CN114425313A - Titanium dioxide-aluminum oxide composite oxide and preparation and application thereof - Google Patents
Titanium dioxide-aluminum oxide composite oxide and preparation and application thereof Download PDFInfo
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- CN114425313A CN114425313A CN202011097844.4A CN202011097844A CN114425313A CN 114425313 A CN114425313 A CN 114425313A CN 202011097844 A CN202011097844 A CN 202011097844A CN 114425313 A CN114425313 A CN 114425313A
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- composite oxide
- titanium dioxide
- alumina
- titanium
- titanate
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- PHTHEUNUXVDUOD-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[O-2].[Al+3] PHTHEUNUXVDUOD-UHFFFAOYSA-N 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 32
- 239000011593 sulfur Substances 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- -1 titanium alkoxide Chemical class 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910006415 θ-Al2O3 Inorganic materials 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 239000002912 waste gas Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 150000002910 rare earth metals Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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Abstract
The invention provides a titanium dioxide-alumina composite oxide, a preparation method and application thereof. In the composite oxide, titanium dioxide nanoparticles cover the surface of alumina, the mass of the titanium dioxide accounts for 5-20% of the total mass of the composite oxide, and further, the specific surface area of the composite oxide is not less than 80m2Per g, pore volume is not less than 0.4cm3G, sulfur adsorption capacity not higher than 30 mu g/m3. The composite oxide provided by the invention can be used as a carrier to prepare a supported noble metal catalyst, and the catalyst shows excellent sulfur resistance and high temperature resistance, and is suitable for application in the field of waste gas purification.
Description
Technical Field
The invention relates to a composite oxide capable of being used as a catalyst carrier, a preparation method and application thereof, in particular to a titanium dioxide-alumina composite oxide with excellent sulfur resistance and high temperature resistance, and a preparation method and application thereof. The composite oxide can be used for preparing catalysts in the field of tail gas purification.
Background
Alumina is one of common catalyst carriers and is widely applied to the purification of motor vehicle exhaust and the catalytic combustion process of organic waste gas in various industries. In addition to requiring long-term operation at high temperatures, such catalytic processes often encounter various types of impurities, with elemental sulfur being the most typical impurity element and often being present in various types of tail gases as sulfur oxides. The accumulation of sulfur on alumina for a long time will gradually form aluminum sulfate species, resulting in the reduction of surface hydroxyl content and the coverage of catalytic active sites, reducing the performance of the catalyst.
Titanium dioxide, particularly titanium dioxide in the anatase crystalline phase, has good sulfur resistance and has the property of promoting catalytic reactions in specific reactions. However, in the above reaction, since the catalyst needs to be operated at a high temperature for a long time, the anatase type titanium dioxide is gradually transformed into the rutile crystalline phase at a temperature ranging from 400 ℃ to 600 ℃, and the specific surface area of the titanium dioxide of the crystalline phase is greatly reduced (<10m2/g), thereby limiting the use of titanium dioxide in the above-mentioned catalytic fieldsThe use of (1). Compounding titanium dioxide and aluminum oxide by different preparation methods to obtain TiO2-Al2O3The composite oxide can be utilized to TiO2The sulfur resistance of the alloy can be improved, and the crystal phase transformation temperature of the alloy can be improved to inhibit the reduction of the specific surface area of the alloy. Patent CN 110935432 a discloses a titanium oxide-alumina composite oxide and a preparation method thereof. The composite oxide obtained by the method has higher specific surface area and pore volume, but the preparation conditions are complicated, and the chemical property change after high-temperature treatment is not given; US 5922294 discloses a thermally stable TiO prepared by hydrolysis of mixed alkoxides2-Al2O3The oxide obtained by the method has smaller specific surface area after high-temperature treatment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide TiO2-Al2O3The composite oxide has strong high temperature resistance and good sulfur resistance, and can be used as a carrier of a catalyst in the field of tail gas purification.
The first aspect of the present invention is to provide a titania-alumina composite oxide having the following properties: the mass of the titanium dioxide accounts for 5-20% of the total mass of the composite oxide, and the titanium dioxide nano particles only cover the surface of the alumina without independent titanium dioxide aggregates.
In the present invention, the specific surface area of the composite oxide is not less than 80m2Preferably 80 to 170 m/g2(ii)/g; pore volume of not less than 0.4cm3Preferably 0.4 to 0.6 cm/g3/g。
In the present invention, the sulfur adsorption amount of the composite oxide is not more than 30 μ g/m2Preferably 20 to 30 μ g/m2. The sulfur adsorption amount of the composite oxide is calculated by the following formula:
wherein V represents the sulfur adsorption amount of the composite oxide, m is the weight gain of the sample after adsorption experiment, and SA is the ratio table of the sampleArea.
Another aspect of the present invention provides a method for preparing a titania-alumina composite oxide, comprising the steps of:
(1) dispersing alumina in an anhydrous alcohol solution to obtain a dispersion liquid;
(2) adding titanium alkoxide into the anhydrous alcohol solution, and fully stirring and dissolving; then mixing the dispersion liquid obtained in the step (1) with the solution, and carrying out reflux reaction for 2-6 h at the temperature of 60-80 ℃;
(3) after the reaction is finished, filtering, washing, drying and roasting to obtain the titanium dioxide-aluminum oxide composite oxide.
In the present invention, the alumina in the step (1) may be γ -Al2O3、θ-Al2O3、α-Al2O3And the like, any of the common commercial aluminas. The alumina may also be doped with any auxiliary agent, such as alkali metal, alkaline earth metal or rare earth metal.
In the invention, the feeding amount of the titanium alkoxide in the step (2) is controlled in a way that the molar ratio of Ti to Al is 1: 20-1: 5.
the absolute alcohol solutions in the step (1) and the step (2) can be the same or different and are both liquid monoalcohols at normal temperature and normal pressure. Such as one or more of methanol, ethanol, isopropanol, n-propanol, n-butanol, etc., preferably ethanol and/or isopropanol.
In the invention, the titanium alkoxide in the step (2) can be one or more of common tetrabutyl titanate, tetraethyl titanate, isopropyl titanate, titanium tetramethoxide, titanium isooctanolate and the like; preferably one or more of tetrabutyl titanate, tetraethyl titanate, isopropyl titanate.
In the present invention, the order of mixing and adding the dispersion and the solution in the step (2) is not particularly limited, and the dispersion may be added to the solution, or the solution may be added to the dispersion. In the reflux process in the step (2), the whole system is preferably protected by inert gas (such as nitrogen). Preferably, the refluxing is carried out under stirring.
In the present invention, the washing in step (3) is performed using an anhydrous alcohol solution. The drying is ordinary normal pressure drying, the drying temperature is 40-120 ℃, and the preferable drying temperature is 60-80 ℃. The roasting is carried out for 4-8 hours at 500-800 ℃.
It is a further aspect of the present invention to provide a use of the aforementioned composite oxide in the field of exhaust gas purification. The catalyst has excellent sulfur resistance and high temperature resistance.
The invention has the advantages that: 1) common commercial alumina is adopted as a modification object, only common titanium alkoxide is added in the preparation process, and the hydrolysis rate and the deposition part of the titanium alkoxide are controlled by utilizing the solution phase molecular deposition process that hydroxyl on the surface of the alumina and the alkoxide are slowly hydrolyzed in an alcohol solution, so that the titanium dioxide is ensured to form a nano oxidation state thin layer only on the surface of the alumina, and the problems of formation of a free titanium dioxide structure and consequent alumina pore volume blockage are avoided. 2) The obtained alumina composite oxide with the surface covered with titanium dioxide has high specific surface area and sulfur resistance, can be used as a carrier of a heterogeneous catalyst, is particularly suitable for the heterogeneous catalyst applied in the field of tail gas purification, and can adsorb and decompose pollutants in tail gas.
Drawings
The foregoing summary of the invention has been presented in some detail. The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is an XRD spectrum of a composite oxide prepared in example 1;
FIG. 2 is an XRD spectrum of the composite oxide prepared in comparative example 2;
FIG. 3 is a HAADF-STEM-EDS element distribution diagram of the composite oxide prepared in example 1.
Representative TiO is not shown in FIG. 1 at 25.3 ℃ 2. theta2Characteristic diffraction peaks of the crystalline phase, indicating TiO2The dispersion is uniform and the structure is stable; the most intense characteristic peak in FIG. 2 at 25.3 ℃ 2 θ is anatase TiO2Characteristic diffraction peaks of (a); drawings3 white part of the large graph represents a composite oxide; and the area in the white frame was scanned for three elements, Al, O and Ti, and the results showed that the shapes of the three elements could overlap, indicating that Ti was only present in Al and O (i.e., Al)2O3) Is present within a range of (a); meanwhile, the Ti element scanning result shows that the Ti is uniformly distributed and distributed on the whole Al2O3Surface of (2) indicates that Ti is only in Al2O3The surface is uniformly distributed.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. It should be noted that the following detailed description is only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
The specific surface area and pore volume of the samples were tested on a Micromeritics TriStar 3000 instrument. The adsorption-desorption curve of the sample is tested at-196 ℃ after the sample is subjected to vacuum desorption for 4 hours at 200 ℃ before the test, and the specific surface area and the pore volume of each sample are calculated by adopting a BET method.
The XRD spectrum detection of each sample was performed on a Bruker D8 advanced X-ray diffractometer. Using K alpha rays of a Cu target
As a radiation source. The tube voltage and tube current of the X-ray were 40kV and 40mA, respectively. The diffraction scan range is 10-80 deg., and the scan rate is 6 deg./min.
Dark field electron microscope and element scanning analysis of the samples were analyzed and examined using a FEI Tecnai 20S-TWIN electron microscope with an operating voltage of 200 kV.
Additionally, a sulfur adsorption experiment is adopted in the invention to verify that the coverage of the titanium dioxide improves the sulfur resistance of the composite oxide, and the method can further judge the uniformity of the coverage of the titanium dioxide. In the course of the test, TiO in anatase form2The sulfur adsorption amount of (2) is used as a reference. Assuming pure anatase TiO2Has a sulfur adsorption amount of 30. mu.g/m2Since sulfur adsorption occurs only on the surface, if the sulfur adsorption amount of the composite oxide is not so different from that, it is considered thatThe surface of the composite oxide is TiO2Structure i.e. TiO2The surface of the alumina is uniformly covered.
The specific steps of the experiment were as follows: a50 mg sample was taken for thermogravimetric analysis. The sample was first treated at 300 ℃ for 1h under high purity nitrogen at a flow rate of 100mL/min to remove impurities on the surface. Followed by 100ppm SO2/10％O2Treating the sample with mixed gas of/He, controlling the flow at 100mL/min, and treating for 4h until SO2The adsorption of (b) has reached saturation. SO was calculated over 4 hours2And (3) carrying out normalization treatment on the specific surface of the sample to obtain the sulfur adsorption quantity of the composite oxide. The formula is as follows:
wherein V represents the sulfur adsorption amount of the composite oxide, m is the weight gain of the sample after the adsorption experiment, and SA is the specific surface area of the sample.
Example 1
45g of commercial gamma-Al2O3(5wt％La2O3Doped, huaminghana rare earth new material limited) was fully dispersed in 500mL of an anhydrous ethanol solution to obtain a dispersion. At the same time, 21.25g of tetrabutyl titanate was added to 200mL of anhydrous isopropanol and dissolved with sufficient stirring. The two solutions are mixed well, refluxed for 3 hours at 80 ℃, filtered, soaked and washed by 100mL of absolute ethanol solution, dried overnight at 60 ℃, and roasted for 4 hours at 700 ℃. The specific surface area of the sample was tested to be 162m2Per g, pore volume of 0.51cm3/g；TiO2The content of (A) was 8.6% by XRF test, and the sulfur adsorption amount was 25. mu.g/m as measured by sulfur adsorption experiment2The specific data are shown in table 1.
Example 2
45g of commercial gamma-Al2O3(5wt％La2O3Doped, huaminghana rare earth new material limited) was fully dispersed in 500mL of an anhydrous ethanol solution to obtain a dispersion. While simultaneously mixing 42.5g of tetrabutyl titanateAdded to 200mL of isopropanol and dissolved with sufficient stirring. The two parts are mixed well, refluxed for 3 hours at 80 ℃, filtered, soaked and washed by 100mL of absolute ethanol solution, dried overnight at 60 ℃, and roasted for 4 hours at 700 ℃. The specific surface area of the sample was determined to be 148m2Per g, pore volume of 0.50cm3/g；TiO2The content of (A) was 14.8% by XRF test, and the sulfur adsorption amount was 30. mu.g/m by sulfur adsorption experiment2The specific data are shown in table 1.
Example 3
45g of commercial theta-Al2O3(Huaming Ganna rare earth new material Co., Ltd.) was sufficiently dispersed in 500mL of an anhydrous ethanol solution to obtain a dispersion. At the same time, 14.5g of tetraethyl titanate was added to 200mL of anhydrous methanol and dissolved by stirring thoroughly. The two solutions were mixed well, refluxed at 60 ℃ for 5 hours, filtered, washed by soaking in 100mL of anhydrous methanol solution, dried at 100 ℃ overnight, and calcined at 750 ℃ for 6 hours. The specific surface area of the sample was measured to be 90m2Per g, pore volume of 0.43cm3/g；TiO2Specific data of the content (c) and the sulfur adsorption amount are shown in table 1.
Example 4
45g of commercial alpha-Al2O3(Huaming Ganna rare earth new material Co., Ltd.) was sufficiently dispersed in 500mL of an anhydrous ethanol solution to obtain a dispersion. At the same time, 17.9g of isopropyl titanate was added to 200mL of anhydrous isopropyl alcohol and dissolved with sufficient stirring. The two solutions are mixed well, refluxed for 4 hours at 70 ℃, filtered, soaked and washed by 100mL of absolute ethanol solution, dried overnight at 40 ℃, and roasted for 8 hours at 550 ℃. The specific surface area of the sample was found to be 83m2Per g, pore volume of 0.47cm3/g；TiO2Specific data of the content (c) and the sulfur adsorption amount are shown in table 1.
Example 5
Application example, a noble metal Pt-supported catalyst was prepared using the support obtained in example 1. By means of H2PtCl6The precursor is used as Pt and is subjected to equal-volume impregnation and roasting to obtain Pt/TiO2-Al2O3Noble metal catalyst, Pt as sample1% of the total mass. The catalyst is applied to the catalytic oxidation reaction of ethylene in purified tail gas, and the evaluation conditions of the reaction are as follows: 2000ppm C2H4+20ppm SO2+10vol％O2The balance gas is N2. The reaction temperature is 320 ℃, and the reaction space velocity is 20,000h-1。C2H4The removal efficiency of (3) was 97.9%.
Comparative example 1
This comparative example prepared a titanium oxide-alumina composite oxide by the preparation method in the prior art document ("Effects of the addition of titanium on the thermal characterization of aluminum-supported palladium", Journal of Molecular Catalysis A,2002,180, 285-291). Taking gamma-Al2O3(5wt％La2O3Doping, Huaming Gannan rare earth new materials Co., Ltd.) 20g, and dissolving 7.2g of isopropyl titanate in 15mL of isopropanol, and fully stirring. Followed by the reaction of gamma-Al2O3Dispersed in the isopropanol solution of the isopropyl titanate, dried at 110 ℃ overnight, and then roasted at 600 ℃ for 6 hours. TiO 22The content of (A) was 9.9% by XRF test, and the sulfur adsorption amount was 41. mu.g/m by sulfur adsorption experiment2The specific data are shown in table 1.
Comparative example 2
In the comparative example, tetrabutyl titanate is loaded on the surface of the alumina powder by adopting an isometric impregnation method. The preparation process comprises the following steps: taking gamma-Al2O3(5wt％La2O3Doping, Huaming Gannan rare earth new materials Co., Ltd.) 20g, and dissolving tetrabutyl titanate 7.6g in anhydrous ethanol 15 mL. Mixing gamma-Al2O3Dispersed in the above solution, dried overnight at 60 ℃ and then calcined at 700 ℃ for 4 hours. TiO 22The content of (A) was 9.3% by XRF test, and the sulfur adsorption amount was 47. mu.g/m by sulfur adsorption experiment2The specific data are shown in table 1.
Comparative example 3
This comparative example used the noble metal Pt-supported carrier catalyst prepared in comparative example 2. By means of H2PtCl6The precursor is used as Pt and is subjected to equal-volume impregnation and roasting to obtain Pt/TiO2-Al2O3Noble metal catalyst, Pt accounts for 1% of the total mass of the sample. The catalyst is applied to the catalytic oxidation reaction of ethylene in purified tail gas, and the evaluation conditions of the reaction are as follows: 2000ppm C2H4+20ppm SO2+10vol％O2The balance gas is N2. The reaction temperature is 320 ℃, and the reaction space velocity is 20,000h-1。C2H4The removal efficiency of (3) was 83.2%.
TABLE 1 composition of composite oxides obtained in various examples and comparative examples and adsorption test results
As can be seen from the data in Table 1, the TiO of the present invention2-Al2O3The composite oxide has strong high temperature resistance and good sulfur resistance, and can be used as a carrier of a heterogeneous catalyst.
Claims (11)
1. A titanium dioxide-alumina composite oxide, characterized in that the composite oxide has the following properties: the mass of the titanium dioxide accounts for 5-20% of the total mass of the composite oxide, and the titanium dioxide nano particles only cover the surface of the alumina without independent titanium dioxide aggregates.
2. The composite oxide according to claim 1, wherein the specific surface area of the composite oxide is not less than 80m2Preferably 80 to 170 m/g2(ii)/g; pore volume of not less than 0.4cm3Preferably 0.4 to 0.6 cm/g3/g。
3. The composite oxide according to claim 1, wherein the sulfur adsorption amount of the composite oxide is not more than 30 μ g/m2Preferably 20 to 30 μ g/m2。
4. A method for preparing a titanium dioxide-alumina composite oxide is characterized by comprising the following steps:
(1) dispersing alumina in an anhydrous alcohol solution to obtain a dispersion liquid;
(2) adding titanium alkoxide into the anhydrous alcohol solution, and fully stirring and dissolving; then mixing the dispersion liquid obtained in the step (1) with the solution, and carrying out reflux reaction for 2-6 h at the temperature of 60-80 ℃;
(3) after the reaction is finished, filtering, washing, drying and roasting to obtain the titanium dioxide-aluminum oxide composite oxide.
5. The method according to claim 4, wherein the alumina of step (1) is γ -Al2O3、θ-Al2O3、α-Al2O3One or more of (a).
6. The method according to claim 4, wherein the amount of the titanium alkoxide charged in the step (2) is controlled so that the molar ratio of Ti to Al is 1: 20-1: 5.
7. the process according to claim 4, wherein the anhydrous alcohol solution in the steps (1) and (2) is a monohydric alcohol which is liquid at normal temperature and pressure, preferably one or more selected from methanol, ethanol, isopropanol, n-propanol and n-butanol, more preferably ethanol and/or isopropanol.
8. The method according to claim 4, wherein the titanium alkoxide in the step (2) is one or more of tetrabutyl titanate, tetraethyl titanate, isopropyl titanate, titanium tetramethoxide, and titanium isooctanolate; preferably one or more of tetrabutyl titanate, tetraethyl titanate, isopropyl titanate.
9. The method according to claim 4, wherein the entire system is protected by inert gas during the refluxing in step (2).
10. The method according to claim 4, wherein the drying temperature for the drying in the step (3) is 40 ℃ to 120 ℃, preferably 60 ℃ to 80 ℃; the roasting is carried out for 4-8 hours at 500-800 ℃.
11. Use of the composite oxide according to any one of claims 1 to 3 or the composite oxide produced by the production method according to any one of claims 4 to 10 in the field of exhaust gas purification.
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