CN106732578A - A kind of mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst of efficient cryogenic, preparation method and applications - Google Patents
A kind of mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst of efficient cryogenic, preparation method and applications Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
- -1 cerium zirconium aluminum Chemical compound 0.000 title claims abstract description 66
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 36
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 13
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims description 7
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 2
- 238000004140 cleaning Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 27
- 239000001301 oxygen Substances 0.000 abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 abstract description 27
- 238000003860 storage Methods 0.000 abstract description 15
- 238000005470 impregnation Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 17
- 239000011232 storage material Substances 0.000 description 10
- 239000006104 solid solution Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
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Abstract
一种低温高催化活性介孔铈锆铝负贵金属纳米催化剂、制备方法及其应用，属于催化剂技术领域。在三维有序介孔铈锆铝复合氧化物孔壁上负载一定量贵金属。制备方法为采用负压法制备介孔铈锆铝载体，然后采用等体积浸渍法将贵金属负载在介孔铈锆铝表面即得到介孔铈锆铝负载贵金属的纳米催化剂。在CO浓度为1.6％、HC浓度为0.05％、NOx浓度为0.1％、O2浓度为1.0％、H2浓度为0.23％、N2平衡，空速为300,000mL/(g h)条件下，该催化剂载体具有较大的比表面积，较高的储氧里，该催化剂具有在较低温度下具有较高的转化效率。本发明原料廉价易得，制备过程简单，产物形貌和孔径可控，催化性能优异。A mesoporous cerium-zirconium-aluminum negative noble metal nanocatalyst with low temperature and high catalytic activity, a preparation method and application thereof, belonging to the technical field of catalysts. A certain amount of noble metal is supported on the pore wall of the three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide. The preparation method is to prepare a mesoporous cerium-zirconium-aluminum carrier by a negative pressure method, and then use an equal-volume impregnation method to load noble metals on the surface of the mesoporous cerium-zirconium-aluminum catalyst to obtain a nano-catalyst of the mesoporous cerium-zirconium-aluminum-supported noble metal. Under the conditions of CO concentration of 1.6%, HC concentration of 0.05%, NOx concentration of 0.1%, O2 concentration of 1.0%, H2 concentration of 0.23%, N2 balance, and space velocity of 300,000mL/(gh), the The catalyst carrier has a larger specific surface area, a higher oxygen storage capacity, and the catalyst has a higher conversion efficiency at a lower temperature. The invention has cheap and easy-to-obtain raw materials, simple preparation process, controllable product appearance and pore diameter, and excellent catalytic performance.
Description
技术领域technical field
本发明涉及一种三维有序介孔铈锆铝复合氧化物负载贵金属纳米催化剂，本发明还涉及制备这种三维有序介孔铈锆铝复合氧化物载体的制备方法，具体地说涉及负压法制备铈锆铝复合氧化物载体，本发明还涉及这种纳米催化剂在汽车尾气净化领域的应用，属于催化剂技术领域。The invention relates to a three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide supported noble metal nano-catalyst, and the invention also relates to a preparation method for preparing the three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide carrier, specifically related to negative pressure The method prepares the cerium-zirconium-aluminum composite oxide carrier, and the invention also relates to the application of the nano-catalyst in the field of automobile exhaust purification, which belongs to the technical field of catalysts.
背景技术Background technique
汽车尾气排放已成为北京、上海和广州等大型城市最主要的污染源之一，为此，国家不断提高汽车污染物排放标准。汽油车三效催化剂由Pt、Rh、Pd等贵金属活性组分、铈基储氧材料和用于支撑活性组分的γ-Al2O3载体组成。储氧材料对贵金属的分散和稳定起关键作用，可以改善贵金属的高温热稳定性和储氧能力、扩大其空燃比操作窗口、稳定γ-Al2O3载体的比表面积、阻止γ-Al2O3因烧结而造成的相转变和提高载体γ-Al2O3的高温热稳定性。储氧材料的储氧能力、氧化还原性能和比表面积等物化性能对三效催化剂的性能有较大影响。Automobile exhaust emissions have become one of the most important sources of pollution in large cities such as Beijing, Shanghai, and Guangzhou. For this reason, the state has continuously improved the emission standards of automobile pollutants. The three-way catalyst for gasoline vehicles consists of noble metal active components such as Pt, Rh, and Pd, cerium-based oxygen storage materials, and γ-Al 2 O 3 supports for supporting the active components. Oxygen storage materials play a key role in the dispersion and stabilization of noble metals, which can improve the high-temperature thermal stability and oxygen storage capacity of noble metals, expand their air-fuel ratio operating window, stabilize the specific surface area of γ-Al 2 O 3 carriers, prevent γ-Al 2 Phase transformation of O3 due to sintering and improving the high temperature thermal stability of the support γ - Al2O3 . The physical and chemical properties of oxygen storage materials, such as oxygen storage capacity, redox performance and specific surface area, have a great influence on the performance of three-way catalysts.
铈基储氧材料得到广泛研究及应用，在三效催化剂中的应用经历了三个阶段:第一阶段为CeO2的应用，但在850℃以上，CeO2容易发生高温烧结，仅有表面氧参与催化反应，导致催化剂失活。第二阶段将ZrO2掺入CeO2中，形成铈锆固溶体，能有效抑制CeO2烧结，储氧能力与热稳定性均明显提高，但仍无法满足日益严格的汽车污染物排放标准。第三阶段为三元铈基氧化物的应用，即采用贵金属、过渡金属、稀土金属及Al2O3等对铈锆固溶体改性掺杂，进一步提高铈基储氧材料的储氧能力及水热稳定性。Cerium-based oxygen storage materials have been widely studied and applied, and their application in three-way catalysts has gone through three stages: the first stage is the application of CeO2, but above 850 °C, CeO2 is prone to high - temperature sintering, and only the surface oxygen Participate in catalytic reactions, leading to catalyst deactivation. In the second stage, ZrO 2 is mixed into CeO 2 to form a cerium-zirconium solid solution, which can effectively inhibit the sintering of CeO 2 , and the oxygen storage capacity and thermal stability are significantly improved, but it still cannot meet the increasingly stringent emission standards of automobile pollutants. The third stage is the application of ternary cerium-based oxides, that is, the use of noble metals, transition metals, rare earth metals, and Al 2 O 3 to modify and dope cerium-zirconium solid solutions to further improve the oxygen storage capacity and water content of cerium-based oxygen storage materials. thermal stability.
公开号为CN1200954A的中国发明专利申请公开了一种采取浸渍法制备铈基储氧材料的方法，即通过浸渍法将氧化铈及氧化铈稳定剂负载到高比表面积的氧化铝上，900℃焙烧10小时制得。所制备的铈基储氧材料比表面积最高为30m2/g左右。从X射线衍射谱图中观察到CeO2和Al2O3的特征衍射峰，该专利未涉及所制备储氧材料的储氧性能。中国发明专利CN101112683A公开了铈锆铝复合氧化物的一步制备法，在沉淀前加入了表面活性剂，滤饼烘干后焙烧，其工艺简单，但是所得产物的比表面积较低，其高温稳定性较差。专利CN102886526A公开一种铈锆铝复合氧化物储氧材料及其制备方法，虽然新鲜及老化后均获得大的孔容和比表面积，但也没有相关储氧量的相关数据。有文献报道(赵明，陈耀强等，CeO2-ZrO2-AL2O3的制备及其负载钯三效催化剂的催化性[J].Chin.J.Catal,2010,31:429-434)，采用共沉淀法制备的铈锆铝复合氧化物载体及浸渍法制得的钯基催化剂，虽然具有较大的比表面积及较高的储氧量，但是其三效催化活性还有待提高。共沉淀法制备的样品具有较大比表面积，但是其孔道结构却为颗粒堆积形成的无序孔道结构，不利于贵金属活性组分的高度分散，同时也不利于反应物和产物分子的扩散，其催化活性有待提高。因此，研发一种既具有高比表面积、高储氧性能的三维有序介孔储氧材料用作汽车尾气催化剂的载体对于三效催化剂性能的提高具有重要意义。The Chinese invention patent application with publication number CN1200954A discloses a method of preparing cerium-based oxygen storage materials by impregnation method, that is, cerium oxide and cerium oxide stabilizer are loaded on alumina with high specific surface area by impregnation method, and calcined at 900°C Made in 10 hours. The specific surface area of the prepared cerium-based oxygen storage material is up to about 30m 2 /g. The characteristic diffraction peaks of CeO 2 and Al 2 O 3 are observed in the X-ray diffraction spectrum, and this patent does not involve the oxygen storage performance of the prepared oxygen storage material. Chinese invention patent CN101112683A discloses a one-step preparation method of cerium-zirconium-aluminum composite oxide. Before precipitation, a surfactant is added, and the filter cake is dried and then roasted. The process is simple, but the specific surface area of the obtained product is low, and its high temperature stability poor. Patent CN102886526A discloses a cerium-zirconium-aluminum composite oxide oxygen storage material and its preparation method. Although it obtains large pore volume and specific surface area both freshly and after aging, there is no relevant data on the oxygen storage capacity. It has been reported in the literature (Zhao Ming, Chen Yaoqiang, etc., the preparation of CeO 2 -ZrO 2 -AL 2 O 3 and its catalytic performance of supported palladium three-way catalyst[J].Chin.J.Catal,2010,31:429-434) , the cerium-zirconium-aluminum composite oxide carrier prepared by co-precipitation method and the palladium-based catalyst prepared by impregnation method have larger specific surface area and higher oxygen storage capacity, but their three-way catalytic activity needs to be improved. The samples prepared by the co-precipitation method have a large specific surface area, but the pore structure is a disordered pore structure formed by the accumulation of particles, which is not conducive to the high dispersion of the noble metal active components, and is also not conducive to the diffusion of reactants and product molecules. Catalytic activity needs to be improved. Therefore, it is of great significance to develop a three-dimensional ordered mesoporous oxygen storage material with high specific surface area and high oxygen storage performance as a carrier for automobile exhaust catalysts to improve the performance of three-way catalysts.
贵金属Pt、Rh、Pd是传统汽车三效催化剂的活性组分，Pd对CO、HC及氮氧化物均具有较好的催化作用，尤其贵金属中Pd的价格相对Pt、Rh较低，本发明主要针对三维有序介孔铈锆铝复合氧化物负载Pd纳米催化剂展开。Noble metals Pt, Rh, and Pd are active components of traditional three-way catalysts for automobiles. Pd has a good catalytic effect on CO, HC, and nitrogen oxides. Especially, the price of Pd in noble metals is relatively low compared to Pt and Rh. The present invention mainly Development of three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide supported Pd nanocatalysts.
发明内容Contents of the invention
针对上述问题，本发明提供了一种三维有序介孔铈锆铝复合氧化物及其负载贵金属纳米催化剂的制备方法，该方法工艺简单、可控，适合规模化生产。所得铈锆铝复合氧化物具有规则的三维有序介孔结构，较高的比表面积，优良的储氧能力及高温热稳定性，1000℃老化5h后没有析出Al2O3相，仍为均一的铈基固溶体结构，所得催化剂中贵金属组分高度分散。本发明还提供了这种纳米催化剂在汽车尾气催化净化领域中的应用，该纳米催化剂具有优良的三效催化性能。In view of the above problems, the present invention provides a preparation method of a three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide and its loaded noble metal nano-catalyst. The method is simple in process, controllable and suitable for large-scale production. The obtained cerium-zirconium-aluminum composite oxide has a regular three-dimensional ordered mesoporous structure, high specific surface area, excellent oxygen storage capacity and high temperature thermal stability, and no Al 2 O 3 phase is precipitated after aging at 1000°C for 5 hours, and it is still uniform The cerium-based solid solution structure, the noble metal component in the obtained catalyst is highly dispersed. The invention also provides the application of the nano-catalyst in the field of automobile tail gas catalytic purification, and the nano-catalyst has excellent three-way catalytic performance.
三维有序介孔铈锆铝复合氧化物负载贵金属纳米催化剂，其特征在于，具有三维有序介孔结构的铈锆铝复合氧化物的孔壁上负载有一定量贵金属纳米粒子，其中贵金属纳米颗粒的负载量为0-3wt％。铈锆的摩尔比例为1-1.5:1，优选铈锆摩尔比为6:4，The three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide-loaded noble metal nanocatalyst is characterized in that a certain amount of noble metal nanoparticles is loaded on the pore wall of the cerium-zirconium-aluminum composite oxide with a three-dimensional ordered mesoporous structure, wherein the noble metal nanoparticles The loading is 0-3wt%. The molar ratio of cerium to zirconium is 1-1.5:1, preferably the molar ratio of cerium to zirconium is 6:4,
铈锆铝复合氧化物中氧化铝的质量百分含量0-80％；优选铈锆铝复合氧化物中氧化铝的质量百分含量为40％。The mass percentage of alumina in the cerium-zirconium-aluminum composite oxide is 0-80%; preferably, the mass percentage of alumina in the cerium-zirconium-aluminum composite oxide is 40%.
本发明作为三维有序介孔铈锆铝复合氧化物负载贵金属纳米催化剂的一种制备方法，其中铈锆铝复合氧化物的孔径为2-10nm，新鲜比表面积为100-250m2/g，1000℃，5h老化后比表面积为50-90m2/g(见表2)。The invention is a preparation method of a three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide loaded noble metal nanocatalyst, wherein the cerium-zirconium-aluminum composite oxide has a pore diameter of 2-10nm, a fresh specific surface area of 100-250m 2 /g, and 1000 °C, after aging for 5 hours, the specific surface area is 50-90m 2 /g (see Table 2).
本发明提供了一种制备三维有序介孔铈锆铝复合氧化物负载贵金属纳米催化剂的方法，其特征在于，包括以下步骤：The invention provides a method for preparing a three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide-loaded noble metal nanocatalyst, which is characterized in that it comprises the following steps:
(1)制备三维有序介孔铈锆铝复合氧化物载体，称取一定量的KIT-6粉末，置于干燥的抽滤瓶中，抽真空，整个制备过程中抽滤瓶一直在负压状态下；另外称取化学计量比的六水合硝酸铈(Ce(NO3)3·6H2O)、五水合硝酸锆(Zr(NO3)3·5H2O)和九水合硝酸铝(Al(NO3)3·9H2O)置于烧杯中，向其中加入无水乙醇，三种硝酸盐完全溶解后得到铈锆铝复合氧化物的前驱体溶液，并将其转入分液漏斗中；在负压条件下，打开分液漏斗旋塞，使前驱体溶液缓慢滴加到KIT-6粉末中，滴加完毕后，继续在负压条件下抽滤，直至抽滤瓶中无多余液体，得到KIT-6和前驱体的复合物；待复合物干燥后进行焙烧，焙烧条件如下：在马弗炉中以1℃/min的速率由室温升至550℃，保温3h，自然降温得浅黄色固体；用热NaOH溶液浓度(2mol/L)去除KIT-6模板，洗涤、干燥后即得到介孔铈锆铝复合氧化物载体；(1) To prepare a three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide carrier, weigh a certain amount of KIT-6 powder, put it in a dry suction filter bottle, and vacuumize it. The suction filter bottle has been under negative pressure during the whole preparation process. In addition, weigh cerium nitrate hexahydrate (Ce(NO 3 ) 3 6H 2 O), zirconium nitrate pentahydrate (Zr(NO 3 ) 3 5H 2 O) and aluminum nitrate nonahydrate (Al (NO 3 ) 3 9H 2 O) was placed in a beaker, absolute ethanol was added to it, and the precursor solution of cerium-zirconium-aluminum composite oxide was obtained after the three nitrates were completely dissolved, and it was transferred into a separatory funnel ;Under negative pressure, open the cock of the separatory funnel to slowly add the precursor solution to the KIT-6 powder dropwise. After the dropwise addition, continue to filter under negative pressure until there is no excess liquid in the filter bottle. The composite of KIT-6 and the precursor was obtained; after the composite was dried, it was roasted, and the roasting conditions were as follows: in a muffle furnace, the temperature was raised from room temperature to 550 °C at a rate of 1 °C/min, kept for 3 hours, and the temperature was naturally lowered Yellow solid; remove the KIT-6 template with a hot NaOH solution concentration (2mol/L), wash and dry to obtain a mesoporous cerium-zirconium-aluminum composite oxide carrier;
(2)称取步骤(1)所得介孔载体放入容器中待用，称取一定量的贵金属可溶性盐镀液(如镀液中贵金属含量为15wt％)，加入去离子水稀释，然后将稀释液放入盛有介孔载体的烧杯中；将容器放入超声装置中60℃超声3h，待溶剂完全挥发后，放入马弗炉中焙烧，焙烧条件为1℃/min从室温升到500℃，保温3h，得到介孔铈锆铝复合氧化物负载贵金属催化剂。(2) Weigh the mesoporous carrier obtained in step (1) and put it into a container for use, take a certain amount of precious metal soluble salt plating solution (as the precious metal content is 15wt% in the plating solution), add deionized water to dilute, and then Put the diluted liquid into a beaker containing a mesoporous carrier; put the container into an ultrasonic device for 3 h at 60°C, and after the solvent is completely evaporated, put it into a muffle furnace for roasting, the roasting condition is 1°C/min from room temperature to Temperature is kept at 500° C. for 3 hours to obtain a mesoporous cerium-zirconium-aluminum composite oxide-supported noble metal catalyst.
优选步骤(1)中抽真空使得真空度为0.7-1Mpa，加入前驱体溶液前抽真空时间至少1h。Preferably, in step (1), the vacuum is evacuated so that the degree of vacuum is 0.7-1 Mpa, and the evacuation time is at least 1 h before adding the precursor solution.
优选前驱体溶液的滴加速率为10-50滴/min，每滴约0.2ml。步骤(1)中热NaOH的浓度为2mol/L，每1g介孔载体用100ml热NaOH溶液。Preferably, the dropping rate of the precursor solution is 10-50 drops/min, and each drop is about 0.2ml. The concentration of hot NaOH in step (1) is 2mol/L, and 100ml of hot NaOH solution is used for every 1g of mesoporous carrier.
优选采用真空浸渍法制备了铈锆摩尔比为6:4，氧化铝的质量分数为0-80％的载体，其中铈锆比为6:4、氧化铝含量为40wt％的复合氧化物具有更规则的介孔结构、较高的比表面积和较大的储氧量，因此选择这一比例的铈锆铝复合氧化物作为载体。采用浸渍法在其上分别负载了不同质量分数的贵金属(优选1-2.0wt％)，即得三维有序介孔铈锆铝复合氧化物负载贵金属纳米催化剂。Preferably, a vacuum impregnation method is used to prepare a carrier with a molar ratio of cerium to zirconium of 6:4 and a mass fraction of alumina of 0-80%, wherein the composite oxide with a ratio of cerium to zirconium of 6:4 and a content of alumina of 40wt% has more Regular mesoporous structure, high specific surface area and large oxygen storage capacity, so this ratio of cerium-zirconium-aluminum composite oxide is selected as the carrier. Different mass fractions of precious metals (preferably 1-2.0wt%) are loaded thereon by an impregnation method to obtain a three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide-supported noble metal nano catalyst.
上述贵金属选自Pt、Rh、Pd，优选Pd。The above-mentioned noble metal is selected from Pt, Rh, Pd, preferably Pd.
本发明涉及三维有序介孔铈锆铝复合氧化物负载贵金属纳米催化剂在汽车尾气催化净化领域中的应用。The invention relates to the application of a three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide loaded noble metal nano-catalyst in the field of automobile tail gas catalytic purification.
本发明具有原料廉价易得，制备过程简单，所得产物形貌、粒径和孔径可控等特征。The invention has the characteristics of cheap and easy-to-obtain raw materials, simple preparation process, controllable appearance, particle diameter and pore diameter of the obtained product, and the like.
本发明制备的三维有序介孔载体比表面积高、储氧量大，且以其为载体的钯催化剂在较低温度对CO、CH、NOx同时具有较高的转化率，在汽车尾气催化净化领域具有良好的应用前景。The three-dimensional ordered mesoporous carrier prepared by the present invention has a high specific surface area and a large oxygen storage capacity, and the palladium catalyst using it as a carrier has a high conversion rate for CO, CH, and NOx at a lower temperature, and is used in the catalytic purification of automobile exhaust. The field has good application prospects.
利用D8ADVANCE型X射线衍射仪(XRD)、JEOL-2010型透射电子显微镜(TEM)和FEIG2 80-200/Chem-STEM等仪器表征所得目标产物的晶体结构、粒子形貌、粒子结构与孔结构。结果表明，依照本发明方法所制得的介孔铈锆铝复合氧化物负载贵金属纳米催化剂呈现优异的三效催化性能。The crystal structure, particle morphology, particle structure and pore structure of the obtained target product were characterized by D8ADVANCE X-ray diffractometer (XRD), JEOL-2010 transmission electron microscope (TEM) and FEIG2 80-200/Chem-STEM. The results show that the mesoporous cerium-zirconium-aluminum composite oxide-loaded noble metal nano-catalyst prepared according to the method of the present invention exhibits excellent three-way catalytic performance.
附图说明Description of drawings
图1为实施例2所制得的介孔铈锆铝复合氧化物载体(铈锆比为6:4、氧化Fig. 1 is the mesoporous cerium-zirconium-aluminum composite oxide carrier (cerium-zirconium ratio is 6:4, oxide
铝含量为40wt％)的小角XRD谱图。Aluminum content is 40wt%) small-angle XRD pattern.
图2为实施例2-4所制得的介孔铈锆铝复合氧化物载体(铈锆比为6:4、氧Fig. 2 is the mesoporous cerium-zirconium-aluminum composite oxide carrier (cerium-zirconium ratio is 6:4, oxygen
化铝含量为20、40、60wt％)载体新鲜及老化样品的广角XRD谱图。The wide-angle XRD patterns of the fresh and aged samples of the carrier with aluminum content of 20, 40, 60wt%.
图3为实施例2所制得的介孔铈锆铝复合氧化物载体复合氧化物载体(铈Fig. 3 is the mesoporous cerium-zirconium-aluminum composite oxide carrier composite oxide carrier (cerium
锆比为6:4、铝氧化含量为40wt％)的TEM图片。TEM image of zirconium ratio 6:4, aluminum oxide content 40wt%.
图4为所制得的铈锆铝复合氧化物复合氧化物载体(铈锆比为6:4、铝氧化含量为40wt％)负载钯(Pd的负载量为1％，2％)纳米催化剂的催化活性曲线，反应气体组成为：CO浓度1.6％、HC浓度为0.05％(丙烷和丙烯的摩尔浓度比为1:3)、NOx浓度为0.1％、O2浓度为1.0％、H2浓度为0.23％、N2为平衡气，空速为300,000mL/(g·h)。Fig. 4 is the prepared cerium-zirconium-aluminum composite oxide composite oxide carrier (cerium-zirconium ratio is 6:4, aluminum oxide content is 40wt%) supported palladium (the loading capacity of Pd is 1%, 2%) nanocatalyst Catalytic activity curve, the reaction gas composition is: CO concentration 1.6%, HC concentration 0.05% (the molar concentration ratio of propane and propylene is 1:3), NOx concentration is 0.1%, O2 concentration is 1.0%, H2 concentration is 0.23%, N 2 is the balance gas, and the space velocity is 300,000mL/(g·h).
具体实施方式detailed description
下面结合实施例只是用于详细说明本发明，并不以任何方式限制发明的保护范围。抽真空使得真空度为0.7-1Mpa，加入前驱体溶液前抽真空时间至少为1h。The following examples are only used to describe the present invention in detail, and do not limit the protection scope of the invention in any way. Vacuum so that the degree of vacuum is 0.7-1Mpa, and the vacuum time is at least 1h before adding the precursor solution.
实施例1：Example 1:
三维有序介孔铈锆固溶体的制备：取2g的KIT-6粉末置于干燥的抽滤瓶中，抽真空1.5小时；称取5.96g六水合硝酸铈和7.35g五水合硝酸锆置于烧杯中，向其中加入40ml无水乙醇，待完全溶解后得前驱体溶液，将所得溶液转入分液漏斗中；在负压条件下打开分液漏斗旋塞，使前驱体溶液缓慢滴加到KIT-6粉末中，滴加完毕后，继续在同一真空度下保持至抽滤瓶中无多余液体，得到KIT-6模板和前驱体溶液的复合物，将其在马弗炉中焙烧得到KIT-6模板和铈锆固溶体的复合物，焙烧条件为：以1℃/min的速率由室温升温至550℃，保温3h，自然降至室温；用2mol/L的热NaOH溶液去除KIT-6模板，洗涤、干燥，得到三维有序介孔铈锆固溶体。Preparation of three-dimensional ordered mesoporous cerium-zirconium solid solution: Take 2g of KIT-6 powder and put it in a dry suction filter bottle, vacuumize for 1.5 hours; weigh 5.96g of cerium nitrate hexahydrate and 7.35g of zirconium nitrate pentahydrate and put them in a beaker 40ml of absolute ethanol was added to it, and the precursor solution was obtained after it was completely dissolved, and the resulting solution was transferred to a separatory funnel; the cock of the separatory funnel was opened under negative pressure, and the precursor solution was slowly added dropwise to the KIT- 6 powder, after the dropwise addition, continue to maintain under the same vacuum until there is no excess liquid in the suction filter bottle to obtain a composite of KIT-6 template and precursor solution, which is roasted in a muffle furnace to obtain KIT-6 The composite of the template and the cerium-zirconium solid solution is calcined under the following conditions: the temperature is raised from room temperature to 550 °C at a rate of 1 °C/min, kept for 3 hours, and then naturally lowered to room temperature; the KIT-6 template is removed with 2 mol/L hot NaOH solution, washed and drying to obtain a three-dimensional ordered mesoporous cerium-zirconium solid solution.
实施例2：Example 2:
三维有序介孔铈锆铝复合氧化物(氧化铝含量为20wt％)的制备：称取2g KIT-6粉末置于干燥的抽滤瓶中，抽真空1小时；称取5.96g六水合硝酸铈、7.35g五水合硝酸锆和3.33g九水合硝酸铝，向其中加入80ml无水乙醇，待完全溶解后，将所得溶液转入分液漏斗中；之后的实验步骤与实施例1相同，最终的得到三维有序介孔铈锆铝复合氧化物，其中氧化铝的含量为20wt％。Preparation of three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide (alumina content is 20wt%): Weigh 2g of KIT-6 powder and put it in a dry suction filter bottle, vacuumize for 1 hour; weigh 5.96g of nitric acid hexahydrate Cerium, 7.35g zirconium nitrate pentahydrate and 3.33g aluminum nitrate nonahydrate, add 80ml dehydrated alcohol wherein, after dissolving completely, the gained solution is transferred in the separating funnel; Afterwards experimental procedure is identical with embodiment 1, finally A three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide is obtained, wherein the content of alumina is 20wt%.
实施例3：Example 3:
三维有序介孔铈锆铝复合氧化物(氧化铝含量为40wt％)的制备：实施例3的实验步骤与实施例2相同，只是前驱体盐的量不同于实施例2。本实施例中六水合硝酸铈为5.96g，五水合硝酸锆为7.35g，九水合硝酸铝为8.87g，所得三维有序介孔铈锆铝复合氧化物中氧化铝的含量为40wt％。从图1可以看出样品在小角处有明显的衍射峰，说明样品中有介孔结构存在。从图3透射电镜中可以看出该样品形成了良好的三维有序介孔结构。Preparation of three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide (alumina content: 40wt%): the experimental procedure of Example 3 is the same as that of Example 2, except that the amount of precursor salt is different from Example 2. In this example, the content of cerium nitrate hexahydrate was 5.96g, that of zirconium nitrate pentahydrate was 7.35g, and that of aluminum nitrate nonahydrate was 8.87g. The content of alumina in the obtained three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide was 40wt%. It can be seen from Figure 1 that the sample has obvious diffraction peaks at small angles, indicating that there is a mesoporous structure in the sample. It can be seen from the transmission electron microscope in Figure 3 that the sample has formed a good three-dimensional ordered mesoporous structure.
实施例4：Example 4:
三维有序介孔铈锆铝复合氧化物(氧化铝含量为60wt％)的制备：实施例4的实验步骤与实施例2和3相同，只是前驱体盐的量不同于实施例2和3。本实施例中六水合硝酸铈为5.96g，五水合硝酸锆为7.35g，九水合硝酸铝为16.98g，所得三维有序介孔铈锆铝复合氧化物中氧化铝的含量为60wt％。从图2 XRD中可以看出实施例2-4所得新鲜样品老化后峰强度增强，峰宽无明显变化，并且没有出现Al2O3的特征峰，说明样品形成了均一稳定的铈锆铝固溶体。Preparation of three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide (alumina content: 60wt%): the experimental procedure of Example 4 is the same as that of Examples 2 and 3, except that the amount of precursor salt is different from Examples 2 and 3. In this example, the content of cerium nitrate hexahydrate was 5.96g, that of zirconium nitrate pentahydrate was 7.35g, and that of aluminum nitrate nonahydrate was 16.98g. The content of alumina in the obtained three-dimensional ordered mesoporous cerium-zirconium-aluminum composite oxide was 60wt%. From Figure 2 XRD, it can be seen that the peak intensity of the fresh sample obtained in Example 2-4 increases after aging, the peak width does not change significantly, and there is no characteristic peak of Al2O3 , indicating that the sample has formed a uniform and stable cerium-zirconium-aluminum solid solution .
实施例5：Example 5:
负载量为1wt％的介孔铈锆铝复合氧化物负载钯纳米催化剂的制备：按实施例3的步骤制备介孔载体(氧化铝含量为40wt％)，称取2g载体放入25ml的小烧杯中；称取0.134g的硝酸钯镀液(质量分数为15％)，加入5ml去离子水稀释后，移入呈放载体的烧杯中，将烧杯放入超声波清洗器中，以60℃超声3h后，将中间产物放入马弗炉中焙烧，焙烧条件：以1℃/min的速率从室温升到500℃，保温3h，得到负载量为1wt％的介孔铈锆铝复合氧化物负载钯纳米催化剂。The preparation of the mesoporous cerium-zirconium-aluminum composite oxide-loaded palladium nanocatalyst with a loading capacity of 1wt%: prepare the mesoporous carrier (aluminum oxide content is 40wt%) according to the steps of Example 3, weigh 2g of the carrier and put it into a 25ml small beaker Middle; take by weighing 0.134g of palladium nitrate plating solution (mass fraction is 15%), add 5ml of deionized water to dilute, move into the beaker that is to put the carrier, put the beaker into an ultrasonic cleaner, and after ultrasonic 3h at 60°C , the intermediate product is put into a muffle furnace for roasting, the roasting condition: the rate of 1 °C/min is raised from room temperature to 500 °C, and the temperature is kept for 3 hours to obtain a mesoporous cerium-zirconium-aluminum composite oxide-supported palladium with a loading capacity of 1 wt%. nanocatalyst.
实施例6：Embodiment 6:
负载量为2wt％的介孔铈锆铝复合氧化物负载钯纳米催化剂的制备：该实施例与实施例5的制备步骤相同，只是所用硝酸钯渡液的量不同，该实施例中硝酸钯渡液的用量为0.268g，所得催化剂中Pd的负载量为2wt％。从图4可以看出实施例5和6涉及催化剂在200℃以前对三种污染物都能达到较高转化率，表现出优异的催化活性。The preparation of the mesoporous cerium-zirconium-aluminum composite oxide-supported palladium nanocatalyst with a loading capacity of 2wt%: the preparation steps of this embodiment are the same as in Example 5, except that the amount of the palladium nitrate solution used is different. In this embodiment, the palladium nitrate The amount of liquid used was 0.268g, and the loading amount of Pd in the obtained catalyst was 2wt%. It can be seen from Fig. 4 that the catalysts of Examples 5 and 6 can achieve relatively high conversion rates for the three pollutants before 200° C., showing excellent catalytic activity.
其中上述实施例涉及介孔铈锆铝复合氧化物载体的储氧量及老化前后的比表面积分别见表1和表2。由表中数据可知，样品具有优良的储氧能力，和较高的比表面积。The oxygen storage capacity of the mesoporous cerium-zirconium-aluminum composite oxide carrier and the specific surface area before and after aging in the above-mentioned embodiments are shown in Table 1 and Table 2, respectively. It can be seen from the data in the table that the sample has excellent oxygen storage capacity and high specific surface area.
表1为所制得的不同氧化铝含量的介孔铈锆铝复合氧化物的储氧量Table 1 shows the oxygen storage capacity of the prepared mesoporous cerium-zirconium-aluminum composite oxides with different alumina contents
表2为所制得的不同氧化铝含量介孔铈锆铝复合氧化物老化前后的比表面积Table 2 shows the specific surface area of the prepared mesoporous cerium-zirconium-aluminum composite oxides with different alumina contents before and after aging
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