CN103011186B - Mica and preparation method thereof - Google Patents
Mica and preparation method thereof Download PDFInfo
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- CN103011186B CN103011186B CN201210549892.1A CN201210549892A CN103011186B CN 103011186 B CN103011186 B CN 103011186B CN 201210549892 A CN201210549892 A CN 201210549892A CN 103011186 B CN103011186 B CN 103011186B
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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, particularly relate to a kind of multilevel hierarchy mica and preparation method thereof, belong to non-metallic material preparation field.
Background technology
Mica is a kind of rock forming mineral, is tabular, sheet, the column crystalline form of false six sides or rhombus usually.The characteristic of mica is insulation, high temperature resistant, glossy, physical and chemical performance is stablized, and has good thermal insulation, elasticity and toughness.The mica powder be processed to form also has good sliding and stronger sticking power.
Industrially with the most use is white mica, is secondly phlogopite.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 as the functional stuffing of plastics, coating, paint, rubber etc., can also can improve its physical strength, increases toughness, sticking power, anti-aging, resistance to corrosion etc.Because mica has insulation, heat-resisting, antiacid, alkali resistant, be widely used as the insulating material of electric installation and electrical material.
CN 102659129A(publication date is on 09 12nd, 2012) disclose a kind of preparation method of ultrathin synthetic mica crystal powder, by SiO
2, Al
2o
3, MgO, CaO, F by a certain percentage in electric capacity smelting furnace melting prepare fluorine mica, then through waterpower pulverize obtain ultra-thin mica ultra thin wafer, can see that mica wafer thickness is about 400 ~ 500nm from its SEM figure.
CN 1034521A(publication date is on 08 09th, 1989) disclose a kind of preparation method of fluorine mica, the mixture containing alkalization silicofluoride, alkalization fluoride and talcum powder is heated to 700 ~ 900 DEG C and obtains fluorine mica.
CN 1903721A(publication date is on 01 31st, 2007) with quartz sand, magnesium oxide, aluminum oxide, potassium silicofluoride and salt of wormwood for raw material, prepare fluorine mica through electrically heated melting.
CN 101037208A(publication date is on 09 19th, 2007) be raw material with kaolin, the mixture of kaolin and Sodium Silicofluoride, magnesium compound is heated to 850 ~ 900 DEG C and prepares bloating tendency fluorine mica.
In aforesaid method, all need the raw material Hybrid Heating melting containing fluorochemical, expensive raw material price, heating and melting energy consumption is high.
The micro/nano material with special appearance, size and level has great importance in basic scientific research and practical application, has received people and has paid close attention to widely.The material of multilevel hierarchy is by nano materials such as the nano particle of low dimension, nanometer rod or pipe, nano wire and nanometer sheet as primary structure units, the aggregation structure formed by the assembling of certain order.The material of multilevel hierarchy is except the characteristic of low-dimension nano material, again owing to having different patterns, different particle diameters or special structure simultaneously, give the material structure unit coupling effect that self-assembly produces and systemic effect etc., make certain or several effect more outstanding, there is certain special property, having broad application prospects, is the popular thinking of one of current design and development novel material.
Hu Hanmei etc. are with CuCl
22H
2o, SnCl
2be raw material with thiocarbamide, under ethylene glycol solvent heat condition, the obtained flower-shaped Cu of Chinese rose with multilevel hierarchy
3snS
4microballoon.Obtained microballoon is assembled to surrounding radiation growth from same nucleation centre by certain thickness sheet petal, and petal is then (the Cu of solvent-thermal process multilevel hierarchy be stacked up by Van der Waals force by the nano flake with single crystal structure
3snS
4chinese rose flower-like microsphere, Hu Hanmei, Chinese Journal of Inorganic Chemistry, in July, 2010, the 26th volume the 7th phase: 1189-1194).Design and preparation have the multilevel hierarchy micro/nano material of special appearance, size, and the structure and properties relation of research material is one of direction of multilevel structure material research.
Although mica is industrially widely used, there is the mica of multilevel hierarchy and synthesize and there is not been reported.The preparation of current mica mineral focuses mostly in the preparation of fluorine mica, for multilevel hierarchy mica, and rare report.Therefore, there is a kind of demand with the mica of multilevel hierarchy of exploitation this area.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of mica with multilevel hierarchy.Described multilevel hierarchy mica is formed in three-dimensional arrangement by nano mica sheet.
As optimal technical scheme, the three-dimensional structure of described mica is connected by face-face primarily of nano mica sheet, face-end connects or hold-hold any a kind or at least 2 kinds of formations in mode of connection.
Further preferably, the primary structure of described multilevel hierarchy mica is nano mica sheet, and secondary structure is the Chinese rose flower-like structure be made up of from same center to external irradiation nano mica sheet, and tertiary structure is by the macroscopic particles of the flower-shaped build stack of Chinese rose.
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, such as 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, such as 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 object of the present invention is the preparation method of the mica providing a kind of multilevel hierarchy as described in one of object, described method is: after being activated by kaolin powder, mix with alkali metal compound and water, hydrothermal treatment consists is carried out in heating, and solid product is 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 potassium sulfate, described combination is potassium hydroxide/Repone K, potassium sulfate/salt of wormwood, salt of wormwood/potassium hydroxide/Repone K etc. such as, further preferred potassium hydroxide.
Fig. 1 is the process flow sheet preparing 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, obtain activation kaolin powder;
(2) the activation kaolin powder that step (1) obtains is mixed with alkali metal compound, water, obtain slurry;
(3) step (2) gained slurry is heated, carry out hydrothermal treatment consists;
(4) by the product solid-liquid separation after step (3) hydrothermal treatment consists, the solid product obtained is multilevel hierarchy mica.
" kaolin " one word derive from Jiangxi, China Jing Dezhen Gao Lingcun produce a kind of can porcelain making white clay and gain the name.Kaolin ore is that kaolinite subtribe clay mineral reaches the clay or tonstein that can utilize content.Kaolin is primarily of the kaolinite such as small sheet, tubulose, laminated bunch mineral (kaolinite, dickite, nacrite, the halloysite etc.) composition being less than 2 microns, and desirable chemical formula is Al
2o
32SiO
22H
2o.
Kaolinic mineralogical composition is made up 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 is the detrital mineral such as quartz, feldspar, mica mainly, and a small amount of heavy mineral and some spontaneous and secondary mineral, as magnetite, rutile, limonite, alunite, gibbsite, diaspore and boehmite etc.
Preferably, step of the present invention (1) described kaolin is selected from the mineral of combination of any a kind or at least 2 kinds that dominant comprises kaolinite, halloysite, nakrite, dickite mutually, and described combination is kaolinite/halloysite, nakrite/dickite, halloysite/pearl potter's clay, kaolinite/halloysite/nakrite, kaolinite/halloysite/nakrite/dickite etc. such as.
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 is also known as halloysite, halloysite; Nakrite is the one that in kaolinite race, crystalline structure is the most stable, 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, dickite mineral, preferred kaolin mineral, further preferred Coaseries kaolin mineral.Coaseries kaolin is coal gangue again, is hard kaoline raw material that is a kind of and the common association of coal.
Kaolin main component is kaolinite, and in reactivation process, great changes will take place for kaolinite physicochemical property.Preferably, step (1) described activation method comprises calcination process, mechanochemistry process, any a kind of adding in alkali metal compound melting treatment.
Preferably, described calcination process is for carry out roasting by kaolin powder, the temperature of described roasting is 500 DEG C-1000 DEG C, such as 510 DEG C, 534 DEG C, 570 DEG C, 630 DEG C, 750 DEG C, 885 DEG C, 934 DEG C, 965 DEG C, 980 DEG C 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 is after calcining, and alumina octahedral sheet generation dehydroxylation, the ligancy of aluminium atom changes, and the ratio of four-coordination and pentacoordinate aluminium atom increases gradually.The lytic activity of kaolin in alkaline environment after calcining and reactive behavior all strengthen, be conducive under thermal and hydric environment with alkalimetal ion effect, change to mica fast.
Preferably, described mechanochemistry is treated to any a kind in dry ball milling, wet ball grinding, high-energy ball milling and airflow milling.
Mechanochemistry process is the different modes of action by high-energy mechanical force, as shearing, friction, compression and impact etc., the physicochemical property of stressed object (solid, liquids and gases) are changed, thus 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 21st volume the 4th phase: 443-448).
Mechanochemistry process is carried out to kaolin, the surface properties of kaolin particle can be changed, increase kaolin particle surface imperfection, scission of link, free ion and electronics, increase surface energy, thus the reactive behavior of kaolin particle is greatly strengthened, promote that it is to the transformation of mica.
Preferably, described alkali-melting is treated to and is mixed with alkali metal compound by kaolin powder, then carries out 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 DEG C, such as 510 DEG C, 534 DEG C, 570 DEG C, 630 DEG C, 750 DEG C, 885 DEG C, 934 DEG C, 965 DEG C, 980 DEG C 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 potassium sulfate, further preferred potassium hydroxide.
To the process of kaolin alkali-melting, be conducive to alkalimetal ion and kaolinic reaction, the co-ordination state of Silicified breccias atom in kaolinite can be made to change, improve its reactive behavior, promote the contact of kaolinite and alkalimetal ion simultaneously, be conducive to the carrying out of next step hydro-thermal reaction.
Preferably, being mixed into according to the ratio of the amount of substance of kaolin, alkali metal compound, water described in step (2) is 1:(0.01-0.6): (10-300) mixes, and 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.The amount of substance being such as 25.816g(Si when kaolinic quality 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; The amount of substance being 12.908g(Si when kaolinic quality 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 step (2) described kaolin, 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 metallic elements all in periodic table of elements IA race element, amount to lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), francium (Fr) six kinds at present, 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, sodium carbonate, sodium-chlor, potassium sulfate, lithium chloride etc., and concrete which kind of alkali metal compound of selection, 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 potassium sulfate, further preferred potassium hydroxide.
Preferably, the temperature of step (3) described hydrothermal treatment consists is 50-500 DEG C, such as 52 DEG C, 57 DEG C, 63 DEG C, 74 DEG C, 88 DEG C, 102 DEG C, 125 DEG C, 178 DEG C, 200 DEG C, 235 DEG C, 256 DEG C, 287 DEG C, 294 DEG C, 298 DEG C etc., hydrothermal conditions >=0.1h, such as 0.2h, 1.4h, 3.8h, 6h, 18h, 26h, 48h, 120h, 300h, 1000h etc., preferably water heat treatment time is 3-72h.The temperature of the hydrothermal treatment consists described in step of the present invention (3) is more than 50 DEG C, this is because raised temperature can significantly improve the speed of reaction of hydrothermal crystallizing.
Preferably, the method for the solid-liquid separation described in step (4) is selected from the combination of any a kind or at least 2 kinds in natural filtration, suction filtration, centrifugation, gravity settling separation, preferred suction filtration.What any one those skilled in the art can be known solid-liquid separation can obtain the mode of solid product and all can be used for the present invention.
Preferably, after the solid-liquid separation of step (4), carry out step (5): solid product solid-liquid separation obtained, through washing, is dried, then obtained multilevel hierarchy mica;
Preferably, described bake out temperature is 105-130 DEG C, and such as 106 DEG C, 108 DEG C, 115 DEG C, 121 DEG C, 129 DEG C 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 DEG C, and drying time is 4-6h; Most preferably bake out temperature is 120 DEG C, and drying time is 5h.
Three of object of the present invention is to provide a kind of purposes of the mica as described in 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 used as sorbing material, the anionic sites in number produced due to isomorphous substitution can be used for producing contents of many kinds of heavy metal ion, as chromium, cadmium, copper, mercury, nickel, zinc etc. in the Industrial processes such as absorption mining and metallurgy, machinofacture, chemical industry, electronics, instrument.
The mica of multilevel hierarchy provided by the invention is owing to having certain acidity (acidity is 0.01 ~ 0.8mmol/g), simultaneously various active component can in its branch shape structure formation of deposits avtive spot, available and catalytic field, such as can 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;
(2) multilevel hierarchy mica provided by the invention have nano mica sheet-Chinese rose flower-shaped-multilevel hierarchy of macroscopic particles shape, specific surface area height can up to 130m
2/ more than g, the specific surface area of common mica only has 30-50m
2/ g, therefore the present invention is used for the fields such as matrix material, sorbing material, soundproof material, 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, easy to operate, less demanding and be easy to realize, environmentally safe to conversion unit.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention prepares multilevel hierarchy mica;
Fig. 2 is the XRD spectra of the multilevel hierarchy mica that one embodiment of the present invention prepares;
Fig. 3 is scanning electronic microscope (SEM) figure of the multilevel hierarchy mica that one embodiment of the present invention prepares, and enlargement ratio is 10,000;
Fig. 4 is scanning electronic microscope (SEM) figure of the multilevel hierarchy mica that one embodiment of the present invention prepares, and enlargement ratio is 50,000;
Fig. 5 is the adsorption isothermal curve of the multilevel hierarchy mica that one embodiment of the present invention obtains;
Fig. 6 is the pore size distribution curve of the multilevel hierarchy mica that one embodiment of the present invention obtains.
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, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
A preparation method for mica, comprises the steps:
(1) Coaseries kaolin granularity being less than 20 μm is placed in retort furnace, calcines 4h obtained activation kaolin powder at 650 DEG C;
(2) take activation kaolin powder 20g, potassium hydroxide 3.36g, 100mL water that step (1) is obtained, joined the ball grinder of 500mL, add the zirconium oxide balls of 210g simultaneously, ball milling 4h obtains slurry;
(3) take the stainless steel self-pressure reactor that the obtained slurry 60g of step (2) joins 100mL, at 280 DEG C, carry out hydro-thermal reaction crystallization 3h;
(4) after hydro-thermal reaction completes, by hydro-thermal reaction slurry cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained dries 5h at 120 DEG C, namely obtains multilevel hierarchy mica.
As shown in Fig. 2 (XRD spectra of the multilevel hierarchy mica that Fig. 2 obtains for the present embodiment), products therefrom is mica;
(Fig. 3 is the scanning electron microscope diagram of the multilevel hierarchy mica that the present embodiment obtains to pattern such as Fig. 3 of products therefrom, enlargement ratio is 10,000), (Fig. 4 is the scanning electron microscope diagram of the multilevel hierarchy mica that the present embodiment obtains to Fig. 4, enlargement ratio is 50,000) visible, it is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 20nm;
Degassed 3h at 300 DEG C, 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 adsorption isothermal curve figure of the multilevel hierarchy mica that the present embodiment obtains; Fig. 6 is the pore size distribution curve of the multilevel hierarchy mica that the present embodiment obtains; Described mica acidity is 0.5mmol/g.
Embodiment 2
A preparation method for mica, comprises the steps:
(1) granularity is less than the Coaseries kaolin of 20 μm, places in retort furnace at 800 DEG C, calcine 2h obtained activation kaolin powder;
(2) take activation kaolin powder 10g, potassium hydroxide 1.68g, 100mL water that step (1) is obtained, joined in the ball grinder of 500mL, add 210g zirconium oxide balls simultaneously, ball milling 4h obtains slurry;
(3) take the slurry 60g that step (2) is obtained, join the stainless steel self-pressure reactor of 100mL, at 300 DEG C, carry out hydro-thermal reaction crystallization 3h;
(4) after hydro-thermal reaction completes, by reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained is dried 5h and is namely obtained multilevel hierarchy mica in the baking oven of 120 DEG C.
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 20nm; Degassed 3h at 300 DEG C, 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 preparation method for mica, comprises the steps:
(1) granularity is less than the Coaseries kaolin of 20 μm, is placed in retort furnace at 650 DEG C, calcines 2h obtained activation kaolin powder;
(2) take activation kaolin powder 20g, potassium hydroxide 3.36g, 100mL water that step (1) is obtained, joined the ball grinder of 500mL, add 210g zirconium oxide balls simultaneously, ball milling 4h obtains slurry;
(3) take the slurry 60g that step (2) is obtained, join the stainless steel self-pressure reactor of 100mL, at 250 DEG C, carry out hydro-thermal reaction crystallization 24h;
(4) after hydro-thermal reaction completes, by reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained is dried 5h and is namely obtained multilevel hierarchy mica in the baking oven of 120 DEG C.
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 20nm; Degassed 3h at 300 DEG C, 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 preparation method for mica, comprises the steps:
(1) granularity is less than the Coaseries kaolin of 20 μm, is placed in retort furnace at 650 DEG C, calcines 2h obtained activation kaolin powder,
(2) take activation kaolin powder 40g, potassium hydroxide 6.73g, 100mL water that step (1) is obtained, joined the ball grinder of 500mL, add 210g zirconium oxide balls simultaneously, ball milling 10h obtains slurry;
(3) take the slurry 60g that step (2) is obtained, join the stainless steel self-pressure reactor of 100mL, at 250 DEG C, carry out hydro-thermal reaction crystallization 24h;
(4) after hydro-thermal reaction completes, by reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained is dried 5h and is namely obtained multilevel hierarchy mica in the baking oven of 120 DEG C.
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 30nm; Degassed 3h at 300 DEG C, 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 preparation method for mica, comprises the steps:
(1) granularity is less than the Coaseries kaolin of 20 μm, is placed in retort furnace at 650 DEG C, calcines 2h obtained activation kaolin powder;
(2) take activation kaolin powder 20g, potassium hydroxide 3.36g, 100mL water that step (1) is obtained, joined the ball grinder of 500mL, add 210g zirconium oxide balls simultaneously, ball milling 2h obtains slurry;
(3) take the slurry 60g that step (2) is obtained, join the stainless steel self-pressure reactor of 100ml, 200 DEG C, carry out hydro-thermal reaction crystallization under 72h;
(4) after hydro-thermal reaction completes, by reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained is dried 5h and is namely obtained multilevel hierarchy mica in the baking oven of 120 DEG C.
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 20nm; Degassed 3h at 300 DEG C, 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 preparation method for mica, comprises the steps:
(1) granularity is less than the Coaseries kaolin of 20 μm, is placed in retort furnace at 1000 DEG C, calcines 0.1h obtained activation kaolin powder;
(2) take activation kaolin powder 20g, potassium hydroxide 3.36g, 100mL water that step (1) is obtained, joined in the ball grinder of 500mL, add 210g zirconium oxide balls simultaneously, ball milling 4h obtains slurry;
(3) take the stainless steel self-pressure reactor that the obtained slurry 60g of step (2) joins 100mL, 280 DEG C, carry out hydro-thermal reaction crystallization under 3h;
(4) after hydro-thermal reaction completes, by reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained dries 5h at 120 DEG C, namely obtains multilevel hierarchy mica.
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 25nm; Degassed 3h at 300 DEG C, 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 preparation method for mica, comprises the steps:
(1) granularity is less than the Coaseries kaolin of 20 μm, places in retort furnace at 500 DEG C, calcine 1000h obtained activation kaolin powder;
(2) take activation kaolin powder 10g, potassium hydroxide 1.68g, 100mL water that step (1) is obtained, joined in the ball grinder of 500mL, add 210g zirconium oxide balls simultaneously, ball milling 4h obtains slurry;
(3) take above-mentioned obtained slurry 60g, join the stainless steel self-pressure reactor of 100mL, 300 DEG C, carry out hydro-thermal reaction crystallization under 3h;
(4) after hydro-thermal reaction completes, by reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained is dried 5h and is namely obtained multilevel hierarchy mica in the baking oven of 120 DEG C.
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 25nm; Degassed 3h at 300 DEG C, 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 preparation method for mica, comprises the steps:
(1) granularity is less than the Coaseries kaolin of 20 μm, dry ball milling obtained activation kaolin powder;
(2) activation kaolin powder 43g, potassium hydroxide 0.187g, 60mL water that step (1) is obtained is taken, joined in the ball grinder of 500mL, add 210g zirconium oxide balls simultaneously, ball milling 4h obtains slurry, and the mol ratio wherein activating kaolin powder (molar ratio computing with Si), hydrogen-oxygen agent and water is 1:0.01:10;
(3) take above-mentioned obtained slurry 60g, join the stainless steel self-pressure reactor of 100mL, 500 DEG C, carry out hydro-thermal reaction crystallization under 0.1h;
(4) after hydro-thermal reaction completes, by reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained is dried 6h and is namely obtained multilevel hierarchy mica in the baking oven of 105 DEG C.
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 26nm; Degassed 3h at 300 DEG C, 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 preparation method for mica, comprises the steps:
(1) granularity is less than the Coaseries kaolin of 20 μm, alkali-melting process obtained activation kaolin powder; Kaolin powder is mixed by amount of substance 1:0.01 with potassium hydroxide, then at 1000 DEG C, carries out melting activation;
(2) activation kaolin powder 4.3g, potassium hydroxide 0.112g, 180mL water that step (1) is obtained is taken, joined in the ball grinder of 500mL, add 210g zirconium oxide balls simultaneously, ball milling 4h obtains slurry, and the mol ratio wherein activating kaolin powder (molar ratio computing with Si), hydrogen-oxygen agent and water is 1:0.6:300;
(3) take above-mentioned obtained slurry 60g, join the stainless steel self-pressure reactor of 1000mL, 1000 DEG C, carry out hydro-thermal reaction crystallization under 240h;
(4) after hydro-thermal reaction completes, by reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained is dried 3h and is namely obtained multilevel hierarchy mica in the baking oven of 130 DEG C.
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 45nm; Degassed 3h at 300 DEG C, 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.
Embodiment 10
A preparation method for mica, compared with embodiment 9, only the alkali-melting treatment condition of step (1) are different, and all the other are all identical, and step (1) is: Coaseries kaolin granularity being less than 20 μm, alkali-melting process obtained activation kaolin powder; Kaolin powder is mixed by amount of substance 1:0.6 with potassium hydroxide, then at 200 DEG C, carries out melting activation;
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 23nm; Degassed 3h at 300 DEG C, 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 preparation method for mica, comprises the steps:
(1) granularity is less than the Coaseries kaolin of 20 μm, is placed in retort furnace at 650 DEG C, calcines 2h obtained activation kaolin powder;
(2) take activation kaolin powder 20g, Repone K 5.10g, 100mL water that step (1) is obtained, joined the ball grinder of 500mL, add 210g zirconium oxide balls simultaneously, ball milling 2h obtains slurry;
(3) take the slurry 60g that step (2) is obtained, join the stainless steel self-pressure reactor of 100ml .300 DEG C, carry out hydro-thermal reaction crystallization under 72h;
(4) after hydro-thermal reaction completes, by reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained is dried 5h and is namely obtained multilevel hierarchy mica in the baking oven of 120 DEG C.
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 25nm; Degassed 3h at 300 DEG C, 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 preparation method for mica, comprises the steps:
(1) granularity is less than the Coaseries kaolin of 20 μm, is placed in retort furnace at 650 DEG C, calcines 2h obtained activation kaolin powder;
(2) take activation kaolin powder 20g, salt of wormwood 14.90g, 100mL water that step (1) is obtained, joined the ball grinder of 500mL, add 210g zirconium oxide balls simultaneously, ball milling 2h obtains slurry;
(3) take the slurry 60g that step (2) is obtained, join the stainless steel self-pressure reactor of 100ml .300 DEG C, carry out hydro-thermal reaction crystallization under 80h;
(4) after hydro-thermal reaction completes, by reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained is dried 5h and is namely obtained multilevel hierarchy mica in the baking oven of 120 DEG C.
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 27nm; Degassed 3h at 300 DEG C, 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 preparation method for mica, comprises the steps:
(1) granularity is less than the Coaseries kaolin of 20 μm, is placed in retort furnace at 650 DEG C, calcines 2h obtained activation kaolin powder;
(2) take activation kaolin powder 20g, lithium hydroxide 2.52g, 100mL water that step (1) is obtained, joined the ball grinder of 500mL, add 210g zirconium oxide balls simultaneously, ball milling 2h obtains slurry;
(3) take the slurry 60g that step (2) is obtained, join the stainless steel self-pressure reactor of 100ml .300 DEG C, carry out hydro-thermal reaction crystallization under 80h;
(4) after hydro-thermal reaction completes, by reaction paste cool to room temperature suction filtration;
(5) use deionized water wash 3 times, the solid product obtained is dried 5h and is namely obtained multilevel hierarchy mica in the baking oven of 120 DEG C.
Gained multilevel hierarchy mica is arranged on three-dimensional by mica nano flake to form, and mica nano flake thickness is about 27nm; Degassed 3h at 300 DEG C, nitrogen suction-attached desorption records its specific surface area and is about 163m
2/ g, pore volume is about 0.90cm
3/ g.
Applicant states, 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, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (26)
1. a mica, is characterized in that, described mica is the multilevel hierarchy mica arranged at three-dimensional by nano mica sheet;
The three-dimensional structure of described mica is connected by face-face primarily of nano mica sheet, face-end connects or hold-hold any a kind or at least 2 kinds of formations in mode of connection; The thickness of described nano mica sheet is 5-46nm; The specific surface area of described mica is 65-300m
2/ g; The pore volume of described mica is 0.2-20m
3/ g.
2. mica as claimed in claim 1, it is characterized in that, the thickness of described nano mica sheet is 20-46nm.
3. mica as claimed in claim 1, it is characterized in that, the specific surface area of described mica is 65-200m
2/ g.
4. mica as claimed in claim 1, it is characterized in that, the pore volume of described mica is 0.5-1.0m
3/ g.
5. mica as claimed in claim 1, it is characterized in that, the primary structure of described multilevel hierarchy mica is nano mica sheet, and secondary structure is the Chinese rose flower-like structure be made up of from same center to external irradiation nano mica sheet, and tertiary structure is by the macroscopic particles of the flower-shaped build stack of Chinese rose.
6. a preparation method for the mica as described in any one of claim 1-5, is characterized in that, described method is: after being activated by kaolin powder, mix with alkali metal compound and water, hydrothermal treatment consists is carried out in heating, and solid product is multilevel hierarchy mica;
Described alkali metal compound is the compound of basic metal potassium.
7. method as claimed in claim 6, is characterized in that, described alkali metal compound is the combination of any a kind or at least 2 kinds in potassium hydroxide, Repone K, salt of wormwood or potassium sulfate.
8. method as claimed in claim 7, it is characterized in that, described alkali metal compound is potassium hydroxide.
9. method as claimed in claim 6, it is characterized in that, described method comprises the steps:
(1) kaolin powder is activated, obtain activation kaolin powder;
(2) the activation kaolin powder that step (1) obtains is mixed with alkali metal compound, water, obtain slurry;
(3) step (2) gained slurry is heated, carry out hydrothermal treatment consists;
(4) by the product solid-liquid separation after step (3) hydrothermal treatment consists, the solid product obtained is multilevel hierarchy mica.
10. method as claimed in claim 9, is characterized in that, step (1) described kaolin is selected from the mineral of combination of any a kind or at least 2 kinds that dominant comprises kaolinite, halloysite, nakrite, dickite mutually.
11. methods as claimed in claim 9, is characterized in that, step (1) described activation method comprises calcination process, mechanochemistry process, any a kind of adding in alkali metal compound melting treatment.
12. methods as claimed in claim 11, is characterized in that, described calcination process is for carry out roasting by kaolin powder, and the temperature of described roasting is 500 DEG C-1000 DEG C, roasting time >=0.1h.
13. methods as claimed in claim 11, is characterized in that, described mechanochemistry is treated to any a kind in dry ball milling, wet ball grinding, high-energy ball milling and airflow milling.
14. methods as claimed in claim 11, it is characterized in that, described alkali-melting is treated to and is mixed with alkali metal compound by kaolin powder, then carries out melting activation; The blending ratio of described kaolin powder and alkali metal compound counts 1:(0.01-0.6 by amount of substance); The temperature of described melting activation is 200-1000 DEG C.
15. methods as claimed in claim 14, it is characterized in that, described alkali metal compound is the compound of basic metal potassium.
16. methods as claimed in claim 15, is characterized in that, described alkali metal compound is the combination of any a kind or at least 2 kinds in potassium hydroxide, Repone K, salt of wormwood or potassium sulfate.
17. methods as claimed in claim 16, it is characterized in that, described alkali metal compound is potassium hydroxide.
18. methods as claimed in claim 9, it is characterized in that, being mixed into according to the ratio of the amount of substance of kaolin, alkali metal compound, water described in step (2) is 1:(0.01-0.6): (10-300) mixes, wherein, kaolinic amount is in the amount of substance of element silicon.
19. methods as claimed in claim 18, it is characterized in that, described alkali metal compound is the compound of basic metal potassium.
20. methods as claimed in claim 19, is characterized in that, described alkali metal compound is the combination of any a kind or at least 2 kinds in potassium hydroxide, Repone K, salt of wormwood or potassium sulfate.
21. methods as claimed in claim 20, it is characterized in that, described alkali metal compound is potassium hydroxide.
22. methods as claimed in claim 9, is characterized in that, the temperature of step (3) described hydrothermal treatment consists is 50-500 DEG C, hydrothermal conditions >=0.1h.
23. methods as claimed in claim 9, is characterized in that, the method for the solid-liquid separation described in step (4) is selected from the combination of any a kind or at least 2 kinds in natural filtration, suction filtration, centrifugation, gravity settling separation.
24. methods as claimed in claim 9, is characterized in that, carry out step (5) after the solid-liquid separation of step (4): solid product solid-liquid separation obtained, through washing, is dried, then obtained multilevel hierarchy mica.
25. methods as claimed in claim 24, it is characterized in that, described bake out temperature is 105-130 DEG C, and drying time is 3-6h.
The purposes of 26. 1 kinds of micas as claimed in claim 1, is characterized in that, described mica is used for matrix material, sorbing material, catalytic field, lagging material, soundproof material.
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| 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 |
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| 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 |
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