CN101397137A - Globular inorganic oxide material, synthetic method, modification method and use thereof - Google Patents
Globular inorganic oxide material, synthetic method, modification method and use thereof Download PDFInfo
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Abstract
The invention provides a spherical inorganic oxide material with frameworks and perfusion hole structures; the material is composed of inorganic oxide frameworks which are connected with each other; perfusion holes which are crossed and perforated to each other are arranged among the frameworks; the framework surface can be divided into porous structure and/or non-porous structure; when the framework surface is the porous structure, the hole is called a framework hole or a dispersion hole; the framework surface is communicated with the perfusion hole; the framework dimension is ranging from 20 nanometer to 1 centimeter; the aperture of the perfusion hole is ranging from 20 nanometer to 1 micrometer; the aperture of the framework hole is ranging from 1 nanometer to 1 micrometer; the grain diameter of the spherical inorganic oxide material is ranging from 50 nanometer to 10 centimeter; the granularity distribution is a multi-dispersion type or single-dispersion type; the synthesis method comprises the steps as follows: the former body is dissolved or hydrolyzed in water phase or oil phase; pore-foaming agent and surfactant are added and dispersed in the oil phase or the water phase so as to carry out the reaction or spraying and drying reaction; after the reaction, the washing or burning operation is carried out so as to gain the material. After modification, surface performances of the material different from the body can be gained. The spherical inorganic oxide material can be applied to the fields such as chromatographic separation, filtration, catalytic synthesis, micro-reactor, energy storage and drug release.
Description
Technical field
The present invention relates to inorganic spherical oxide material and synthetic method thereof, surface modifying method and purposes that a class has skeleton and perfusion pore structure.
Background technology
With respect to spherical macromolecule polymer material, the inorganic spherical oxide material is because the physical strength height, solvent resistance is excellent, resistance to elevated temperatures good, the easy advantages such as modification in surface, at aspects such as chromatogram, catalysis, reaction carriers, energy storage purposes is more widely arranged.With the chromatographic separation field is example, is based upon inorganic oxide-spherical silica gel and has occupied the market share of liquid chromatography application more than 80% for basic separating medium.
The inorganic spherical oxide material mainly can be divided into two big classes at present according to its pore structure: porous spherical inorganic oxide and atresia inorganic spherical oxide compound.The porous spherical inorganic oxide as its name suggests, is meant that these holes have certain degree of depth and size in inorganic spherical oxide surface and the inner big and small various types of holes that distributing, and is isolated each other between hole and the hole.The porous spherical inorganic oxide is because the existence in hole, thereby big specific surface can be provided, and for separation, then can provide many action sites; For catalysis, then can provide many active centre.But because the hole has certain hole degree of depth, the effect in sample and these sites must be through certain diffusion length.Diffusion is a kind of mass transfer process slowly, and the size in its speed and aperture, the degree of depth in hole are relevant, and the aperture is big more, the hole is shallow more, and then rate of mass transfer is fast more.When the aperture of porous spherical inorganic oxide hour, for application such as micromolecular separation, catalysis, mass-transfer efficiency still can be accepted, and along with molecular weight to be separated, as to treat the catalysis sample increases, as protein molecule, the porous spherical inorganic oxide must provide big aperture could satisfy basic application demand.For some sharp separation, fast preparation, the field of quick catalysis requires the inorganic spherical oxide compound to have bigger aperture, yet along with the increase in aperture, the specific surface of inorganic spherical oxide compound, physical strength all significantly descend, and this becomes a pair of contradiction.For atresia inorganic spherical oxide compound, its mass-transfer efficiency is higher, yet specific surface is less than normal, and action site is limited, though the reduction of microspherulite diameter can the part degree relax this contradiction, reduction along with granularity, the Flow of Goods and Materials resistance increases, and back pressure increases, and high pressure resistant requirement increases to equipment, power consumption increases, and brings very big inconvenience to practical application.
Seemingly oxide-based with inorganic spherical, the spherical polymer material also mainly is divided into porose and atresia two big classes.Yet in porose spherical polymer material, there is a class to have special duct, as shown in drawings, it contains double-pore structure---perfusion hole 1 and diffusion hole 2, reaction precursor body in chromatogram flow phase, the catalyzed reaction can directly be gone into spheroid inside through the perfusion orifice flow, realizes convective mass transfer, and the diffusion hole of spheroid inside is owing to be connected with the perfusion hole, its hole degree of depth is more shallow, thereby also has diffusion mass transfer efficient faster.This special pore structure of spherical polymer material can improve whole mass-transfer efficiency greatly, has especially obtained to use widely in the separation and purification of biomacromolecule such as polypeptide, protein etc. in actual applications.Another advantage of this class diplopore spherical polymer material material is still can keep higher efficient under higher flow velocity, and because the porosity height, the back pressure of material is very low, helps reduction equipment input, reduces energy consumption, enhances productivity.The application of diplopore spherical polymer material in a lot of fields at present fully proved the advantage of this class material.Yet the solvent resistance of polymer materials is poor, and resistance to elevated temperatures is poor, and the surface modification approach is few, and physical strength is low, has greatly restricted the application development of diplopore spherical polymer material, as high-temperature catalytic, high speed catalysis, overcritical separation etc.
Owing to synthetic technology difficulty height, have not yet to see the report of inorganic spherical oxide material with skeleton and perfusion pore structure.
This patent is exactly at this deficiency, proposes to have the inorganic spherical oxide material of skeleton and perfusion pore structure, and illustrates its synthetic method, surface modifying method and purposes.
Summary of the invention
The invention provides inorganic spherical oxide material and synthetic method thereof, surface modifying method and purposes that a class has skeleton and perfusion pore structure.
Technical scheme provided by the invention is: 1. be presoma with inorganic sources or organic source, presoma dissolving or hydrolysis in water/or oil phase in, to wherein adding pore-creating agent and tensio-active agent, be dispersed to oil phase/or aqueous phase react, after scouring is finished in reaction, can obtain to have the inorganic spherical oxide material of skeleton and perfusion pore structure, perhaps after calcination or other thermal treatment, make inorganic spherical oxide material unformed and/or that crystalline form has skeleton and perfusion pore structure; 2. be presoma with inorganic sources or organic source, presoma dissolving or hydrolysis in water/or oil phase in, to wherein adding pore-creating agent, after the reaction, use the drive of high-pressure gas material through the nozzle atomization drying, after scouring is finished in reaction, can obtain to have the inorganic spherical oxide material of skeleton and perfusion pore structure, perhaps after calcination or other thermal treatment, make inorganic spherical oxide material unformed and/or that crystalline form has skeleton and perfusion pore structure.
Above-mentioned inorganic oxide material outward appearance is spherical in shape, constitute by interconnective inorganic oxide skeleton, perfusion hole for being interweaved and running through between skeleton, the skeleton surface can be divided into porose and/or non-porous structure, when when pore structure is arranged, this hole is called skeleton hole or diffusion hole, the skeleton surface is communicated with the perfusion hole, the skeleton size is between 20 nanometers-1 centimetre, perfusion hole aperture size is between 20 nanometers-1 centimetre, skeleton hole aperture size is between 1 nanometer-1 micron, and inorganic spherical oxide material size is between 50 nanometers-10 centimetre, and inorganic spherical oxide material size-grade distribution is polydispersion or single the dispersion.Its surface of inorganic spherical oxide material is divided into two portions: the outer skeleton surface of spheroid, spheroid inner frame surface.
In above-mentioned synthetic method, the inorganic sources presoma is meant water miscible salt, as water glass, potassium silicate, silicic acid, oxalic acid zirconium, zirconium oxychloride, zirconium chloride, titanium tetrachloride, cerous nitrate, magnesium chloride, aluminum nitrate, Tai-Ace S 150 etc.; Described organic source presoma is meant tetraethoxy, methyl silicate, titanium ethanolate, butyl (tetra) titanate, zirconium iso-propoxide, aluminum isopropylate etc.
In above-mentioned synthetic method, pore-creating agent comprises the water miscible tensio-active agent of three classes: a. such as alkylsulfonate, alkyl-sulphate, quaternary ammonium salt, polyvinyl alcohol, polyoxyethylene glycol, polyoxyethylene glycol-polypropylene glycol segmented copolymer etc.; B. be insoluble in the pressed powder of water such as activated carbon granule, lime carbonate, inorganic particle, polymkeric substance small-particle etc., grain diameter is (10nm-2mm); C. functional unit that can polymerization reaction take place is as urea and formaldehyde, trimeric cyanamide and formaldehyde, vinylformic acid, methacrylic acid etc.; Pore-creating agent can use or mix use separately.
In above-mentioned synthetic method, tensio-active agent comprises three classes: a. amphoterics such as amino acid pattern, betaine type etc., b. nonionogenic tenside such as Triton, peregal, sapn, polyvalent alcohol, tween etc., c. ionic surface active agent such as alkyl-sulphate, quaternary ammonium salt etc.; Tensio-active agent can use or mix use separately.
In above-mentioned synthetic method, oil phase is and the immiscible organism of water, as gasoline, sherwood oil, whiteruss etc.; Oil phase reagent can use or mix use separately.
The surface modification of inorganic spherical oxide material comprises to spheroid outer skeleton surface and the modification simultaneously of spheroid inner frame surface spheroid outer skeleton surface and the modification respectively of spheroid inner frame surface.The modification approach is as follows: by bonding reaction, absorption or coated, introduce alkyl, aryl, amino, carboxyl, organism or mineral ions such as sulfydryl, sulfonic group, cyclodextrin, Mierocrystalline cellulose, calixarene, amino acid, protein, DNA, antigen, antibody, coupling agent, intercalating agent, silver ions on inorganic spherical oxide material surface; Vapour deposition is to introduce materials such as charcoal, platinum, palladium, ruthenium, silver, gold by high-temperature physics and/or chemical process on inorganic spherical oxide material surface; Being coated with stagnates is meant through technologies such as colloidal sol-gel, coated, absorption, self-assemblies at the attached titanium oxide of inorganic spherical oxide material surface bag, zirconium white, magnesium oxide, calcium oxide, phosphatic rock etc.
Of the present invention have the inorganic spherical oxide material of skeleton and perfusion pore structure and an inorganic spherical oxide material that surface modification has skeleton and perfusion pore structure, is used for that chromatographic separation, filtration, catalysis are synthetic, microreactor, energy storage, medicament slow release.
Embodiment
Embodiment 1: spherical diplopore earth silicon material synthetic
40 gram water glass are dissolved in 110 ml distilled waters; to wherein adding 18 gram urea; 40 gram formaldehyde; regulating the pH value is 5.8; be mixed into a uniform phase; above-mentioned mixed solution is poured in the there-necked flask, added 18 gram sapn and 800 milliliters of industrial napthas, mechanical stirring; keep stirring velocity at 600 rev/mins; react after 6 hours, to wherein dripping dilute hydrochloric acid, after solution becomes white opacity gradually; stir and continue reaction shutdown after 24 hours down; use methanol wash, oven dry promptly gets spherical diplopore earth silicon material; perhaps continue 600 degrees centigrade of calcinations 10 hours, the spherical diplopore earth silicon material that can be strengthened.Particle diameter is between 50 microns-300 microns, and aperture, perfusion hole is between between 100 nanometers-10 micron, and aperture, skeleton hole is between 50 nanometers-500 nanometer.
Embodiment 2: spherical diplopore silica sphere deposition of carbon material synthetic
The spherical diplopore earth silicon material of synthetic among the embodiment 1 is put into tube furnace, be warming up to 900 degrees centigrade, toluene is entered tube furnace through the continuous spraying of nozzle, at high temperature toluene evaporates becomes steam and is deposited on skeleton surface (comprising internal surface and outside surface) by charing, postcooling took out in 2 hours, just obtained spherical diplopore silica sphere deposition of carbon material.
Embodiment 3: spherical diplopore silica sphere deposition of carbon material is used for environmental wastewater to be handled
Pack the spherical diplopore silica sphere deposition of carbon material that embodiment 2 obtains into long 10 centimetres, in the stainless steel tube that internal diameter is 1 centimetre, get 1 liter of the flow velocity of water sample that contains micro-dihydroxyphenyl propane and flow through stainless steel column, the content of dihydroxyphenyl propane in the mass spectrometric detection effluent liquid with 5 ml/min.Experiment shows, can't detect dihydroxyphenyl propane in the effluent liquid, illustrates that this pollutent is successfully adsorbed.Embodiment 4: the coated calcia material of spherical diplopore silica sphere synthetic
With synthesizing spherical diplopore earth silicon material among the embodiment 1 through pickling, washing fully after the activation, with the calcium chloride saturated aqueous solution silicon oxide microsphere of flowing through, filter out silicon oxide microsphere and this microballoon is exposed in the ammonia atmosphere 2 hours, after this step repeats 2 times, dry also high temperature sintering obtains the coated calcia material of spherical diplopore silica sphere.
Embodiment 5: the emulsification of spherical high purity diplopore earth silicon material mechanical stirring is synthetic
20 milliliters of tetraethoxys, 30 ml waters, appropriate hydrochloric acid is mixed, under 60 degrees centigrade, be hydrolyzed into an even phase, put into encloses container, vacuum-treat 60 minutes, after removing the ethanol of hydrolysis generation, to wherein adding cetyl trimethylammonium bromide 0.8 gram, Zulkovsky starch 0.5 gram, methacrylic acid microballoon (size range 50 nanometers-5 micron) 3.2 grams, stir into suspension liquid, pour in the there-necked flask, add 17 gram tween and 300 milliliters of gasoline, mechanical stirring, keep stirring velocity at 4000 rev/mins, shut down after 12 hours with heating in water bath for reaction while stirring, use methanol wash, promptly get the spherical diplopore earth silicon material of high purity; Perhaps continue 800 degrees centigrade of calcinations 10 hours, the spherical diplopore earth silicon material of the high purity that can be strengthened.Particle diameter is between between 200 nanometers-500 micron, and aperture, perfusion hole is between between 50 nanometers-20 micron, and aperture, perfusion hole can be different and regulate and control according to the particle diameter of selected microballoon.
Embodiment 6: spherical high purity diplopore earth silicon material spraying emulsification is synthetic
20 milliliters of tetraethoxys, 30 ml waters, appropriate hydrochloric acid is mixed, under 60 degrees centigrade, be hydrolyzed into an even phase, put into encloses container, vacuum-treat 60 minutes, after removing the ethanol of hydrolysis generation, to wherein adding cetyl trimethylammonium bromide 0.8 gram, Zulkovsky starch 0.5 gram, methacrylic acid microballoon (size range 50 nanometers-5 micron) 3.2 grams, stir into suspension liquid, pour in the there-necked flask, add 17 gram tweens, use high pressure gas or liquid driven material to be scattered in 500 milliliters of gasoline through nozzle atomization, mechanical stirring is kept stirring velocity at 4000 rev/mins, shuts down after 12 hours with heating in water bath for reaction while stirring, use methanol wash, promptly get the spherical diplopore earth silicon material of high purity; Perhaps continue 800 degrees centigrade of calcinations 10 hours, the spherical diplopore earth silicon material of the high purity that can be strengthened.Particle diameter is between between 500 nanometers-400 micron, and aperture, perfusion hole is between between 50 nanometers-9 micron, and aperture, perfusion hole can be different and regulate and control according to the particle diameter of selected microballoon.
Embodiment 7: spherical high purity diplopore earth silicon material film emulsion process is synthetic
20 milliliters of tetraethoxys, 30 ml waters, appropriate hydrochloric acid is mixed, under 60 degrees centigrade, be hydrolyzed into an even phase, put into encloses container, vacuum-treat 60 minutes, after removing the ethanol of hydrolysis generation, to wherein adding cetyl trimethylammonium bromide 0.8 gram, Zulkovsky starch 0.5 gram, methacrylic acid microballoon (size range 50 nanometers-5 micron) 3.2 grams, stir into suspension liquid, pour in the there-necked flask, add 17 gram tweens, use high pressure gas or liquid driven material to be scattered in 500 milliliters of gasoline through porous film material, mechanical stirring is kept stirring velocity at 4000 rev/mins, shuts down after 12 hours with heating in water bath for reaction while stirring, use methanol wash, promptly get the spherical diplopore earth silicon material of high purity; Perhaps continue 800 degrees centigrade of calcinations 10 hours, the spherical diplopore earth silicon material of the high purity that can be strengthened.Particle diameter is between between 300 nanometers-5 centimetre, and aperture, perfusion hole is between between 50 nanometers-50 micron, and aperture, perfusion hole can be different and regulate and control according to the particle diameter of selected microballoon.
Embodiment 8: spherical high purity diplopore earth silicon material spray-drying process is synthetic
20 milliliters of tetraethoxys, 30 ml waters, appropriate hydrochloric acid is mixed, under 60 degrees centigrade, be hydrolyzed into an even phase, put into encloses container, vacuum-treat 60 minutes, after removing the ethanol of hydrolysis generation, to wherein adding cetyl trimethylammonium bromide 0.8 gram, Zulkovsky starch 0.5 gram, methacrylic acid microballoon (size range 50 nanometers-5 micron) 3.2 grams, stir into suspension liquid, pour in the there-necked flask, stirring reaction 5 hours uses the drive of high-pressure gas material through nozzle, spraying drying, the collecting granules product is used methanol wash, promptly gets the spherical diplopore earth silicon material of high purity; Perhaps continue 800 degrees centigrade of calcinations 10 hours, the spherical diplopore earth silicon material of the high purity that can be strengthened.Particle diameter is between between 500 nanometers-2 centimetre, and aperture, perfusion hole is between between 50 nanometers-50 micron, and aperture, perfusion hole can be different and regulate and control according to the particle diameter of selected microballoon.
Embodiment 9: the coated La Ni of spherical high purity diplopore silica sphere material is synthetic
With the spherical high purity diplopore of synthetic among the embodiment 5 earth silicon material, it is dry to get 8 grams, evenly mixed with the aqueous solution of 20 milliliter 30% La (NO3) 26H2O, 100 degrees centigrade of dryings, 600 degrees centigrade of sintering after 20 hours then, use the aqueous solution dipping 24 hours of 20 milliliters of 20%Ni (NO3) 26H2O again, and repeat above-mentioned drying and calcination procedure 3 times; Use hydrogen reducing 4 hours then under 450 degrees centigrade, the catalyzer after the reduction is reduced to room temperature in drying nitrogen.
Embodiment 10: the coated La Ni of spherical high purity diplopore silica sphere material is used for the Meta-dinitrobenzene shortening
The coated La Ni of the spherical high purity diplopore silica sphere of synthetic among the embodiment 9 material is transferred in 200 milliliters of autoclaves for 300 milligrams.2.72 gram Meta-dinitrobenzenes are dissolved in 100 milliliters of dehydrated alcohols, join in the autoclave, feed hydrogen exchange and go out air in the still, be forced into 2.3MPa then, slowly behind the heating high-pressure still to 100 degree centigrade, the turn on agitator reaction.Meta-dinitrobenzene transformation efficiency and mphenylenediamine yield reach 94.1% and 96.5%. respectively
Embodiment 11: spherical amino bonded diplopore earth silicon material synthetic
After the spherical high purity diplopore earth silicon material that embodiment 6 is obtained refluxed 24 hours in concentrated hydrochloric acid, distilled water wash was to neutral, 120 degrees centigrade of vacuum bakeouts after 10 hours the secluding air cooling standby.Silicon-dioxide, 100 milliliters of toluene of 10 gram drying treatment mix under mechanical stirring, keep 80 degrees centigrade of temperature of reaction, the speed of 1 ml/min drips 20 milliliters of amino Trimethoxy silane liquid, stopped reaction after 24 hours, with toluene, methyl alcohol, water washing oven dry, get spherical amino bonded diplopore earth silicon material successively.
Embodiment 12: the diplopore earth silicon material of spherical alkyl functional group synthetic
After the spherical high purity diplopore earth silicon material that embodiment 7 is obtained refluxed 24 hours in concentrated hydrochloric acid, distilled water wash was to neutral, 120 degrees centigrade of vacuum bakeouts after 10 hours the secluding air cooling standby.Silicon-dioxide, 100 milliliters of toluene of 10 gram drying treatment mix under mechanical stirring, keep 80 degrees centigrade of temperature of reaction, the speed of 1 ml/min drips 20 milliliters of octadecyl Trimethoxy silane liquid, stopped reaction after 24 hours, with toluene, methyl alcohol, water washing oven dry, get spherical alkyl linked diplopore earth silicon material successively.
Embodiment 13: spherical diplopore zirconium dioxide material synthetic
20 gram oxalic acid zirconiums are dissolved in 110 ml distilled waters; to wherein adding 9 gram urea; 22 gram formaldehyde; be mixed into a uniform phase; above-mentioned mixed solution is poured in the there-necked flask; add 15 gram Triton and 600 milliliters of industrial napthas; mechanical stirring; keep stirring velocity at 4000 rev/mins, react after 1 hour, to wherein dripping weak ammonia; solution becomes white opacity gradually about 10 minutes; stir and continue reaction shutdown after 3 hours down, use methanol wash, promptly get spherical diplopore zirconium dioxide material; perhaps continue 600 degrees centigrade of calcinations 10 hours, the spherical diplopore zirconium dioxide material that can be strengthened.Particle diameter is between 1 micron-40 microns, and aperture, perfusion hole is between between 100 nanometers-100 micron, and aperture, skeleton hole is between between 2 nanometers-1 micron.
Embodiment 14: spherical alkyl functional is rolled into a ball the synthetic of diplopore zirconium dioxide material
Behind the spherical diplopore zirconium dioxide material thorough washing among the embodiment 13, mix with octadecyl phosphonic acids toluene solution, refluxed 10 hours under the magnetic agitation, then clean with toluene, acetone, ethanol successively, obtain octadecyl modified spherical alkyl functional group diplopore zirconium dioxide material.
Embodiment 15: spherical alkyl diplopore zirconium dioxide material is used for chromatographic separation
After homogenate, pack long 25 centimetres into obtaining spherical alkyl diplopore zirconium dioxide material among the embodiment 14, in the chromatographic column that internal diameter is 4.6 millimeters, UV-detector detects wavelength 254 nanometers, moving phase consists of methyl alcohol: water (80:20, v/v) mixed solution, flow velocity 2 ml/min have realized the baseline separation of benzene, naphthalene, anthracene three kinds of hydrophobic compounds in 5 minutes
Embodiment 16: spherical high purity dual-porosity titanium dioxide material synthetic
10 gram titanium tetrachlorides, 5 milliliters of hydrochloric acid, 10 ml waters mix, to wherein adding polyvinyl alcohol 1.2 grams, micro activated carbon particle 2.3 grams, stir, pour in the there-necked flask, add beet alkali surface activator 2.1 grams, 100 milliliters in gasoline, 5000 rev/mins of mechanical stirring 15 minutes, drip weak ammonia, after solution becomes white opacity gradually, continue stirring reaction and shut down after 2 hours, use methanol wash, promptly get spherical high purity dual-porosity titanium dioxide material; Perhaps continue 500 degrees centigrade of calcinations 10 hours, the spherical high purity dual-porosity titanium dioxide material that can be strengthened.Particle diameter is between 3 microns-20 microns, and aperture, perfusion hole is between 5 nanometers-500 nanometer, and aperture, perfusion hole can be regulated and control according to the particle diameter difference of selected microballoon.According to the difference of calcination temperature, the titanium oxide crystal formation can be anatase titanium dioxide or brilliant red stone type.
Embodiment 17: spherical single the synthetic of dual-porosity titanium dioxide material that disperse
20 milliliters of isopropyl titanates, 20 milliliters of ethanol, 2 milliliters of methyl ethyl diketones, appropriate hydrochloric acid were mixed stirring after 12 hours, add phenylethylene micro ball 3 grams, mix, utilize high pressure gas or liquid driven then, by being extruded in the porous-film in the aqueous solution that contains amino acid type surfactant, reaction solution reacts rapidly produces equally distributed microballoon, aging 30 hours, use methanol wash, promptly get spherical monodisperse titanium dioxide diplopore material; Perhaps continue 600 degrees centigrade of calcinations 3 hours, the spherical monodisperse titanium dioxide diplopore material that can be strengthened.Particle diameter is between 1 micron-40 microns.
Embodiment 18: spherical high purity diplopore zirconium-magnesium hydridization oxide material synthetic
12 gram zirconium oxychlorides, 8 gram magnesium chlorides are dissolved in 110 ml distilled waters, to wherein adding 9 gram urea, 22 gram formaldehyde, mix, pour in the there-necked flask, add 15 gram Triton and 600 milliliters of industrial napthas, mechanical stirring is kept stirring velocity at 4000 rev/mins, react after 1 hour, drip weak ammonia, after solution becomes white opacity gradually, continue to stir after 24 hours and shut down, use methanol wash, promptly get spherical high purity diplopore zirconium-magnesium hydridization oxide material; Perhaps continue 600 degrees centigrade of calcinations 3 hours, the spherical high purity diplopore zirconium-magnesium hydridization oxide material that can be strengthened.Particle diameter is between 1 micron-40 microns.
Embodiment 19: spherical diplopore zirconium-cerium hydridization oxide material synthetic
16 gram zirconium oxychlorides, 4 gram cerous nitrates are dissolved in 110 ml distilled waters, to wherein adding 9 gram urea, 22 gram formaldehyde, are mixed into a uniform phase, above-mentioned mixed solution is poured in the there-necked flask, add 15 gram Triton and 600 milliliters of industrial napthas, mechanical stirring is kept stirring velocity at 4000 rev/mins, react after 1 hour, drip weak ammonia, after solution becomes white opacity gradually, continue to stir after 24 hours and shut down, use methanol wash, promptly get spherical high purity diplopore zirconium-cerium hydridization oxide material; Perhaps continue 600 degrees centigrade of calcinations 3 hours, the spherical high purity diplopore zirconium-cerium hydridization oxide material that can be strengthened.Particle diameter is between 1 micron-40 microns.
Description of drawings
Description of drawings: accompanying drawing is the synoptic diagram of " the inorganic spherical oxide material with skeleton and perfusion pore structure " proposed by the invention.
Claims (10)
1. a class has the inorganic spherical oxide material of skeleton and perfusion pore structure, it is characterized in that: this inorganic spherical oxide material is made of interconnective inorganic oxide skeleton, perfusion hole for being interweaved and running through between skeleton, the skeleton surface can be divided into porose and/or non-porous structure, when when pore structure is arranged, this hole is called skeleton hole or diffusion hole, the skeleton surface is communicated with the perfusion hole, the skeleton size is between 20 nanometers-1 centimetre, aperture, perfusion hole is between 20 nanometers-1 centimetre, and aperture, skeleton hole is between 1 nanometer-1 micron; Inorganic spherical oxide material particle diameter is between 50 nanometers-10 centimetre, and inorganic spherical oxide material size-grade distribution is polydispersion or single the dispersion.Its surface of inorganic spherical oxide material is divided into two portions: the outer skeleton surface of spheroid, spheroid inner frame surface.
2. inorganic spherical oxide material according to claim 1, it is characterized in that: the inorganic spherical oxide material consists of single component and/or polycomponent inorganic oxide, as silicon-dioxide, zirconium dioxide, titanium dioxide, cerium oxide, magnesium oxide, aluminum oxide or the complex spherical inorganic oxide of arbitrary combination wherein.Inorganic spherical oxide material crystal formation is: unformed and/or crystal formation.
3. the synthetic method of inorganic spherical oxide material according to claim 1, it is characterized in that: the preparation of inorganic spherical oxide material can be selected the inorganic sources presoma for use, organic precursor, the formation of vesicular structure is mainly obtained by pore-creating agent, presoma dissolving or hydrolysis in water/or oil phase in, to wherein adding pore-creating agent and tensio-active agent, mechanical stirring or film emulsification or spraying be dispersed to oil phase/or aqueous phase react, after scouring is finished in reaction, can obtain to have the inorganic spherical oxide material of skeleton and perfusion pore structure, perhaps after calcination or other thermal treatment, make inorganic spherical oxide material unformed and/or that crystal formation has skeleton and perfusion pore structure.
4. the synthetic method of inorganic spherical oxide material according to claim 1, it is characterized in that: the preparation of inorganic oxide can be selected the inorganic sources presoma for use, organic precursor, the formation of vesicular structure mainly is derived from pore-creating agent and obtains, presoma dissolving or hydrolysis in water/or oil phase in, to wherein adding pore-creating agent, after the reaction, use the drive of high-pressure gas material through the nozzle atomization drying, after scouring is finished in reaction, can obtain to have the inorganic spherical oxide material of skeleton and perfusion pore structure, perhaps after calcination or other thermal treatment, make inorganic spherical oxide material unformed and/or that crystalline form has skeleton and perfusion pore structure.
5. according to the synthetic method of claim 3 and the described inorganic spherical oxide material of claim 4, the inorganic sources presoma is meant water miscible salt, as water glass, potassium silicate, silicic acid, oxalic acid zirconium, zirconium oxychloride, zirconium chloride, titanium tetrachloride, cerous nitrate, magnesium chloride, aluminum nitrate, Tai-Ace S 150 etc.; Described organic source presoma is meant tetraethoxy, methyl silicate, titanium ethanolate, butyl (tetra) titanate, zirconium iso-propoxide, aluminum isopropylate etc.
6. according to the synthetic method of claim 3 and the described inorganic spherical oxide material of claim 4, pore-creating agent comprises the water miscible tensio-active agent of three classes: a. such as alkylsulfonate, alkyl-sulphate, quaternary ammonium salt, polyvinyl alcohol, polyoxyethylene glycol, polyoxyethylene glycol-polypropylene glycol segmented copolymer etc.; B. be insoluble in the pressed powder of water such as activated carbon granule, lime carbonate, inorganic particle, polymkeric substance small-particle etc., grain diameter is (10nm-2mm); C. functional unit that can polymerization reaction take place is as urea and formaldehyde, trimeric cyanamide and formaldehyde, vinylformic acid, methacrylic acid etc.; Pore-creating agent can use or mix use separately.
7. the synthetic method of inorganic spherical oxide material according to claim 3, tensio-active agent comprises three classes: a. amphoterics such as amino acid pattern, betaine type etc., b. nonionogenic tenside such as Triton, peregal, sapn, polyvalent alcohol, tween etc., c. ionic surface active agent such as alkyl-sulphate, quaternary ammonium salt etc.; Tensio-active agent can use or mix use separately.
8. the synthetic method of inorganic spherical oxide material according to claim 3, oil phase are and the immiscible organism of water, as gasoline, sherwood oil, whiteruss etc.; Oil phase reagent can use or mix use separately.
9. inorganic spherical oxide material according to claim 1, it is characterized in that: the inorganic spherical oxide material can be by chemical bonding, vapour deposition, be coated with means such as stagnant carries out surface modification, obtains and the different surface property of inorganic spherical oxide material body.The surface modification of inorganic spherical oxide material comprises to spheroid outer skeleton surface and the modification simultaneously of spheroid inner frame surface spheroid outer skeleton surface and the modification respectively of spheroid inner frame surface.The modification approach is as follows: by bonding reaction, absorption or coated, introduce alkyl, aryl, amino, carboxyl, organism or mineral ions such as sulfydryl, sulfonic group, cyclodextrin, Mierocrystalline cellulose, calixarene, amino acid, protein, DNA, antigen, antibody, coupling agent, intercalating agent, silver ions on inorganic spherical oxide material surface; Vapour deposition is to introduce materials such as charcoal, platinum, palladium, ruthenium, silver, gold by high-temperature physics and/or chemical process on inorganic spherical oxide material surface; Being coated with stagnates is meant through technologies such as colloidal sol-gel, coated, absorption, self-assemblies at the attached titanium oxide of inorganic spherical oxide material surface bag, zirconium white, magnesium oxide, calcium oxide, phosphatic rock etc.
10. according to claim 1, claim 3, described inorganic spherical oxide material of claim 4 and claim 9 and surface modified spherical inorganic oxide material are used for that chromatographic separation, filtration, catalysis are synthetic, microreactor, energy storage, medicament slow release.
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Cited By (19)
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