormwood or the vitriolate of tartar, further preferred potassium hydroxide.
6. such as claim 4 or 5 described methods, it is characterized in that, the ratio that step (2) is described to be mixed into according to the amount of substance of kaolin, alkali metal compound, water is 1:(0.01-0.6): (10-300) mix, wherein, kaolinic amount is in the amount of substance of element silicon;
Preferably, described alkali metal compound is the compound of basic metal potassium, the combination of any a kind or at least 2 kinds in preferred potassium hydroxide, Repone K, salt of wormwood or the vitriolate of tartar, further preferred potassium hydroxide.
7. such as the described method of one of claim 4-6, it is characterized in that the temperature of the described hydrothermal treatment consists of step (3) is 50-500 ℃, hydrothermal treatment consists time 〉=0.1h, preferably water heat treatment time are 3-72h.
8. such as the described method of one of claim 4-7, it is characterized in that the method for the described solid-liquid separation of step (4) is selected from the combination of any a kind or at least 2 kinds in normal pressure filtration, suction filtration, centrifugation, the gravity settling separation, preferred suction filtration.
9. such as the described method of one of claim 4-8, it is characterized in that, carry out step (5) after the solid-liquid separation of step (4): the solid product that solid-liquid separation is obtained is through washing, and then oven dry obtains the multilevel hierarchy mica;
Preferably, described bake out temperature is 105-130 ℃, and drying time is 3-6h; Preferred bake out temperature is 115-125 ℃, and drying time is 4-6h; Most preferably bake out temperature is 120 ℃, and drying time is 5h.
10. the purposes of a mica as claimed in claim 1 or 2 is characterized in that, described mica can be used for matrix material, sorbing material, catalytic field, lagging material, soundproof material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210549892.1A CN103011186B (en) | 2012-12-17 | 2012-12-17 | Mica and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210549892.1A CN103011186B (en) | 2012-12-17 | 2012-12-17 | Mica and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103011186A true CN103011186A (en) | 2013-04-03 |
| CN103011186B CN103011186B (en) | 2015-05-20 |
Family
ID=47960368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210549892.1A Expired - Fee Related CN103011186B (en) | 2012-12-17 | 2012-12-17 | Mica and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103011186B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602003A (en) * | 2016-02-02 | 2016-05-25 | 安徽恒昊科技有限公司 | Preparation method of sericite-quartz powder |
| CN109694078A (en) * | 2018-12-18 | 2019-04-30 | 长春市泰元氟金云母有限公司 | A kind of preparation method of Fluororystal mica and its application in two dimensional crystal preparation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037208A (en) * | 2006-03-14 | 2007-09-19 | 中国科学院过程工程研究所 | Method for preparing swelled fluorine mica by kaoline |
| CN102616797A (en) * | 2012-05-02 | 2012-08-01 | 厦门大学 | Purification method for mica |
| CN102659129A (en) * | 2012-05-04 | 2012-09-12 | 杨修直 | Method for preparing ultrathin synthetic mica crystal powder |
-
2012
- 2012-12-17 CN CN201210549892.1A patent/CN103011186B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037208A (en) * | 2006-03-14 | 2007-09-19 | 中国科学院过程工程研究所 | Method for preparing swelled fluorine mica by kaoline |
| CN102616797A (en) * | 2012-05-02 | 2012-08-01 | 厦门大学 | Purification method for mica |
| CN102659129A (en) * | 2012-05-04 | 2012-09-12 | 杨修直 | Method for preparing ultrathin synthetic mica crystal powder |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602003A (en) * | 2016-02-02 | 2016-05-25 | 安徽恒昊科技有限公司 | Preparation method of sericite-quartz powder |
| CN109694078A (en) * | 2018-12-18 | 2019-04-30 | 长春市泰元氟金云母有限公司 | A kind of preparation method of Fluororystal mica and its application in two dimensional crystal preparation |
| CN109694078B (en) * | 2018-12-18 | 2022-05-20 | 长春市泰元氟金云母有限公司 | Preparation method of fluorine crystal mica and application of fluorine crystal mica in preparation of two-dimensional crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103011186B (en) | 2015-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lyu et al. | CuNi alloy/carbon foam nanohybrids as high-performance electromagnetic wave absorbers | |
| Xiao et al. | Tunable and improved microwave absorption of flower-like core@ shell MFe2O4@ MoS2 (M= Mn, Ni and Zn) nanocomposites by defect and interface engineering | |
| He et al. | N-doped residual carbon from coal gasification fine slag decorated with Fe3O4 nanoparticles for electromagnetic wave absorption | |
| Guan et al. | The controllable porous structure and s-doping of hollow carbon sphere synergistically act on the microwave attenuation | |
| He et al. | Hydrothermal preparation of boehmite nanorods by selective adsorption of sulfate | |
| Hu et al. | Hollow carbon microspheres modified with NiCo2S4 nanosheets as a high-performance microwave absorber | |
| Ren et al. | Mechanism of low temperature sintered high-strength ferric-rich ceramics using bauxite tailings | |
| CN100497762C (en) | Method for preparing mullite crystal whisker from coal refuse and aluminum oxide | |
| Wang et al. | Facile synthesis of cobalt nanoparticles embedded in a rod-like porous carbon matrix with excellent electromagnetic wave absorption performance | |
| Liu et al. | MnO 2-based materials for supercapacitor electrodes: challenges, strategies and prospects | |
| Gholami et al. | Novel green synthesis of ZnAl2O4 and ZnAl2O4/graphene nanocomposite and comparison of electrochemical hydrogen storage and Coulombic efficiency | |
| CN105688943A (en) | Method for preparing layered MoS2-TiO2 nano composite material | |
| Wu et al. | Preparation and thermal shock resistance of cordierite-spodumene composite ceramics for solar heat transmission pipeline | |
| CN100469436C (en) | Bentonite for purifying water and its preparation | |
| Tanaka et al. | Prussian blue derived iron oxide nanoparticles wrapped in graphene oxide sheets for electrochemical supercapacitors | |
| CN104150525A (en) | Oxide porous materials and universal preparation method thereof | |
| CN115432993B (en) | Solid heat storage material and preparation method and application thereof | |
| Sánchez et al. | Ultrasounds and microwave-assisted synthesis of mesoporous hectorites | |
| WO2020113958A1 (en) | Method for preparing high-performance iron oxide red/clay mineral hybrid pigment by mechanochemistry | |
| Zhang et al. | Enhanced microwave absorption performance of nitrogen-doped porous carbon dodecahedrons composite embedded with ceric dioxide | |
| Zheng et al. | Metal organic frameworks derived nano materials for energy storage application | |
| CN103011186B (en) | Mica and preparation method thereof | |
| Yang et al. | Three-dimensional spherical composite of layered double hydroxides/carbon nanotube for ethanol electrocatalysis | |
| Qian et al. | A design of core-shell structure for γ-MnO2 microspheres with tunable electromagnetic wave absorption performance | |
| Chen et al. | Fabrication of novel CuO/layered double oxide microspheres and its high efficiency adsorption performance for Congo red |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150520 Termination date: 20211217 |