CN1884047A - General method for preparing spherical porous metal oxide - Google Patents
General method for preparing spherical porous metal oxide Download PDFInfo
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- CN1884047A CN1884047A CN 200610014735 CN200610014735A CN1884047A CN 1884047 A CN1884047 A CN 1884047A CN 200610014735 CN200610014735 CN 200610014735 CN 200610014735 A CN200610014735 A CN 200610014735A CN 1884047 A CN1884047 A CN 1884047A
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Abstract
The invention discloses a universal method and utility of porous metal oxide and preparing method of organic spherical grain in the porous inorganic spherical grain preparing technological domain, which is characterized by the following: adopting ionic exchanging resin as mould; sedimenting complex compound or coordinate through acting metal salt and mould through alkali; drying; sintering to remove organic mould and carbon; synthesizing series of metal oxide ball with multi-size structure of iron scale, aluminium oxide, titanium oxide and cobalt oxide. The invention possesses high specific surface area, multi-size hole diameter, which displays important utility in the catalytic, adsorbing and spectrum domains.
Description
Technical field
The invention belongs to the technical field for preparing porous, inorganic thing spheroidal particle with organism spheroidal particle template, particularly universal method of preparation porous metal oxide ball (from micron order to the millimeter level) and uses thereof.
Background technology
Inorganic porous material is a feature with bigger specific surface area, is widely used in the actual production as catalyzer, support of the catalyst and sorbent material.According to the classification of International Union of Pure and Applied Chemistry (IUPAC), the aperture is called micropore below 2nm, and the aperture is mesoporous between 2～50nm, and is macropore greater than the hole of 50nm.In actual applications, the micropore of porous material and mesoporous part are bigger to the specific surface area contribution of material, make material compare with bulk material and have more active centre, and big bore portion more helps transmission and the transfer of reaction medium between the material duct.Therefore synthetic a kind of material that contains macropore and mesoporous or micropore simultaneously, both so-called multiple dimensioned hole material, more meaningful for the practical application of material.
For the preparation and the application of porous material, all there are both at home and abroad a large amount of documents and monograph to report and sum up.As " Handbook of Porous Solids " that people such as FerdiSch ü th write " and a series of survey articles of delivering (see also F.Sch ü th, K.S.W.Sing, J.Weitkamp.Handbook of Porous Solids.Wiley-VCH, Weinheim, 2002; F.Sch ü th.Angew.Chem.Int.Ed.2003,42,3604; F.Sch ü th.Chem.Mater.2001,13,3184; F.Sch ü th.Chem.Mater.2005,17,4577.).The researchist of U.S. Mobil Oil Corp. in 1992 has broken through the bottleneck of preparation mesopore oxide material, they are template with the self-assembly aggregate that tensio-active agent forms, synthesized Metaporous silicon dioxide material with regular orderly pore passage structure by sol-gel process, specific surface area is big, the aperture is adjustable between 1.5～10nm, thereby the new era of having opened the molecular sieve science (sees also C.T.Kresge, M.E.Leonowicz, W.J.Roth, et al.Nature 1992,359,710.).This report causes the attention of international academic community immediately, has from then on started the upsurge of research mesoporous material.Thereafter, people such as Stucky successfully are extended to aforesaid method in the synthetic non-silicon oxide series mesoporous material, obtain having than bigger serface, contain order mesoporous porous metal oxide.But the porous material that these methods obtain is to exist with powder type mostly, and preparation cycle long (generally needing a week), the expensive raw material price of use.Powdered material can run in actual applications such as be difficult for recovery and separate, augmenting response system pressure degradation problem, and macrobead shape (millimeter level), the porous material of especially spherical macrobead shape has its original advantage on these are used.Effective ways for the porous material for preparing the macrobead shape are confined to unformed binding agent active ingredient be bonded together moulding then.This method has two shortcomings at least: the one, and binding agent usually can block a lot of holes, thereby has reduced the specific surface area of material; The 2nd, the existence of binding agent can influence the specified property of active ingredient, such as the unicity of forming component, katalysis etc.Therefore explore a kind of cost of material low, be easy to suitability for industrialized production and the strong synthetic method with the big ball of multiple dimensioned pore structure of universality is very necessary.Sterte and his co-worker utilize anionite-exchange resin to prepare a series of zeolite or molecular sieve big ball materials with multiple dimensioned pore structure as template and (see also L.Tosheva, V.V.altchev, J.Sterte.Micropor.Mesopor.Mater.2000,35～36,621; L.Tosheva, V.V.altchev, J.Sterte.J.Mater.Chem.2000,10,2330.).Yet for the rare report of the preparation of the big ball of porous metal oxide.
Summary of the invention
The purpose of this invention is to provide a kind of is template by ion exchange resin, by forming resin-metal oxyhydroxide mixture, prepares the spherical particulate method of metal oxide then.
Another purpose of the present invention provides and a kind ofly constitutes method from micron order to millimeter level porous oxide ball by nanocrystal, and the oxide compound ball of preparation has higher specific surface area, contains macropore and mesoporous simultaneously, and voidage is higher, and apparent density is lower.
Related ion exchange resin, not only can be used as template, guarantee the spherical appearance of final material, and the functional group (as acid group, sulfonate radical or other chelation groups) that is rich in of its surface, duct, has good hydrophilicity, can form complex compound or chelate with the metal ion in the aqueous solution or other polar solvent, the method by in-situ precipitate is converted into metal hydroxides with metal ion.Sintering under air atmosphere can be removed as the resin of template and stays hole, simultaneously, transfers metal hydroxides to corresponding metal oxide, obtains having the oxide compound ball of multiple dimensioned pore structure.Therefore, this method has very strong universality, and is simple to operate, and cost of material is cheap, is easy to industrialization.
The objective of the invention is to be achieved through the following technical solutions:
The universal method of preparation spherical porous metal oxide comprises following processing step:
1) preparation of precursor complex
Get commercially available ion exchange resin, add the aqueous solution or the polar solvent of excessive 1～5 times metal-salt, stirred under the room temperature 2～24 hours, filter, be washed till filtrate with distilled water and be neutral; Add excess base, stirred under the room temperature 2～24 hours, filter, be washed till filtrate with distilled water and be neutral.
2) the above-mentioned resin-metal oxyhydroxide mixture that makes was placed 100～200 ℃ of baking ovens dry 2 hours.The composite ball that drying is good places retort furnace, rises to 400～1200 ℃ with the heat-up rate of 5～30 ℃/min; Take out after being cooled to room temperature, promptly get the big ball of porous metal oxide.
Described metal-salt has following properties:
1) in the water-soluble or polar solvent;
2) with the functional group complexing or the chelating of resin;
3) Dui Ying oxyhydroxide is insoluble or be slightly soluble in water.
Described ion exchange resin is spherical, contains a large amount of mesoporous or macropores, and complexing group or chelation group are contained in the surface, duct, with complexing of metal ion or chelating.Ion exchange resin is: strongly-acid or weakly acidic cation-exchange resin, resin and anyly can exchange with metal ion, the resin of complexing or chelating.
Described metal-salt can bore or cobalt chloride for aluminum nitrate, aluminum chloride, Tai-Ace S 150, iron protochloride, iron nitrate, titanium sulfate solution, nitric acid.
The feature of the spherical porous metal oxide of method for preparing is: the mean diameter of spherical porous oxide compound is from 1 μ m to 2mm, form for nano-metal-oxide crystal from 5nm to 400nm by size, has multiple dimensioned pore structure, contain the mesoporous of the macropore of 0.1～10 μ m and 2～20nm simultaneously, specific surface area is 20～600m
2/ g, pore volume are 0.2～2.0cm
3/ g, density is 0.3～2.2g/cm
3
The big ball of described porous metal oxide is applied to vehicle exhaust processing, tobacco filter, oil catalytic pyrolysis, gas sensor, sewage disposal, photocatalytic degradation, sorbent material or support of the catalyst.
Description of drawings
Accompanying drawing 1 is X-ray diffraction (XRD) figure of embodiment 1,2 and 3 prepared porous ferric oxide, aluminum oxide and titanium oxide, illustrates that these materials are made up of corresponding pure α type ferric oxide, γ type aluminum oxide, anatase titanium dioxide crystal.
Accompanying drawing 2a, b and c are respectively scanning electron microscope (SEM) figure of embodiment 1,2 and 3 prepared porous ferric oxide, titanium oxide and aluminum oxide, the existence of these material macropores is described, illustration is the SEM figure (scale is 250 μ m in the illustration) of corresponding low magnification, and the spherical appearance of these materials is described.
Accompanying drawing 3a, b and c are respectively transmission electron microscope (TEM) figure of embodiment 1,2 and 3 prepared porous ferric oxide, titanium oxide and aluminum oxide, illustration is corresponding height explanation transmission electron microscope (HRTEM) figure (scale is 2nm in the illustration), illustrates that these materials are that the nanocrystal of 20～100nm, 5～15nm and 6～20nm is formed by particle diameter respectively.
Accompanying drawing 4 is the N of prepared porous ferric oxide (a, d), aluminum oxide (b, e) and titanium oxide (c, f) of embodiment 1,2 and 3
2Adsorption curve and corresponding pore size distribution curve illustrate the existence that these materials are mesoporous and have bigger specific surface area.The specific surface area of porous ferric oxide, aluminum oxide and titanium oxide is respectively 20.5m
2/ g, 92.7m
2/ g and 173.5m
2/ g.
Specific implementation method
The present invention is further described below in conjunction with embodiment.
Embodiment 1
Adding the commercially available particle diameter of 10g in the container is 500～700 μ m Zeo-karb D072 and 10% solution of ferrous chloride 60mL, stirs 8 hours under the room temperature, makes resin that ion-exchange fully take place, and filters then, is washed till filtrate with distilled water and is neutral; Add excessive alkali lye in the resin, stirred 8 hours under the room temperature, filter, be washed till filtrate with distilled water and be neutral, obtain resin-ferric hydroxide composite.After mixture placed 120 ℃ of dry 2h of baking oven, be transferred in the retort furnace, heat-up rate with 5～10 ℃/min is warming up to 400 ℃, and insulation 1h continues to be warming up to 550 ℃, be incubated 6 hours, power cutoff takes out after being cooled to room temperature, the big ball of porous metal ferric oxide, diameter is 300～450 μ m, and specific surface area is 20.5m
2/ g, pore volume are 0.26cm
3/ g, pore size distribution are at 0.1～1.5 μ m and 2～16nm, and apparent density is 2.22g/cm
3, form by the α type ferric oxide crystal that 20～90nm is pure.
Embodiment 2
Adding the commercially available particle diameter of 10g in the container is 500～700 μ m Zeo-karb D072 and 10% aluminum nitrate solution 70mL, stirs 8 hours under the room temperature, makes resin that ion-exchange fully take place, and filters then, is washed till filtrate with distilled water and is neutral; Add excessive alkali lye in the resin, stirred 8 hours under the room temperature, filter, obtain resin-aluminium hydroxide mixture.Place 120 ℃ of baking ovens after dry 2 hours mixture, be transferred in the retort furnace, be warming up to 800 ℃ with the heat-up rate of 5～10 ℃/min, be incubated 6 hours, power cutoff takes out after being cooled to room temperature, get the big ball of porous metal aluminum oxide, diameter is 220～380 μ m, and specific surface area is 92.7m
2/ g, pore volume are 0.23cm
3/ g, pore size distribution are at 2～200nm, and apparent density is 2.08g/cm
3, form by the γ type alpha-alumina crystals that 6～20nm is pure.
Embodiment 3
Adding the commercially available particle diameter of 10g in the container is 500～700 μ m Zeo-karb D072 and 10% titanium sulfate solution 50mL, stirs 8 hours under the room temperature, makes resin that ion-exchange fully take place, and filters then, is washed till filtrate with distilled water and is neutral; Add excessive alkali lye in the resin, stirred 8 hours under the room temperature, filter, be washed till filtrate with distilled water and be neutral, obtain resin-titanium hydroxide mixture.Place 120 ℃ of baking ovens after dry 2 hours mixture, be transferred in the retort furnace, be warming up to 600 ℃ with the heat-up rate of 5～10 ℃/min, be incubated 6 hours, power cutoff takes out after being cooled to room temperature, get the big ball of porous metal ferric oxide, diameter is 350～500 μ m, and specific surface area is 173.5m
2/ g, pore volume are 0.77cm
3/ g, pore size distribution are at 0.2～3.0 μ m and 2～20nm, and apparent density is 0.98g/cm
3, form by the anatase titanium dioxide crystal that 5～13nm is pure.
Claims (7)
1. universal method for preparing spherical porous metal oxide is characterized in that described method comprises following processing step:
1) preparation of precursor complex
Get commercially available ion exchange resin, add the aqueous solution or the polar solvent of excessive 1～5 times metal-salt, stirred under the room temperature 2～24 hours, filter, be washed till filtrate with distilled water and be neutral; Add excess base, stirred under the room temperature 2～24 hours, filter, be washed till filtrate with distilled water and be neutral.
2) the above-mentioned resin-metal oxyhydroxide mixture that makes was placed 100～200 ℃ of baking ovens dry 2 hours.The composite ball that drying is good places retort furnace, rises to 400～1200 ℃ with the heat-up rate of 5～30 ℃/min; Take out after being cooled to room temperature, promptly get the porous metal oxide ball.
2. the universal method of preparation spherical porous metal oxide as claimed in claim 1 is characterized in that: described metal-salt has following properties:
1) in the water-soluble or polar solvent;
2) with the functional group complexing or the chelating of resin;
3) Dui Ying oxyhydroxide is insoluble or be slightly soluble in water.
3. the universal method of preparation spherical porous metal oxide as claimed in claim 1 is characterized in that: described ion exchange resin contains a large amount of mesoporous or macropores for spherical, and complexing group or chelation group are contained in the surface, duct, with complexing of metal ion or chelating.
4. the universal method of preparation spherical porous metal oxide as claimed in claim 1 is characterized in that: described ion exchange resin is: strongly-acid or weakly acidic cation-exchange resin, resin and anyly can exchange with metal ion, the resin of complexing or chelating.
5. the universal method of preparation spherical porous metal oxide as claimed in claim 2 is characterized in that: described metal-salt can be aluminum nitrate, aluminum chloride, Tai-Ace S 150, iron protochloride, iron nitrate, titanium sulfate solution, Xiao Suangu or cobalt chloride.
6. as the spherical porous metal oxide of each described method preparation of claim 1～5, it is characterized in that: the mean diameter of spherical porous oxide compound is from 1 μ m to 2mm, form for nano-metal-oxide crystal from 5nm to 400nm by size, has multiple dimensioned pore structure, contain the mesoporous of the macropore of 0.1～10 μ m and 2～20nm simultaneously, specific surface area is 20～600m
2/ g, pore volume are 0.2～2.0cm
3/ g, density is 0.3～2.2g/cm
3
7. as the application method of each described porous metal oxide ball of claim 1～5, it is characterized in that: the big ball of described porous metal oxide is applied to vehicle exhaust processing, tobacco filter, oil catalytic pyrolysis, gas sensor, sewage disposal, photocatalytic degradation, sorbent material or support of the catalyst.
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