技术领域technical field
本发明涉及一种高性能铈锆铝储氧材料的制备方法。The invention relates to a preparation method of a high-performance cerium-zirconium-aluminum oxygen storage material.
背景技术Background technique
铈锆铝复合氧化物是一种新型的稀土储氧材料，兼有储氧材料和活性氧化铝的共同优点。因而其在三效催化净化(TWC)、催化燃烧、柴油机DOC、POC净化表现出更为优异的热稳定性和储氧能力。Cerium-zirconium-aluminum composite oxide is a new type of rare earth oxygen storage material, which has the common advantages of oxygen storage materials and activated alumina. Therefore, it exhibits more excellent thermal stability and oxygen storage capacity in three-way catalytic purification (TWC), catalytic combustion, diesel DOC, and POC purification.
目前制备铈锆铝复合氧化物的方法主要有浸渍法、共沉淀法、溶胶-凝胶法、微乳液法、机械混合法等。其中，共沉淀法因工艺简单、条件易于控制、产品均一性好、生产成本较低、便于工业化生产等优点得到了广泛的应用，但是现有共沉淀法步骤复杂，生产成本高。At present, the methods for preparing cerium-zirconium-aluminum composite oxide mainly include impregnation method, co-precipitation method, sol-gel method, microemulsion method, mechanical mixing method and so on. Among them, the co-precipitation method has been widely used due to the advantages of simple process, easy control of conditions, good product uniformity, low production cost, and convenience for industrial production. However, the existing co-precipitation method has complicated steps and high production cost.
发明内容Contents of the invention
为解决上述技术问题，本发明提供一种高性能铈锆铝储氧材料的制备方法，步骤简单，所制得的铈锆铝储氧材料具有优异的热稳定性和储氧能力。In order to solve the above technical problems, the present invention provides a method for preparing a high-performance cerium-zirconium-aluminum oxygen storage material with simple steps, and the prepared cerium-zirconium-aluminum oxygen storage material has excellent thermal stability and oxygen storage capacity.
本发明的高性能铈铬铝储氧材料的制备方法，包括以下步骤：The preparation method of the high-performance cerium-chromium-aluminum oxygen storage material of the present invention comprises the following steps:
1)将拟薄水铝石用硝酸反应制成铝溶胶，水铝石∶去离子水∶硝酸溶液的质量比为1∶10-20∶0.1-0.5进行混合搅拌，得到分散均匀的铝溶胶，水铝石中Al2O3的质量分数为70％，硝酸溶液中硝酸的质量分数为60％；1) Pseudoboehmite is reacted with nitric acid to make aluminum sol, and the mass ratio of boehmite: deionized water: nitric acid solution is 1: 10-20: 0.1-0.5 for mixing and stirring to obtain uniformly dispersed aluminum sol,The mass fraction ofAl2O3 in the diaspore is 70%, and the mass fraction of nitric acid in the nitric acid solution is 60%;
2)取锆和铈及稀土掺杂元素镧、钇、镨、釹的可溶性盐，加去离子水制成总离子浓度为0.5-1.5mol/l的铈锆混合水溶液，所述混合液中Ce和Zr的摩尔比为1∶0.5-3；稀土掺杂元素为镧、钇、镨、釹中的一种或多种，重量占铈锆的2-10％；2) Take the soluble salts of zirconium, cerium, and rare earth doping elements lanthanum, yttrium, praseodymium, and neodymium, add deionized water to make a mixed aqueous solution of cerium and zirconium with a total ion concentration of 0.5-1.5mol/l, and Ce in the mixed solution The molar ratio to Zr is 1:0.5-3; the rare earth doping element is one or more of lanthanum, yttrium, praseodymium, and neodymium, and the weight accounts for 2-10% of cerium-zirconium;
3)将步骤1)获得的铝溶胶和步骤2)获得的铈锆混合液按(Ce-Zr)∶Al2O3质量比为1∶0.1-3进行混合搅拌，得到分散均匀的铈锆铝复合溶胶，并控制其氧化物总浓度为50-100g/l；3) Mix and stir the aluminum sol obtained in step 1) and the cerium-zirconium mixed solution obtained in step 2) at a mass ratio of (Ce-Zr):Al2 O3 of 1:0.1-3 to obtain uniformly dispersed cerium-zirconium-aluminum Composite sol, and control its total oxide concentration to be 50-100g/l;
4)将有机高分子改性剂与2-6mol的碱性沉淀剂按照5-10∶90-95的质量比相互混合均匀，得到改性碱性沉淀剂；4) Mixing the organic polymer modifier and 2-6mol of the alkaline precipitant evenly with each other according to the mass ratio of 5-10:90-95 to obtain the modified alkaline precipitant;
5)将步骤3)获得的铈锆铝复合溶胶和步骤4)获得的改性碱性沉淀剂进行混合共沉淀，控制终点PH＞8，得到铈锆铝氢氧化物凝胶；5) Mixing and co-precipitating the cerium-zirconium-aluminum composite sol obtained in step 3) and the modified alkaline precipitating agent obtained in step 4), controlling the endpoint pH to >8 to obtain cerium-zirconium-aluminum hydroxide gel;
6)将铈锆铝氢氧化物凝胶进行真空抽滤及洗涤，控制水洗电导率＜20ms/cm；6) Carry out vacuum filtration and washing of the cerium-zirconium-aluminum hydroxide gel, and control the water-washing conductivity to <20ms/cm;
7)将步骤6)获得的铈锆铝氢氧化物凝胶置于马弗炉内煅烧，控制温度700-800℃，煅烧2-6小时；7) Calcining the cerium-zirconium-aluminum hydroxide gel obtained in step 6) in a muffle furnace, controlling the temperature at 700-800°C, and calcining for 2-6 hours;
8)将步骤7)获得的烧成物经机械粉碎或气流粉碎获得不同粒径的铈锆铝产品。8) The fired product obtained in step 7) is subjected to mechanical pulverization or jet pulverization to obtain cerium-zirconium-aluminum products with different particle sizes.
本发明的高性能铈锆铝储氧材料的制备方法，在步骤2)中：所述铈的可溶性盐为硝酸亚铈、硝酸铈铵、醋酸铈、氯化铈，所述锆的可溶性盐为硝酸锆、醋酸锆、氧氯化锆，所述稀土掺杂元素镧、钇、镨、釹的可溶性盐为硝酸盐、醋酸盐、氯化物。The preparation method of the high-performance cerium-zirconium-aluminum oxygen storage material of the present invention, in step 2): the soluble salt of cerium is cerous nitrate, ammonium cerium nitrate, cerium acetate, cerium chloride, and the soluble salt of zirconium is Zirconium nitrate, zirconium acetate, zirconium oxychloride, the soluble salts of the rare earth doping elements lanthanum, yttrium, praseodymium, neodymium are nitrate, acetate, chloride.
本发明的高性能铈锆铝储氧材料的制备方法，在步骤4)中：所述有机高分子改性剂有机高分子酸类或醇类。In the preparation method of the high-performance cerium-zirconium-aluminum oxygen storage material of the present invention, in step 4): the organic polymer modifier organic polymer acids or alcohols.
本发明的高性能铈锆铝储氧材料的制备方法，在步骤4)中：所述碱性沉淀剂为氨水、碳酸铵、碳酸氢铵中的一种或多种。In the preparation method of the high-performance cerium-zirconium-aluminum oxygen storage material of the present invention, in step 4): the alkaline precipitating agent is one or more of ammonia water, ammonium carbonate, and ammonium bicarbonate.
与现有技术相比本发明的有益效果为：本发明的高性能铈锆铝储氧材料的制备方法步骤简单，以拟薄水铝石、可溶性的锆盐和铈盐为原料，进行胶溶反应制成溶胶，以碱为沉淀剂，有机高分子酸类、醇类为改性剂，将溶胶经有机改性的碱液沉淀后，对沉淀物进行过滤、洗涤、煅烧、粉碎制得。所制得的铈锆铝储氧材料在700℃-800℃的条件下灼烧2-6小时，测试其新鲜比表面积120-140m2/g，1000℃的条件下灼烧10小时老化比表面积＞60m2/g，1100℃的条件下灼烧10小时老化比表面积＞40m2/g，所制得的铈锆铝储氧材料具有很好的高热稳定性。Compared with the prior art, the beneficial effect of the present invention is: the preparation method of the high-performance cerium-zirconium-aluminum oxygen storage material of the present invention has simple steps, and the peptization is carried out by using pseudoboehmite, soluble zirconium salt and cerium salt as raw materials The sol is made by reaction, using alkali as the precipitating agent, organic polymer acids and alcohols as the modifying agent, precipitating the sol with organically modified lye, and then filtering, washing, calcining and pulverizing the precipitate. The prepared cerium-zirconium-aluminum oxygen storage material is burned at 700°C-800°C for 2-6 hours, and its fresh specific surface area is 120-140m2 /g, and its aging specific surface area is measured at 1000°C for 10 hours >60m2 /g, the aging specific surface area is >40m2 /g under the condition of burning for 10 hours at 1100°C, and the prepared cerium-zirconium-aluminum oxygen storage material has good thermal stability.
具体实施方式detailed description
下面结合实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。Below in conjunction with the examples, the specific implementation of the present invention will be further described in detail. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
实施例1Example 1
取64.3g拟薄水铝石(Al2O3：70％)，加去离子水800ml，硝酸溶液(硝酸质量分数为60％)12ml混合搅拌得到铝溶胶；分别取硝酸亚铈66.7ml(TREO：225g/L)、硝酸锆148.5ml(ZrO2：202g/L)、硝酸镧20.8ml(TREO：240g/L)、硝酸钇20.8ml(TREO：240g/L)混合后，加入到铝溶胶中，并加纯水稀释至1500ml，得到质量比为CeO2∶ZrO2∶La2O3∶Y2O3∶Al2O3＝15∶30∶5∶5∶45的铈锆铝溶胶；将改性铝溶胶在室温下加入到溶有7.6％高分子有机酸的4.6mol/L的氨水中沉淀，控制最终PH为8.3，沉淀完毕后真空抽滤及洗涤至洗液中的电导率为18ms/cm，得到铈锆铝氢氧化物凝胶。将铈锆铝凝胶在700℃煅烧4小时得到铈锆铝氧化物，测试其比表面积为132.6m2/g，1000℃10小时老化比表面积为66.8m2/g，1100℃10小时老化比表面积为45.5m2/g。Get 64.3g pseudo- boehmite (Al2O3 : 70%), add 800ml of deionized water, and mix and stir 12ml of nitric acid solution (the mass fraction of nitric acid is 60%) to obtain aluminum sol; respectively take 66.7ml of cerous nitrate (TREO : 225g/L), 148.5ml of zirconium nitrate (ZrO2 : 202g/L), 20.8ml of lanthanum nitrate (TREO: 240g/L), and 20.8ml of yttrium nitrate (TREO: 240g/L) were mixed and added to the aluminum sol , and add pure water to dilute to 1500ml to obtain a cerium-zirconium-aluminum sol with a mass ratio of CeO2 : ZrO2 : La2 O3 : Y2 O3 : Al2 O3 =15:30:5:5:45; The modified aluminum sol is added to 4.6mol/L ammonia water with 7.6% high molecular organic acid for precipitation at room temperature, and the final pH is controlled to be 8.3. After the precipitation is completed, it is vacuum filtered and washed until the conductivity of the lotion is 18ms /cm, to obtain cerium zirconium aluminum hydroxide gel. The cerium-zirconium-aluminum gel was calcined at 700°C for 4 hours to obtain cerium-zirconium-aluminum oxide. The specific surface area was 132.6m2 /g, and the aging specific surface area was 66.8m 2/ g at 1000°C for 10 hours, and the aging ratio at 1100°C for 10 hours The surface area is 45.5 m2 /g.
实施例2Example 2
取64.3g拟薄水铝石(Al2O3：70％)，加去离子水800ml，硝酸溶液(硝酸质量分数为60％)15ml混合搅拌得到铝溶胶；分别取硝酸铈133.3ml(TREO：225g/L)、硝酸锆74.2ml(ZrO2：202g/L)、硝酸镧20.8ml(TREO：240g/L)、硝酸钇20.8ml(TREO：240g/L)混合后，加入到铝溶胶中，并加纯水稀释至1500ml，得到质量比为CeO2∶ZrO2∶La2O3∶Y2O3∶Al2O3＝30∶15∶5∶5∶45的铈锆铝溶胶；将改性铝溶胶在室温下加入到溶有6.5％高分子有机酸的3.2mol/L的氨水中沉淀，控制最终PH为8.5，沉淀完毕后真空抽滤及洗涤至洗液中的电导率为16ms/cm，得到铈锆铝氢氧化物凝胶。将铈锆铝凝胶在700℃的条件下煅烧4小时得到铈锆铝氧化物，测试其比表面积为126.3m2/g，1000℃的条件下煅烧10小时老化比表面积为62.6m2/g，1100℃的条件下煅烧10小时老化比表面积为42.7m2/g。Take 64.3g of pseudo-boehmite (Al2 O3 : 70%), add 800ml of deionized water, 15ml of nitric acid solution (the mass fraction of nitric acid is 60%) and mix and stir to obtain aluminum sol; respectively take 133.3ml of cerium nitrate (TREO: 225g/L), zirconium nitrate 74.2ml (ZrO2 : 202g/L), lanthanum nitrate 20.8ml (TREO: 240g/L), yttrium nitrate 20.8ml (TREO: 240g/L), after mixing, add to the aluminum sol, And add pure water to dilute to 1500ml, obtain the cerium-zirconium-aluminum sol that mass ratio is CeO2 : ZrO2 : La2 O3 : Y2 O3 : Al2 O3 =30: 15: 5: 5: 45; The permanent aluminum sol is added to 3.2mol/L ammonia water with 6.5% polymeric organic acid for precipitation at room temperature, and the final pH is controlled to be 8.5. After the precipitation is completed, vacuum filtration and washing until the conductivity of the lotion is 16ms/ cm, to obtain cerium zirconium aluminum hydroxide gel. The cerium-zirconium-aluminum gel was calcined at 700°C for 4 hours to obtain cerium-zirconium-aluminum oxide, and its specific surface area was 126.3m2 /g when tested at 1000°C for 10 hours. The aging specific surface area was 62.6m2 /g , calcined at 1100°C for 10 hours, the aging specific surface area was 42.7m2 /g.
实施例3Example 3
取42.8g拟薄水铝石(Al2O3：70％)，加去离子水600ml，硝酸溶液(硝酸质量分数为60％)10ml混合搅拌得到铝溶胶；分别取硝酸铈133.3ml(TREO：225g/L)、硝酸锆148.5ml(ZrO2：202g/L)、硝酸镧20.8ml(TREO：240g/L)、硝酸钇20.8ml(TREO：240g/L)混合后，加入到铝溶胶中，并加纯水稀释至1500ml，得到质量比为CeO2∶ZrO2∶La2O3∶Y2O3∶Al2O3＝30∶30∶5∶5∶30的铈锆铝溶胶；将改性铝溶胶在室温下加入到溶有8％高分子有机酸的4mol/L的氨水中沉淀，控制最终PH为9.2，沉淀完毕后真空抽滤及洗涤至洗液中的电导率为12ms/cm，得到铈锆铝氢氧化物凝胶。将铈锆铝凝胶在700℃煅烧4小时得到铈锆铝氧化物，测试其比表面积为125m2/g，1000℃的条件下煅烧10小时老化比表面积为63m2/g，1100℃的条件下煅烧10小时老化比表面积为41m2/g。Take 42.8g of pseudoboehmite (Al2 O3 : 70%), add 600ml of deionized water, 10ml of nitric acid solution (the mass fraction of nitric acid is 60%) and mix and stir to obtain aluminum sol; respectively take 133.3ml of cerium nitrate (TREO: 225g/L), zirconium nitrate 148.5ml (ZrO2: 202g/L), lanthanum nitrate 20.8ml (TREO: 240g/L), yttrium nitrate 20.8ml (TREO: 240g/L) after mixing, add in the aluminum sol, and Add pure water and dilute to 1500ml, obtain the cerium-zirconium-aluminum sol that mass ratio is CeO2 : ZrO2 : La2 O3 : Y2 O3 : Al2 O3 =30:30:5:5:30; Aluminum sol was added to 4mol/L ammonia water with 8% polymeric organic acid for precipitation at room temperature, and the final pH was controlled to be 9.2. After the precipitation was completed, it was vacuum filtered and washed until the conductivity of the lotion was 12ms/cm. A cerium zirconium aluminum hydroxide gel is obtained. The cerium-zirconium-aluminum gel was calcined at 700°C for 4 hours to obtain cerium-zirconium-aluminum oxide, and its specific surface area was measured to be 125m2/g. Calcined at 1000°C for 10 hours, the aging specific surface area was63m2 /g at 1100°C. Calcined for 10 hours, the aging specific surface area was 41m2 /g.
本发明的高性能铈锆铝储氧材料的制备方法步骤简单，以拟薄水铝石、可溶性的锆盐和铈盐为原料，进行胶溶反应制成溶胶，以碱为沉淀剂，有机高分子酸类、醇类为改性剂，将溶胶经有机改性的碱液沉淀后，对沉淀物进行过滤、洗涤、煅烧、粉碎制得。所制得的铈锆铝储氧材料在700℃-800℃的条件下灼烧2-6小时，测试其新鲜比表面积为120-140m2/g，1000℃的条件下灼烧10小时老化比表面积＞60m2/g，1100℃的条件下灼烧10小时老化比表面积＞40m2/g，所制得的铈锆铝储氧材料具有很好的高热稳定性。The preparation method of the high-performance cerium-zirconium-aluminum oxygen storage material of the present invention has simple steps. Pseudo-boehmite, soluble zirconium salt and cerium salt are used as raw materials to perform peptization reaction to prepare a sol, and alkali is used as a precipitating agent. Molecular acids and alcohols are used as modifiers. After the sol is precipitated by organically modified lye, the precipitate is filtered, washed, calcined, and pulverized. The prepared cerium-zirconium-aluminum oxygen storage material is burned at 700°C-800°C for 2-6 hours, and its fresh specific surface area is 120-140m2 /g, and its aging ratio is measured at 1000°C for 10 hours. The surface area is greater than 60m2 /g, and the aging specific surface area is greater than 40m2 /g after burning for 10 hours under the condition of 1100°C. The prepared cerium-zirconium-aluminum oxygen storage material has good high thermal stability.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the technical principle of the present invention, some improvements and modifications can also be made, these improvements and modifications It should also be regarded as the protection scope of the present invention.
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| CN201210148884.6ACN102716733B (en) | 2012-05-08 | 2012-05-08 | A kind of preparation method of high performance cerium zirconium aluminum oxygen-storage material |
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