CN102716735B - Preparation method of ATP/ Ce-Ti sold soluble oxide composite material - Google Patents
Preparation method of ATP/ Ce-Ti sold soluble oxide composite material Download PDFInfo
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- CN102716735B CN102716735B CN201210209040.8A CN201210209040A CN102716735B CN 102716735 B CN102716735 B CN 102716735B CN 201210209040 A CN201210209040 A CN 201210209040A CN 102716735 B CN102716735 B CN 102716735B
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Abstract
The invention relates to a preparation method of an ATP (attapulgite)/ Ce-Ti (cerium-titanium ) sold soluble oxide composite material, and belongs to the technical field of finish machining of nonmetallic minerals and the inorganic chemical industry. The preparation method of the ATP/Ce-Ti sold soluble oxide composite material comprises the steps that a proper amount of cerium salt and titanium alkoxide at a molar ratio of 9:1 to 3:7 are solved in anhydrous ethanol and evenly mixed with the anhydrous ethanol to serve as a component A; a proper amount of ethanol, deionized water and glacial acetic acid are additionally taken and mixed to serve a component B; the component B is dropwise added to the component A under a continuous stirring condition, the pH (potential of hydrogen) value A is regulate to 2 to 4 by using nitric acid, and the ATP is added to an obtained solution and continuously stirred for 24 hours; and an obtained mixture is placed in a thermostat to be aged for several days to form xerogel, and after the xerogel is calcined, the ATP/Ce-Ti sold soluble oxide composite material is obtained. The method is simple to operate, requires a low cost and facilitates the realization of large-scale industrial production; and prepared ATP/CeO2-TiO2 is evenly loaded, has good dispersity and has very high industrial application value.
Description
Technical field
The present invention relates to nonmetallic mineral fine finishining and technical field of inorganic chemical industry, that concrete is the preparation method of attapulgite/cerium titanium solid solution oxide nano composite material.
Background technology
Along with industrial fast development, water pollution problems becomes increasingly conspicuous, and wherein waste water from dyestuff is one of main industrial pollution source, contains a large amount of hardly degraded organic substances in waste water from dyestuff, and colourity is high, toxicity is large, is the difficult point that current industrial pollution is administered.
Rare earth cerium oxide is the Multifunction material that a kind of cheapness and purposes are extremely wide, has unique cubic fluorite structure, higher storage/put oxygen ability and oxidation/reduction performance (Ce
3+/ Ce
4+), be widely used in the fields such as vehicle tail gas triple effect catalyzed conversion, catalytic hydrogenation and water treatment catalytic purification in catalytic field; But the heat endurance of cerium oxide is poor, easily there is high temperature sintering and cause cubic fluorite destructurized, store oxygen ability and reduce even disappearance, limited its application and development.Therefore people improve the storage of cerium oxide/put oxygen ability by different means, and the second component element that wherein adulterates is major way; Compare with pure zirconia cerium, the redox property of titanium doped cerium oxide increases, and in recent years, titanium doped cerium oxide base composite material is widely applied at catalytic field.
In actual catalytic degradation process, catalyst powder itself exists and is difficult to problem separated and that reclaim, restricted the practical application of catalyst and further promoted, being loaded on the carrier material of being convenient to reclaim is to solve at present one of the dispersiveness of catalyst and main method of reusing; Attapulgite (ATP) is a kind of natural minerals cheaply, on microcosmic, there is one dimension layer chain nano pore structure, hydrone and a certain size organic molecule all can directly be adsorbed in its duct, in macroscopic view, show as large specific area and stronger absorption and ion-exchange performance, therefore, attapulgite can be used as a kind of good catalyst carrier material; Chinese patent 200810019827.1 discloses a kind of method of attapulgite loading with nano cerium oxide, it is characterized in that adopting sluggish precipitation to prepare the material of the nanoscale cerium oxide particle of Load Balanced, good dispersion on concave convex rod; But the preparation and application research about attapulgite load cerium titanium solid solution oxide have not been reported so far.
The present invention is directed to the problem existing in cerium oxide catalyst material, take attapulgite as carrier, propose the method that two kinds of technology of a kind of combination doping and load are prepared attapulgite load cerium titanium solid solution oxide.
Summary of the invention
It is primary raw material that attapulgite, cerium salt, titanium alkoxide are take in the present invention, adopt easy sol-gel process to synthesize, by optimizing the technological parameters such as cerium titanium mol ratio, reaction and calcination condition, control pattern and the Particles Distribution of attapulgite/cerium titanium solid solution oxide composite, thereby obtain the product of Load Balanced, good dispersion.
Specific embodiment of the present invention is: get a certain amount of cerium salt and titanium alkoxide and be dissolved in appropriate absolute ethyl alcohol, mix, as component A under 20～40 ℃ of water bath with thermostatic control magnetic agitation conditions; Separately get appropriate absolute ethyl alcohol, deionized water and complexing agent mix and blend until form colourless transparent solution, as B component; Under continuing stirring condition, B component is dropwise splashed in component A, with salpeter solution, regulate pH=2～4, obtain solution C, add appropriate attapulgite, continue to stir 24 h, be placed on ageing a couple of days formation xerogel in 40～80 ℃ of insulating boxs, through 200～400 ℃ of calcining 1～5 h, obtain attapulgite/cerium titanium solid solution oxide composite.
Described cerium salt is a kind of in cerous nitrate, cerium chloride and cerous acetate, and titanium alkoxide is a kind of in isopropyl titanate and butyl titanate, and complexing agent is a kind of in glacial acetic acid, citric acid and softex kw.
The mol ratio of described cerium salt and titanium alkoxide is between 9:1～3:7, and the consumption of cerium salt and titanium alkoxide is in the quality of the cerium titanium solid solution oxide of generation, CeO
2-TiO
2gross mass accounts for 10%～80% of attapulgite quality, and attapulgite is 5～30 g/L with respect to the concentration range of solution C, and in solution, complexing agent is 2～30 g/L with respect to the concentration range of solution C.
The present invention has adopted a kind of comparatively easy chemical technology to prepare attapulgite/cerium titanium solid solution oxide nano composite material of Load Balanced, good dispersion, without complicated equipment, chemical raw material low price used, experiment favorable repeatability, has very high industrial promotional value.
Attapulgite self has abundant microcellular structure and larger specific area, and the large molecule of organic matter is had to good original position adsorption capacity, simultaneously the Mg in the layer chain structure of its uniqueness
2+, Al
3+deng cation can with carrier surface active component in cation there is possible exchange, thereby increase the conducting power in Lattice Oxygen room, promote CeO
2redox ability; The introducing of titanium is conducive to improve the redox ability of material, improves the concerted catalysis oxidability between carrier and active component, and this class composite has very large potential using value at aspects such as vehicle exhaust processing and organic dye waste water degradeds.
Accompanying drawing explanation
Fig. 1 is ATP, ATP/CeO
2and ATP/CeO
2-TiO
2(Ce:Ti=5:5) XRD spectra of sample;
Fig. 2 is ATP/CeO
2-TiO
2(Ce:Ti=5:5) the TEM photo of sample 50 nm scale scopes;
Fig. 3 is ATP/CeO
2and ATP/CeO
2-TiO
2(Ce:Ti=5:5) the COD degradation rate curve of sample to rhodamine B.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment:
Embodiment 1: the 0.0016 mol cerous nitrate that is first 5:5 by cerium titanium mol ratio under 30 ℃ of water-bath magnetic agitation, 0.0016 mol butyl titanate evenly mix with 20 mL absolute ethyl alcohols, as component A; By other 10 mL absolute ethyl alcohols, 3 mL deionized waters and 0.2 g glacial acetic acid mix and blend until form colourless transparent solution, as B component; Under continuing stirring condition, B component is slowly splashed in component A, then with red fuming nitric acid (RFNA), regulate pH=4, obtain solution C, add 1 g attapulgite, continue to stir 24 h, be placed on ageing a couple of days formation xerogel in 60 ℃ of insulating boxs, at 400 ℃, calcine 3 h, obtain attapulgite load CeO
2-TiO
2(Ce:Ti=5:5) composite.
Gained sample is carried out to X-ray powder diffraction experiment, and observe its pattern and structure under transmission electron microscope, the attapulgite load CeO making according to the technological parameter of embodiment 1
2-TiO
2(Ce:Ti=5:5) with attapulgite, attapulgite load CeO
2xRD Comparative map as shown in Figure 1, preparation attapulgite load CeO
2-TiO
2(Ce:Ti=5:5) in, there is obvious CeO
2characteristic diffraction peak, formed cerium oxide after reaction is described, simultaneously and attapulgite load CeO
2in diffraction maximum compare, the introducing of titanium makes CeO
2(111) angle of diffraction of crystal face is to high angle direction generation slight shift, and diffraction maximum relative intensity weakens, and may be by Ti
4+ionic radius (0.068 nm) is less than Ce
4+the reason of radius (0.0993 nm) causes.
ATP/CeO
2-TiO
2(Ce:Ti=5:5) the TEM photo of sample as shown in Figure 2, as can be seen from the figure, CeO
2-TiO
2oxide particle uniform load is at attapulgite surface, oxide particle diameter 5-10 nm.
ATP/CeO
2and ATP/CeO
2-TiO
2(Ce:Ti=5:5) sample to the COD degradation rate curve of rhodamine B as shown in Figure 3, as can be seen from the figure, ATP/CeO
2to the COD degradation rate of rhodamine B, be 80%; Mix after Ti CeO
2-TiO
2grain diameter reduces, ATP/CeO
2-TiO
2(Ce:Ti=5:5) sample reaches more than 96% the COD degradation rate of rhodamine B.
Embodiment 2: changing cerium titanium mol ratio is 9:1, cerium salt is that cerium chloride, titanium alkoxide are isopropyl titanate, the addition of cerium chloride is 0.00225 mol, the addition of isopropyl titanate is 0.00025 mol, and the quality of attapulgite is 0.5 g, and change complexing agent is softex kw, the quality of softex kw is 0.8 g, 20 ℃ of water-bath 24 h, then through 200 ℃ of calcining 2 h, subsequent detection effect is as embodiment 1.
Embodiment 3: changing cerium titanium mol ratio is 3:7, cerium salt is that cerous acetate, titanium alkoxide are isopropyl titanate, the addition of cerous acetate is 0.0011 mol, the addition of isopropyl titanate is 0.0026 mol, and the quality of attapulgite is 1 g, and change complexing agent is citric acid, the quality of citric acid is 0.2 g, 40 ℃ of water-bath 24 h, through 400 ℃ of calcining 2 h, subsequent detection effect is as embodiment 1.
Embodiment 4: changing cerium titanium mol ratio is 8:2, cerium salt is that cerium chloride, titanium alkoxide are butyl titanate, the addition of cerium chloride is 0.0020 mol, the addition of isopropyl titanate is 0.0005 mol, the quality of attapulgite is 0.4 g, and the quality of glacial acetic acid is 0.6 g, 40 ℃ of water-bath 24 h, through 400 ℃ of calcining 3 h, subsequent detection effect is as embodiment 1.
Embodiment 5: changing cerium titanium mol ratio is 6:4, cerium salt is that cerous acetate, titanium alkoxide are butyl titanate, the addition of cerous acetate is 0.0018 mol, the addition of butyl titanate is 0.0012 mol, the quality of attapulgite is 1.2 g, and the quality of glacial acetic acid is 0.4 g, 30 ℃ of water-bath 24 h, through 300 ℃ of calcining 4 h, subsequent detection effect is as embodiment 1.
Claims (2)
1. the preparation method of attapulgite/cerium titanium solid solution oxide nano composite material, it is characterized in that comprising the steps: to get a certain amount of cerium salt and titanium alkoxide is dissolved in appropriate absolute ethyl alcohol, under 20～40 ℃ of water bath with thermostatic control magnetic agitation conditions, mix, as component A; Separately get appropriate absolute ethyl alcohol, deionized water and complexing agent mix and blend until form colourless transparent solution, as B component; Under continuing stirring condition, B component is dropwise splashed in component A, with salpeter solution, regulate pH=2～4, obtain solution C, add appropriate attapulgite, continue to stir 24 h, be placed on ageing a couple of days formation xerogel in 40～80 ℃ of insulating boxs, through 200～400 ℃ of calcining 1～5 h, obtain attapulgite/cerium titanium solid solution oxide composite;
The mol ratio of described cerium salt and titanium alkoxide is between 9:1～3:7, and the consumption of cerium salt and titanium alkoxide is in the quality of the cerium titanium solid solution oxide of generation, CeO
2-TiO
2gross mass accounts for 10%～80% of attapulgite quality, and attapulgite is 5～30 g/L with respect to the concentration range of solution C, and in solution, complexing agent is 2～30 g/L with respect to the concentration range of solution C.
2. the preparation method of attapulgite/cerium titanium solid solution oxide nano composite material as claimed in claim 1, it is characterized in that: described cerium salt is a kind of in cerous nitrate, cerium chloride and cerous acetate, titanium alkoxide is a kind of in isopropyl titanate and butyl titanate, and complexing agent is a kind of in glacial acetic acid, citric acid and softex kw.
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