技术领域technical field
本发明属于催化剂领域，涉及一种机动车尾气净化催化材料的制备方法，具体涉及一种铈锆基固溶体的制备方法。The invention belongs to the field of catalysts, and relates to a method for preparing a catalytic material for purifying motor vehicle exhaust, in particular to a method for preparing a cerium-zirconium-based solid solution.
背景技术Background technique
减少汽车尾气污染、保护大气环境质量，实现生态环境和社会的可持续发展，是目前及未来相当长时间内我国环境保护的重要课题之一。Reducing vehicle exhaust pollution, protecting the quality of the atmospheric environment, and realizing the sustainable development of the ecological environment and society are one of the important issues of my country's environmental protection at present and in the future for a long time.
为了减少污染，必须从提高汽油品质、改善发动机燃烧状态和增加尾气净化催化效率三方面进行突破。到目前为止，使用汽车尾气净化催化剂是最有效途径就是通过三元催化装置来降低尾气中HC、CO和NOx三种有毒气体的含量，而铈锆基固溶体催化材料是三元催化转化装置中的重要组成部分，它在尾气净化过程中起到调节气氛的作用，当气氛处于贫燃状态时，铈锆基固溶体催化材料将吸收多余的氧气，当气氛处于富燃状态时，铈锆基固溶体催化材料放出氧气，使三种气体得到有效的转化。因此，铈锆基固溶体催化材料的储氧性能的好坏直接影响尾气的转化效率。同时铈锆基固溶体催化材料可有效稳定活性组分的分散，因此具有大的比表面积、较大的孔体积及合适的孔径分布，并具有良好的抗高温老化性能、优异的低温催化性能的铈锆基储氧材料成为新三效催化剂的关键材料。In order to reduce pollution, breakthroughs must be made in three aspects: improving the quality of gasoline, improving the combustion state of the engine, and increasing the catalytic efficiency of exhaust gas purification. So far, the most effective way to use automobile exhaust purification catalysts is to reduce the content of three toxic gases HC, CO and NOx in exhaust gas through three-way catalytic devices, and cerium-zirconium-based solid solution catalytic materials are used in three-way catalytic conversion devices. An important component, it plays a role in adjusting the atmosphere during the exhaust gas purification process. When the atmosphere is in a lean state, the cerium-zirconium-based solid solution catalytic material will absorb excess oxygen. When the atmosphere is in a rich-burn state, the cerium-zirconium-based solid solution catalytic The material emits oxygen, so that the three gases are effectively converted. Therefore, the oxygen storage performance of cerium-zirconium-based solid solution catalytic materials directly affects the conversion efficiency of exhaust gas. At the same time, the cerium-zirconium-based solid solution catalytic material can effectively stabilize the dispersion of active components, so it has a large specific surface area, a large pore volume and a suitable pore size distribution, and has good high-temperature aging resistance and excellent low-temperature catalytic performance. Zirconium-based oxygen storage materials have become the key materials for new three-way catalysts.
由于单纯的CeO2在高温下容易发生烧结、颗粒长大，导致比表面积减小，从而降低直至失去储氧能力。1987年，M.Ozawa等人开始通过添加氧化锆来改善CeO2的热稳定性。和纯的CeO2相比，高性能稀土储氧材料制备技术已成为高性能汽车尾气净化催化剂的核心技术和源头技术，没有高性能稀土储氧材料，要制备出具有市场竞争力的汽车尾气净化催化剂是不可能的。Because pure CeO2 is prone to sintering and particle growth at high temperature, the specific surface area is reduced, thereby reducing or even losing the oxygen storage capacity. In 1987,M.Ozawa et al began to improve the thermal stability of CeO2 by adding zirconia. Compared with pure CeO2, the preparation technology of high- performance rare earth oxygen storage materials has become the core technology and source technology of high-performance automobile exhaust purification catalysts. Without high-performance rare earth oxygen storage materials, it is necessary to prepare automobile exhaust purification with market competitiveness Catalysts are out of the question.
ZrO2添加到CeO2中，可形成CeO2-ZrO2固溶体而改善CeO2的体相特性，利于体相氧原子的迁移和扩散，使体相反应过程变得活泼，能够提高CeO2的储氧能力和高温稳定性。同时，Pr、Nd、Y、Nb、La和Ba等稀土及碱土元素的加入可进一步增强铈锆基固溶体催化材料的抗高温老化性，提高其储氧量。Adding ZrO2 to CeO2 can form aCeO2-ZrO2 solid solution to improve the bulk phase properties ofCeO2 , facilitate the migration and diffusion of bulk oxygen atoms, make the bulk phase reaction process more active, and improve the oxygen storage capacity ofCeO2 capability and high temperature stability. At the same time, the addition of rare earth and alkaline earth elements such as Pr, Nd, Y, Nb, La, and Ba can further enhance the high-temperature aging resistance of the cerium-zirconium-based solid solution catalytic material and increase its oxygen storage capacity.
中国专利号为ZL200510115874.2的发明专利公开了一种高比表面铈锆复合氧化物固溶体组合物及其制备方法，通过添加在沉淀出的悬浊液中添加表面活性剂或胺盐或无机铵盐或乙醇，并高温晶化，晶化后产品经乙醇洗涤，高温焙烧。The invention patent with Chinese patent number ZL200510115874.2 discloses a high specific surface cerium-zirconium composite oxide solid solution composition and its preparation method, by adding surfactant or amine salt or inorganic ammonium to the precipitated suspension Salt or ethanol, and crystallized at high temperature, the crystallized product is washed with ethanol and roasted at high temperature.
但是，上述制备工艺复杂，同时通过高温晶化，乙醇洗涤，不利于工业生产，且沉淀时为普通液相沉淀，粒子较大。However, the above-mentioned preparation process is complicated, and at the same time, it is crystallized at high temperature and washed with ethanol, which is not conducive to industrial production, and the precipitation is ordinary liquid phase precipitation with relatively large particles.
中国专利公开号为CN101637721B的发明专利公开了一种多孔钇铈锆固溶体及其制备方法，通过加入保护剂、混合稀土金属盐溶液和活性聚苯乙烯微球乳液，常温沉淀，80-100℃陈化，收集沉淀物、水洗、干燥、焙烧得目标产物。The invention patent with the Chinese patent publication number CN101637721B discloses a porous yttrium cerium zirconium solid solution and its preparation method, by adding protective agent, mixed rare earth metal salt solution and active polystyrene microsphere emulsion, precipitation at room temperature, aging at 80-100 °C , collect the precipitate, wash with water, dry, and roast to obtain the target product.
上述制备方法中，聚苯乙烯微球乳液与金属盐溶液无法混合均匀，容易导致产品的均一稳定性。In the above preparation method, the polystyrene microsphere emulsion and the metal salt solution cannot be mixed evenly, which easily leads to the uniform stability of the product.
中国专利公开号为CN100496745C的发明专利公开了一种线状或棒状多晶Ce0.6Zr0.3Y0.1O2固溶体制备方法，通过加入十六烷基三甲基溴化铵作为表面活性美国专利号为US 5,747,401的发明专利和美国专利专利号为US 5,723,101的发明专利公开了采用共水热分解法或共沉淀法得到混合沉淀物，然后用烷氧化合物溶液进行洗涤或浸渍，得到固溶体具有高比表面、均匀粒子分布和高储氧能力。所用铈溶液为四价(可由电解氧化、硝酸铈铵或溶解碳酸盐加双氧水获得)，Ce4+浓度大于85％，900℃，6小时比表面：51.7m2/g。Chinese Patent Publication No. CN100496745C discloses a linear or rod-shaped polycrystalline Ce0.6 Zr0.3 Y0.1 O2 solid solution preparation method, by adding cetyltrimethylammonium bromide as surface active U.S. Patent No. The invention patent of US 5,747,401 and the invention patent of US Patent No. US 5,723,101 disclose that mixed precipitates are obtained by co-hydrothermal decomposition or co-precipitation, and then washed or impregnated with an alkoxide solution to obtain a solid solution with a high specific surface area. , Uniform particle distribution and high oxygen storage capacity. The cerium solution used is tetravalent (obtained by electrolytic oxidation, cerium ammonium nitrate or dissolved carbonate plus hydrogen peroxide), Ce4+ concentration is greater than 85%, 900°C, 6 hours specific surface: 51.7m2 /g.
上述制备方法通过水热处理，需要高压设备，不利于产业化生产。The above preparation method requires high-pressure equipment through hydrothermal treatment, which is not conducive to industrial production.
因此，特别需要一种铈锆基固溶体催化材料及其制备方法，以解决上述现有存在的问题。Therefore, there is a special need for a cerium-zirconium-based solid solution catalytic material and a preparation method thereof to solve the above-mentioned existing problems.
发明内容Contents of the invention
本发明要解决的技术问题，是提供一种铈锆基固溶体催化剂的制备方法，所制备出的铈锆基固溶体具有比表面积大、高温抗老化能力好、储放氧能力高等特点。The technical problem to be solved by the present invention is to provide a method for preparing a cerium-zirconium-based solid solution catalyst. The prepared cerium-zirconium-based solid solution has the characteristics of large specific surface area, good high-temperature anti-aging ability, and high oxygen storage and release ability.
为解决上述技术问题，本发明所采取的技术方案是：In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
一种铈锆基固溶体催化材料的制备方法，它按照以下步骤顺序进行：A preparation method of a cerium-zirconium-based solid solution catalytic material, which is carried out in accordance with the following steps:
(1)酸性溶液A的制备：将硝酸铈铵、除铈以外的其他稀土可溶性硝酸盐和硝酸氧锆溶于水，加入有机络合剂，得酸性溶液A；(1) Preparation of acidic solution A: dissolving ceric ammonium nitrate, other rare earth soluble nitrates except cerium and zirconyl nitrate in water, adding an organic complexing agent to obtain acidic solution A;
(2)碱性溶液B的制备：将质量分数为25％的氨水用纯水稀释至10％，得碱性溶液B；(2) Preparation of alkaline solution B: dilute ammonia water with a mass fraction of 25% to 10% with pure water to obtain alkaline solution B;
(3)沉淀反应：将碱性溶液B加入到加热至70-80℃的酸性溶液A中，至沉淀终点的pH为9-10，然后在搅拌条件下动态陈化2-4h，得固液混合体系C；(3) Precipitation reaction: Add alkaline solution B to acidic solution A heated to 70-80°C until the pH at the end of precipitation is 9-10, and then dynamically age for 2-4h under stirring conditions to obtain solid-liquid Mixed system C;
(4)洗涤：将固液混合体系C脱水，漂洗，过滤，得到湿饼D；(4) Washing: dehydrating the solid-liquid mixed system C, rinsing, and filtering to obtain wet cake D;
(5)湿饼的表面处理：将湿饼D与80-90℃的热水以质量比1:1重新打浆，加入醇类溶剂，剪切分散，得到泥浆E；(5) Surface treatment of wet cake: wet cake D and hot water at 80-90°C are repulped at a mass ratio of 1:1, and alcohol solvent is added to shear and disperse to obtain mud E;
(6)焙烧：将泥浆E在600-800℃下焙烧4-6h，得所述铈锆基固溶体催化材料。(6) Calcination: Calcining the slurry E at 600-800° C. for 4-6 hours to obtain the cerium-zirconium-based solid solution catalytic material.
作为本发明的一种限定，所述除铈以外的其他稀土可溶性硝酸盐为硝酸镧、硝酸钇、硝酸镨和硝酸钕中的两种或三种。As a limitation of the present invention, the rare earth soluble nitrates other than cerium are two or three of lanthanum nitrate, yttrium nitrate, praseodymium nitrate and neodymium nitrate.
作为本发明的另一种限定，所述步骤(1)中的有机络合剂为氨基羧基类络合物。As another limitation of the present invention, the organic complexing agent in the step (1) is an aminocarboxyl complex.
作为上述限定的进一步限定，所述氨基羧酸类络合物为EDTA(乙二胺四乙酸)、HEDTA(羟乙基三胺三乙酸)、DTPA(二乙二胺五乙酸)中的一种。As a further limitation of the above limitation, the aminocarboxylic acid complex is one of EDTA (ethylenediaminetetraacetic acid), HEDTA (hydroxyethyltriaminetriacetic acid), and DTPA (diethylenediaminepentaacetic acid). .
作为上述限定的更进一步限定，所述的有机络合剂，以质量计，加入量为硝酸铈铵、除铈以外的其他稀土可溶性硝酸盐和硝酸氧锆等金属硝酸盐原料总质量的20-30％。As a further limitation of the above-mentioned limitations, the organic complexing agent, in terms of mass, is added in an amount of 20-20% of the total mass of metal nitrate raw materials such as ammonium cerium nitrate, other rare earth soluble nitrates except cerium, and zirconium oxynitrate. 30%.
作为本发明的第三种限定，所述步骤(1)中，各硝酸盐的比例为：As the third limitation of the present invention, in the step (1), the ratio of each nitrate is:
硝酸铈铵 20-50％Ammonium cerium nitrate 20-50%
硝酸氧锆 40-76％Zirconyl nitrate 40-76%
除铈以外的其他稀土可溶性硝酸盐 3-12％。Rare earth soluble nitrates other than cerium 3-12%.
组分的百分比之和为100％；The sum of the percentages of the components is 100%;
作为本发明的另一种限定，所述步骤(1)中，以质量计，硝酸铈铵、除铈以外的其他稀土可溶性硝酸盐和硝酸氧锆等金属硝酸盐占酸性溶液A总质量的10％-15％。As another limitation of the present invention, in the step (1), metal nitrates such as ammonium cerium nitrate, other rare earth soluble nitrates except cerium and zirconium oxynitrate account for 10% of the total mass of acidic solution A by mass. %-15%.
作为上述限定的进一步限定，所述步骤(5)中所述的醇类溶剂，为丙二醇、丙三醇中的一种或几种组合。As a further limitation of the above limitation, the alcohol solvent described in the step (5) is one or more combinations of propylene glycol and glycerin.
作为上述限定的更进一步限定，所述的醇类溶剂，加入量以质量计为硝酸铈铵、除铈以外的其他稀土可溶性硝酸盐和硝酸氧锆的总质量的30-50％。As a further limitation of the above limitation, the added amount of the alcohol solvent is 30-50% by mass of the total mass of ammonium cerium nitrate, soluble nitrates of other rare earths except cerium and zirconium oxynitrate.
本发明还有一种限定，所制得的铈锆基固溶体催化材料由氧化铈、氧化锆和除铈锆以外的其它稀土氧化物组成的复合氧化物组成，其重量百分比如下：氧化铈：30-60％，氧化锆：25-65％，和除铈锆以外其它稀土氧化物：11-14％。The present invention also has a limitation that the prepared cerium-zirconium-based solid solution catalytic material is composed of cerium oxide, zirconia and a composite oxide composed of other rare earth oxides except cerium-zirconium oxide, and its weight percentage is as follows: cerium oxide: 30- 60%, zirconia: 25-65%, and other rare earth oxides except cerium-zirconium: 11-14%.
由于现有的铈锆基固溶体的制备方法有很多种，主要是液相法，包括共沉淀法、溶胶凝胶法、模版法、微乳液法等。而共沉淀法作为常用的制备方法，是将沉淀剂加入到金属的盐溶液中，将可溶性的组分转化为难溶性组分，经过滤、洗涤、干燥、焙烧等步骤得到目标化合物，但是在高温下焙烧会导致比表面积的下降，另外在沉淀、干燥、焙烧等过程中会涉及到粒子的聚集长大、孔径孔容的合理选择等。因此本发明中所涉及的制备方法中的技术参数对于最终制备的产品铈锆基固溶体的指标具有显著的影响。另外，在制备过程中料液浓度、化学反应的温度、沉淀剂的浓度、各种添加剂的筛选与添加量的控制等等均是材料制备的关键因素，这涉及到沉淀物的粒度、均匀性、分散性、沉降性等，也涉及到目标产品的聚集性、形貌、固溶性、孔径孔容等。There are many methods for preparing cerium-zirconium-based solid solutions, mainly liquid-phase methods, including co-precipitation, sol-gel, template, and microemulsion methods. The co-precipitation method, as a commonly used preparation method, is to add a precipitant to the metal salt solution, convert the soluble component into an insoluble component, and obtain the target compound through steps such as filtration, washing, drying, and roasting, but at high temperature Lower calcination will lead to a decrease in the specific surface area. In addition, the aggregation and growth of particles and the reasonable selection of pore size and volume will be involved in the processes of precipitation, drying, and calcination. Therefore, the technical parameters in the preparation method involved in the present invention have a significant impact on the index of the final prepared product cerium-zirconium-based solid solution. In addition, in the preparation process, the concentration of the feed liquid, the temperature of the chemical reaction, the concentration of the precipitating agent, the screening of various additives and the control of the amount of addition are all key factors in the preparation of materials, which involve the particle size and uniformity of the precipitate. , dispersibility, sedimentation, etc., and also involves the aggregation, morphology, solid solubility, pore size and volume of the target product.
由于采用了上述的技术方案，本发明与现有技术相比，所取得的技术进步在于：Owing to having adopted above-mentioned technical scheme, the technical progress that the present invention obtains compared with prior art is:
(1)本发明通过金属硝酸盐溶液含有有机络合剂，通过有机络合剂与稀土及锆离子的络合配位，控制沉淀反应过程中的沉淀速度，得到了粒径均一、稳定的前驱体。(1) The present invention contains an organic complexing agent through the metal nitrate solution, and through the complexation and coordination of the organic complexing agent with rare earth and zirconium ions, the precipitation rate in the precipitation reaction process is controlled, and a uniform and stable precursor with a particle size is obtained. body.
(2)本发明所选用的含铈的原材料选自硝酸铈铵，因为硝酸铈铵中铈的价态为+4价，一方面，作为硬酸类的稀土离子，电荷数越大，静电引力大，配位能力强，增加了稀土离子与络合基的络合能力，提高了络合物的稳定性；另一方面，促进了稀土离子与锆离子的的固溶能力，确保了目标产品具有好的固溶相，即使在1000℃的高温老化下依然没有分相。(2) the selected cerium-containing raw material of the present invention is selected from cerium ammonium nitrate, because the valence state of cerium in cerium ammonium nitrate is +4 valence, on the one hand, as the rare earth ion of hard acid class, the larger the charge number, the electrostatic attraction Large, strong coordination ability, which increases the complexation ability of rare earth ions and complex groups, and improves the stability of complexes; on the other hand, it promotes the solid solution ability of rare earth ions and zirconium ions, ensuring the target product Has a good solid solution phase, even under the high temperature aging of 1000 ℃, there is still no phase separation.
(3)通过醇类溶剂在沉淀物前驱体进行表面处理，一方面，解决了焙烧过程中颗粒的团聚问题；另一方面，通过有机物的焙烧，提高焙烧产物的孔径、孔容，得到热稳定性良好的铈锆基固溶体催化材料。(3) The surface treatment of the precipitate precursor is carried out by alcohol solvents. On the one hand, the problem of particle agglomeration during the roasting process is solved; Good cerium-zirconium-based solid solution catalytic material.
(4)通过混合金属料液选择及浓度、沉淀剂的选择及浓度、添加剂的筛选及添加量的控制，结合反应的条件、焙烧条件等的适宜选择和控制，得到了具有颗粒小，比表面积大、高温抗老化能力和活性高等优点的铈锆基固溶体催化材料。(4) Through the selection and concentration of the mixed metal material liquid, the selection and concentration of the precipitating agent, the screening of additives and the control of the amount of addition, combined with the appropriate selection and control of reaction conditions and roasting conditions, the product with small particles and specific surface area is obtained. It is a cerium-zirconium-based solid solution catalytic material with the advantages of large size, high temperature anti-aging ability and high activity.
本发明适用于铈锆基固溶体的制备，尤其适用于机动车尾气净化催化剂、有机废气消除和天然气催化燃烧等废气净化或催化燃烧的催化剂用载体和助剂。The invention is suitable for the preparation of cerium-zirconium-based solid solution, and is especially suitable for the catalyst carrier and auxiliary agent for exhaust gas purification or catalytic combustion such as motor vehicle exhaust gas purification catalyst, organic waste gas elimination and natural gas catalytic combustion.
本发明下面将结合说明书附图与具体实施例作进一步详细说明。The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.
附图说明Description of drawings
图1为本发明的实施例1制备铈锆基固溶体催化材料的XRD示意图。Fig. 1 is an XRD schematic diagram of a cerium-zirconium-based solid solution catalytic material prepared in Example 1 of the present invention.
图2为本发明的实施例1制备铈锆基固溶体催化材料1000℃焙烧4h的XRD示意图。Fig. 2 is an XRD schematic diagram of the cerium-zirconium-based solid solution catalytic material prepared in Example 1 of the present invention and calcined at 1000° C. for 4 hours.
图3为本发明的对比例1制备铈锆基固溶体催化材料1000℃焙烧4h的XRD示意图。3 is a schematic XRD diagram of the cerium-zirconium-based solid solution catalytic material prepared in Comparative Example 1 of the present invention and calcined at 1000° C. for 4 hours.
具体实施方式detailed description
实施例1一种铈锆基固溶体催化材料的制备方法Embodiment 1 A kind of preparation method of cerium-zirconium-based solid solution catalytic material
制备100kg质量组成为30％氧化铈、5％氧化镧、6％氧化钇、59％的氧化锆的铈锆基固溶体催化材料，根据计算，需要96.77kg硝酸铈铵(稀土总量REO为31％、氧化铈含量CeO2/REO≥99.9％)、13.16kg硝酸镧(稀土总量REO为38％、氧化镧含量La2O3/REO≥99.9％)、16.22kg硝酸钇(稀土总量REO为37％、氧化钇含量Y2O3/REO≥99.9％)、197kg硝酸氧锆(ZrO2含量30％)。Preparation of 100kg mass composition is 30% cerium oxide, 5% lanthanum oxide, 6% yttrium oxide, 59% cerium-zirconium-based solid solution catalytic material of zirconia, according to calculation, need 96.77kg cerium ammonium nitrate (rare earth total amount REO is 31% , cerium oxide content CeO2 /REO≥99.9%), 13.16kg lanthanum nitrate (the total amount of rare earth REO is 38%, and the content of lanthanum oxide La2 O3 /REO≥99.9%), 16.22kg yttrium nitrate (the total amount of rare earth REO is 37%, yttrium oxide content Y2 O3 /REO≥99.9%), 197kg zirconyl nitrate (ZrO2 content 30%).
(1)酸性溶液A的制备：将96.77kg硝酸铈铵、13.16kg硝酸镧、16.22kg硝酸钇、197kg硝酸氧锆，加入到2907kg的纯水中，溶解澄清，得澄清透明的溶液后，加入64.6kgEDTA(乙二胺四乙酸)，待溶解后，加热至70℃得酸性溶液A；(1) Preparation of acidic solution A: 96.77kg cerium ammonium nitrate, 13.16kg lanthanum nitrate, 16.22kg yttrium nitrate, 197kg zirconium oxynitrate were added to 2907kg of pure water, dissolved and clarified to obtain a clear and transparent solution, then added 64.6kg of EDTA (ethylenediaminetetraacetic acid), after being dissolved, was heated to 70°C to obtain acidic solution A;
(2)碱性溶液B的制备：将质量分数为25％的氨水用纯水稀释至10％，得碱性溶液B；(2) Preparation of alkaline solution B: dilute ammonia water with a mass fraction of 25% to 10% with pure water to obtain alkaline solution B;
(3)沉淀反应：将碱性溶液B加入到加热至70℃的酸性溶液A中，至沉淀终点的pH为9，然后在搅拌条件下动态陈化2h，得固液混合体系C；(3) Precipitation reaction: adding the alkaline solution B into the acidic solution A heated to 70°C until the pH at the end of the precipitation is 9, and then dynamically aging for 2 hours under stirring conditions to obtain the solid-liquid mixed system C;
(4)洗涤：将固液混合体系C脱水，漂洗，过滤，得到湿饼D；(4) Washing: dehydrating the solid-liquid mixed system C, rinsing, and filtering to obtain wet cake D;
(5)湿饼的表面处理：将湿饼D与90℃的热水以质量比1:1重新打浆，加入加入97kg丙三醇，剪切分散，得到泥浆E；(5) Surface treatment of the wet cake: re-beat the wet cake D and hot water at 90°C at a mass ratio of 1:1, add 97kg of glycerol, and shear and disperse to obtain mud E;
(6)焙烧：将泥浆E在600℃下焙烧6h，得所述铈锆基固溶体催化材料。(6) Roasting: The slurry E was calcined at 600° C. for 6 hours to obtain the cerium-zirconium-based solid solution catalytic material.
得到的铈锆基固溶体催化材料的比表面积为90.5m2/g，经XRD分析，见图1；该催化材料在1000℃焙烧4h后的比表面积为58.2m2/g，，经XRD分析，见图2；1050℃焙烧12h后的比表面积为38.5m2/g。The specific surface area of the obtained cerium-zirconium-based solid solution catalytic material is 90.5m2 /g, which is analyzed by XRD, as shown in Figure 1; the specific surface area of the catalytic material after calcination at 1000°C for 4 hours is 58.2m2 /g, which is analyzed by XRD. See Figure 2; the specific surface area after calcination at 1050°C for 12 hours is 38.5m2 /g.
实施例2-6铈锆基固溶体催化材料的制备方法The preparation method of embodiment 2-6 cerium-zirconium-based solid solution catalytic material
实施例2-6分别为一种铈锆基固溶体催化材料的制备方法，其方法与实施例1类似，不同之处仅在于其中所涉及的技术参数不同，具体如下表所示：Examples 2-6 are respectively a preparation method of a cerium-zirconium-based solid solution catalytic material, which is similar to that of Example 1, except that the technical parameters involved are different, as shown in the following table:
对比例1Comparative example 1
本实施例制备100kg质量组成为30％氧化铈、5％氧化镧、6％氧化钇、59％的氧化锆的铈锆基固溶体催化材料，根据计算，需要76.9kg硝酸铈(稀土总量REO为39％、氧化铈含量CeO2/REO≥99.9％)、13.16kg硝酸镧(稀土总量REO为38％、氧化镧含量La2O3/REO≥99.9％)、16.22kg硝酸钇(稀土总量REO为37％、氧化钇含量Y2O3/REO≥99.9％)、197kg硝酸氧锆(ZrO2含量30％)。The present embodiment prepares 100kg mass composition and is the cerium-zirconium base solid solution catalytic material of the zirconia of 30% cerium oxide, 5% lanthanum oxide, 6% yttrium oxide, 59%, according to calculation, need 76.9kg cerium nitrate (rare earth total amount REO is 39%, cerium oxide content CeO2 /REO≥99.9%), 13.16kg lanthanum nitrate (total rare earth REO is 38%, lanthanum oxide content La2 O3 /REO≥99.9%), 16.22kg yttrium nitrate (total rare earth REO is 37%, yttrium oxide content Y2 O3 /REO≥99.9%), 197kg zirconyl nitrate (ZrO2 content 30%).
将76.9kg硝酸铈铵、13.16kg硝酸镧、16.22kg硝酸钇、197kg硝酸氧锆，加入到2907kg的纯水中，溶解澄清，得澄清透明的溶液后，加热至70℃得澄清透明的溶液A；在搅拌条件下，往溶液A中缓慢加入10％的氨水，至pH为9.0。然后在搅拌条件下，保温2h后，将得到的固液混合体系经抽滤、洗涤，得铈锆基固溶体催化材料前驱体滤饼。将滤饼转入匣钵，在600℃焙烧6h，得所述的铈锆基固溶体催化材料。Add 76.9kg of cerium ammonium nitrate, 13.16kg of lanthanum nitrate, 16.22kg of yttrium nitrate, and 197kg of zirconium oxynitrate into 2907kg of pure water, dissolve and clarify to obtain a clear and transparent solution, then heat to 70°C to obtain a clear and transparent solution A ; Under stirring conditions, slowly add 10% ammonia water to solution A until the pH is 9.0. Then, under the condition of stirring, after keeping warm for 2 hours, the obtained solid-liquid mixed system is suction-filtered and washed to obtain a filter cake of the precursor of the cerium-zirconium-based solid solution catalytic material. Transfer the filter cake into a sagger and bake at 600° C. for 6 hours to obtain the cerium-zirconium-based solid solution catalytic material.
得到的铈锆基固溶体催化材料的比表面积为80.5m2/g，该催化材料在1000℃焙烧4h后的比表面积为18.2m2/g，经XRD分析，见图3；1050℃焙烧12h后的比表面积为10.5m2/g。其比表面积在高温催化前后均较实施例1-6均有明显下降。The specific surface area of the obtained cerium-zirconium-based solid solution catalytic material is 80.5m2 /g, and the specific surface area of the catalytic material after calcination at 1000°C for 4 hours is 18.2m2 /g, as shown in Figure 3 by XRD analysis; after calcination at 1050°C for 12 hours The specific surface area is 10.5m2 /g. Compared with Examples 1-6, its specific surface area has significantly decreased before and after high-temperature catalysis.
对比例2Comparative example 2
本实施例制备100kg质量组成为30％氧化铈、5％氧化镧、6％氧化钇、59％的氧化锆的铈锆基固溶体催化材料，根据计算，需要96.77kg硝酸铈铵(稀土总量REO为31％、氧化铈含量CeO2/REO≥99.9％)、13.16kg硝酸镧(稀土总量REO为38％、氧化镧含量La2O3/REO≥99.9％)、16.22kg硝酸钇(稀土总量REO为37％、氧化钇含量Y2O3/REO≥99.9％)、197kg硝酸氧锆(ZrO2含量30％)。The present embodiment prepares 100kg mass composition and is 30% cerium oxide, 5% lanthanum oxide, 6% yttrium oxide, the cerium zirconium base solid solution catalytic material of 59% zirconia, according to calculation, need 96.77kg cerium ammonium nitrate (rare earth total amount REO 31%, cerium oxide content CeO2 /REO≥99.9%), 13.16kg lanthanum nitrate (total rare earth REO is 38%, lanthanum oxide content La2 O3 /REO≥99.9%), 16.22kg yttrium nitrate (total rare earth The amount of REO is 37%, the content of yttrium oxide (Y2 O3 /REO≥99.9%), and 197kg of zirconyl nitrate (the content of ZrO2 is 30%).
将96.77kg硝酸铈铵、13.16kg硝酸镧、16.22kg硝酸钇、197kg硝酸氧锆，加入到2907kg的纯水中，溶解澄清，得澄清透明的溶液后，加入64.6kg EDTA(乙二胺四乙酸)，待溶解后，加热至70℃得澄清透明的溶液A；在搅拌条件下，往溶液A中缓慢加入10％的氨水，至pH为9.0。然后在搅拌条件下，保温2h后，将得到的固液混合体系经抽滤、洗涤，得铈锆基固溶体催化材料前驱体滤饼。将滤饼转入匣钵，在600℃焙烧6h，得所述的铈锆基固溶体催化材料。96.77kg cerium ammonium nitrate, 13.16kg lanthanum nitrate, 16.22kg yttrium nitrate, 197kg zirconyl nitrate were added to 2907kg of pure water, dissolved and clarified, and after obtaining a clear and transparent solution, 64.6kg EDTA (ethylenediaminetetraacetic acid) was added ), after being dissolved, heated to 70°C to obtain a clear and transparent solution A; under stirring conditions, slowly add 10% ammonia water to the solution A until the pH is 9.0. Then, under the condition of stirring, after keeping warm for 2 hours, the obtained solid-liquid mixed system is suction-filtered and washed to obtain a filter cake of the precursor of the cerium-zirconium-based solid solution catalytic material. Transfer the filter cake into a sagger and bake at 600° C. for 6 hours to obtain the cerium-zirconium-based solid solution catalytic material.
得到的铈锆基固溶体催化材料的比表面积为90.5m2/g，该催化材料在1000℃焙烧4h后的比表面积为23.2m2/g，1050℃焙烧12h后的比表面积为14.5m2/g。其比表面积在高温催化后均较实施例1-6均有明显下降。The specific surface area of the obtained cerium-zirconium-based solid solution catalytic material is 90.5m2 /g, the specific surface area of the catalytic material is 23.2m2 /g after calcination at 1000°C for 4 hours, and the specific surface area after 12h calcination at 1050°C is 14.5m2 /g. g. After high-temperature catalysis, its specific surface area all significantly decreased compared with Examples 1-6.
对比例3Comparative example 3
本实施例制备100kg质量组成为30％氧化铈、5％氧化镧、6％氧化钇、59％的氧化锆的铈锆基固溶体催化材料，根据计算，需要96.77kg硝酸铈铵(稀土总量REO为31％、氧化铈含量CeO2/REO≥99.9％)、13.16kg硝酸镧(稀土总量REO为38％、氧化镧含量La2O3/REO≥99.9％)、16.22kg硝酸钇(稀土总量REO为37％、氧化钇含量Y2O3/REO≥99.9％)、197kg硝酸氧锆(ZrO2含量30％)。The present embodiment prepares 100kg mass composition and is 30% cerium oxide, 5% lanthanum oxide, 6% yttrium oxide, the cerium zirconium base solid solution catalytic material of 59% zirconia, according to calculation, need 96.77kg cerium ammonium nitrate (rare earth total amount REO 31%, cerium oxide content CeO2 /REO≥99.9%), 13.16kg lanthanum nitrate (total rare earth REO is 38%, lanthanum oxide content La2 O3 /REO≥99.9%), 16.22kg yttrium nitrate (total rare earth The amount of REO is 37%, the content of yttrium oxide (Y2 O3 /REO≥99.9%), and 197kg of zirconyl nitrate (the content of ZrO2 is 30%).
将96.77kg硝酸铈铵、13.16kg硝酸镧、16.22kg硝酸钇、197kg硝酸氧锆，加入到2907kg的纯水中，溶解澄清，得澄清透明的溶液后，加热至70℃得澄清透明的溶液A；在搅拌条件下，往溶液A中缓慢加入10％的氨水，至pH为9.0。然后在搅拌条件下，保温2h后，将得到的固液混合体系经抽滤、洗涤，得铈锆基固溶体催化材料前驱体滤饼。将滤饼与90℃的热纯水按照质量比1：1打浆，加入60kg丙三醇，剪切分散1h后，转入匣钵，在600℃焙烧6h，得所述的铈锆基固溶体催化材料。Add 96.77kg of cerium ammonium nitrate, 13.16kg of lanthanum nitrate, 16.22kg of yttrium nitrate, and 197kg of zirconyl nitrate into 2907kg of pure water, dissolve and clarify to obtain a clear and transparent solution, then heat to 70°C to obtain a clear and transparent solution A ; Under stirring conditions, slowly add 10% ammonia water to solution A until the pH is 9.0. Then, under the condition of stirring, after keeping warm for 2 hours, the obtained solid-liquid mixed system is suction-filtered and washed to obtain a filter cake of the precursor of the cerium-zirconium-based solid solution catalytic material. Beat the filter cake with hot pure water at 90°C at a mass ratio of 1:1, add 60kg of glycerol, shear and disperse for 1 hour, then transfer to a sagger, and roast at 600°C for 6 hours to obtain the cerium-zirconium-based solid solution catalyst Material.
得到的铈锆基固溶体催化材料的比表面积为90.5m2/g，该催化材料在1000℃焙烧4h后的比表面积为28.2m2/g，1050℃焙烧12h后的比表面积为18.5m2/g。其比表面积在高温催化后均较实施例1-6均有明显下降。The specific surface area of the obtained cerium-zirconium-based solid solution catalytic material is 90.5m2 /g, the specific surface area of the catalytic material is 28.2m2 /g after calcination at 1000°C for 4 hours, and the specific surface area after 12h calcination at 1050°C is 18.5m2 /g. g. After high-temperature catalysis, its specific surface area all significantly decreased compared with Examples 1-6.
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述技术内容作为启示加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作出的简单修改，等同变化与改型，仍属于本发明权利要求的保护范围。The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention to other forms. Any skilled person who is familiar with this field may use the above technical content as a revelation to change or remodel it into an equivalent change. Example. However, all simple modifications made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solutions of the present invention, equivalent changes and modifications, still belong to the protection scope of the claims of the present invention.
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