CN1311903C - Method for preparing rare earth base high-performance three-effect catalyst - Google Patents

Method for preparing rare earth base high-performance three-effect catalyst Download PDF

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CN1311903C
CN1311903C CN 200410093861 CN200410093861A CN1311903C CN 1311903 C CN1311903 C CN 1311903C CN 200410093861 CN200410093861 CN 200410093861 CN 200410093861 A CN200410093861 A CN 200410093861A CN 1311903 C CN1311903 C CN 1311903C
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nitrate
catalyst
rare earth
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CN1663680A (en
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肖彦
张燕
薛群山
袁慎忠
刘毅
赵耀武
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天津化工研究设计院
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Abstract

本发明涉及汽车尾气净化技术,是一种稀土基高性能三效催化剂的制备方法。 The present invention relates to automotive exhaust gas purification technology, a method for producing a rare earth-based high-performance three-way catalyst. 特征在于将主要含有稀土复合氧化物、氧化铝、金属或陶瓷蜂窝载体和至少一种贵金属活性组分如氯化铑、硝酸铑、硝酸钯、氯化钯、硝酸铂、氯铂酸等,通过干混预研磨新工艺等制备方法,得到一种具有高活性、高热稳定性、应用在不同汽车上可以满足不同排放标准的净化催化剂。 Characterized in that the rare earth complex oxide mainly containing alumina, a metal or ceramic honeycomb carrier and at least one noble metal active component such as rhodium chloride, rhodium nitrate, palladium nitrate, palladium chloride, platinum nitrate, chloroplatinic acid, by dry blending the pre-ground preparation of the new process and the like, to obtain a high activity and high thermal stability, purification catalyst applied to meet different emission standards on different cars.

Description

一种稀土基高性能三效催化剂的制备方法 Rare earth-based high-performance three-way catalyst preparation

技术领域 FIELD

本发明涉及汽车尾气净化技术,是一种稀土基高性能三效催化剂的制备方法。 The present invention relates to automotive exhaust gas purification technology, a method for producing a rare earth-based high-performance three-way catalyst.

背景技术 Background technique

汽车发动机起动后,燃油燃烧之后产生—氧化碳CO、未完全燃烧的碳氢化合物HC和氮氧化物NOx,这些对人身体有害的物质随废气排出,并通过汽车三效催化剂床层。 Automobile engine start, the fuel after combustion - CO.'S carbon monoxide, unburned hydrocarbons and oxides of nitrogen the NOx HC, these substances harmful to the human body is discharged with the exhaust gases, and by three-way automotive catalyst bed. 在汽车三效催化剂的作用下,可将这些有害物质的大部分转化为无害成分水、二氧化碳和氮气。 In the automotive three-way catalyst effect, these may be most harmful substances into harmless components water, carbon dioxide and nitrogen. 这些催化剂通常是在诸如氧化铝、氧化硅、氧化钛、稀土复合氧化物材料等催化剂载体上负载催化剂活性组分如贵金属铂、钯、铑、钌等和用于提高其催化作用的助剂、添加剂等构成的。 These catalysts are usually on a catalyst support such as alumina, silica, titania, rare earth complex oxide active components supported catalyst materials such as precious metals platinum, palladium, rhodium, ruthenium, and the like for improving its catalytic additives, additives configuration.

其中,作为该催化剂的重要组成部分的催化剂载体如氧化铝、氧化硅、氧化钛、稀土等,主要用于为催化剂的活性组分提供高的比表面和催化反应合适的孔结构。 Wherein the catalyst carrier is an important part of the catalyst such as alumina, silica, titania, rare earth, is mainly suitable for providing a high specific surface and pore structure of the active catalytic component of the catalyst. 这些催化剂载体,其比表面积一般达到130~350m2/g,孔结构参数包括平均孔径和平均孔容均要满足要求,如达到110的孔径和0.3cm3/g的孔容。 These catalyst supports, which typically reaches a specific surface area of ​​130 ~ 350m2 / g, pore structure parameters include an average pore volume and average pore size to meet all the requirements, such as to achieve aperture 110 and 0.3cm3 / g pore volume. 其中的堇青石陶瓷蜂窝基体,具有平行排列的气体通道,这些通道的形状有正方形、三角形等,通道的壁厚可以达到0.1~0.25mm,平均孔密度可以达到200~800孔/平方英寸,甚至更高的能达到1200孔/平方英寸。 Wherein the cordierite ceramic honeycomb substrate having a gas channel arranged in parallel, these channels have the shape of a square, triangular, etc., the wall thickness of the channel can reach 0.1 ~ 0.25mm, an average pore density may be 200 to 800 cells / square inch, and even higher energy up to 1200 holes / square inch.

在催化剂的助剂构成当中,主要的助剂是铈基稀土复合氧化物材料,这种氧化物材料除了起到提高催化剂活性之助催化剂作用外,还具有很好的储氧性能,即具有在氧化气氛下吸收氧、在还原气氛下释放氧的特性,利用这种氧吸收、释放的特性可以拓宽三效催化剂空燃比操作窗口宽度,更加有效地净化废气中的三种有害成份。 Among the additives constituting the catalyst, mainly cerium-based adjuvants are rare earth complex oxide material, oxide material such cocatalyst in addition functions to raise the activity of the catalyst, but also has good oxygen storage performance, i.e., having absorption oxidizing atmosphere of oxygen, the oxygen release characteristics in a reducing atmosphere, use of such an oxygen absorbent, the release properties of three-way catalyst can be broadened operating window width of air-fuel ratio, the exhaust gas more effectively purify harmful components in three. 此外,加入这种稀土复合氧化物可以有效地提高三效催化剂的活性、提高催化剂的耐高温性能、催化剂的抗硫抗铅等有毒物质的性能,并能较大幅度降低贵金属的使用量。 Furthermore, addition of such rare earth complex oxide can be effectively improved three-way catalyst activity, the catalyst to improve the high temperature performance, anti-anti-sulfur performance of the catalyst of toxic substances such as lead, and can more greatly reduce the amount of noble metal. 因此,稀土复合氧化物已成为三效催化剂制备的重要助剂成分,不可替代。 Thus, rare earth complex oxide additives has become an important component of the three-way catalyst preparation, can not be replaced. 同时,不同的催化剂,可以选用不同性能的稀土复合氧化物,可以使催化剂的性能发生很大的变化,使催化剂的制备成本各有很大的不同,以满足不同的使用条件。 Meanwhile, different catalyst, can choose different properties of rare earth complex oxide, the catalyst performance can be greatly changed, so that very different from each catalyst preparation cost, to meet different use conditions. 这些稀土复合氧化物,均是在氧化铈的基础上,添加其它的氧化物成分,包括Zr、La、Pr、Nu、Y等的氧化物,并且能够调整各个组成部分的化学比例,使复合材料的整体性能发生很大的变化,包括这些稀土复合材料的比表面、孔结构、孔径和孔容分布等等。 These rare earth complex oxides are cerium oxide is based on the addition of other oxide components, an oxide comprising Zr, La, Pr, Nu, Y or the like, and is capable of adjusting the chemical composition ratios of the individual parts of the composite material overall performance change a lot, including such rare earth composite materials of the surface area, pore structure, pore size and pore volume distribution and the like.

依据这些变化,可以通过调整催化剂中的载体氧化铝、助剂稀土复合氧化物、催化活性成分贵金属等组成的比例、组成的性能、组成的含量等调变三效催化剂的催化活性、耐高温性能、催化剂的储氧性能等。 Based on the ratio of these changes by adjusting the alumina catalyst carrier, adjuvant rare earth complex oxide, the catalytically active noble metal components and other components, the performance of the composition, the content of other components of the three-way catalyst modulated catalytic activity, high temperature performance , oxygen storage performance of the catalyst. 本发明同样使用稀土复合氧化物催化材料作为重要助剂,并利用这些材料的不同物理化学性能来改变三效催化剂的实用性能。 The present invention is also the use of rare earth complex oxide catalytic material as an important aid, and using different physical and chemical properties of these materials to change the practical performance of the three-way catalyst.

汽油燃料车的尾气燃烧净化温度,因污染物质的含量不同而不同,低时可达700~800℃,高时能达到1300℃。 Gasoline fuel vehicle exhaust gas purifying combustion temperature differs depending on the pollutant content of up to 700 ~ 800 ℃ low, it can reach 1300 ℃ high. 通常的蜂窝催化剂,尽管负载贵金属催化组分的氧化铝载体已由碱土、或稀土金属,氧化锆或氧化硅等进行了稳定化处理,但稳定后的氧化铝在高温下曝露较长时间后仍难以维持要求的比表面积。 After conventional honeycomb catalyst, although alumina supports a noble metal catalyst component by the alkaline earth or rare earth metal, zirconium oxide or silicon oxide, like the stabilizing treatment, the stabilized alumina exposure but a longer time is still at an elevated temperature difficult to maintain the required specific surface area. 有些催化剂在较高温度下稳定性较好,但难以适应尾气中污染物含量较高的情况。 Some preferred catalyst stability at higher temperatures, but it is difficult to adapt to high levels of pollutants in the exhaust case.

尽管目前三效催化剂的专利也有很多,对三效催化剂的改进采取了各种各样的方法,包括在陶瓷蜂窝载体上的结构和成分上、使用的氧化铝载体改进和添加助剂的选择上、使用的不同方法制备的稀土复合氧化物材料和组成上、以及在催化剂中加入各种成分的优化等,均做了很大的努力,并且也取得了很大的进展,三效催化剂的各方面性能取得了很大的提高。 Although the three-way catalyst, there are many patents, for improved three-way catalyst is adopted a variety of methods, including the structure and composition of the ceramic honeycomb substrate, modifications and additions on an alumina carrier used additives selected , rare earth complex oxide materials prepared by different methods and using the composition, and the addition of various components in the catalyst optimization, have done a great deal of effort, and has made great progress, each three-way catalyst aspects of performance achieved greatly improved. 并且依靠这些进步,使得三效催化剂得到广泛的应用,成为汽车工业在满足环保要求前提下快速发展的重要保证。 And rely on these advances, making the three-way catalyst is widely used, has become an important guarantee for the automotive industry to meet the environmental requirements of the rapid development of the premise. 但在目前三效催化剂的使用过程中,仍存在很多问题,主要包括催化剂的耐硫抗铅性能不强,耐高温性能不能满足要求,在较高温度下催化剂的活性下降较快,甚至发生催化剂的涂层脱落,导致催化剂的活性完全丧失等,这些都严重影响了催化剂的使用效果。 But in the current three-way catalyst used in the process, there are still many problems, including sulfur resistant catalyst performance is not strong anti-lead, high temperature performance not meet the requirements, the catalyst activity decreased faster at higher temperatures, the catalyst occurs even the coating off, resulting in complete loss of activity of the catalyst, etc., which are seriously affecting the use of catalytic effect. 尽管人们也提出了很多的解决办法,但目前仍没有很好的解决,不得不从汽车使用的燃油方面加以高标准的要求,包括燃油中有毒物质硫铅等含量的严格控制,燃油中稀烃含量、芳烃含量、烷烃含量比例的严格控制等,一方面要满足催化剂的较高使用要求,另一方面又要最大限度地发挥催化剂的催化作用以使污染物排放降到最低。 Although people have made a lot of solutions, but there is still no good solution, high standards of fuel to be forced to use terms from the car, including strict control of fuel sulfur content of toxic substances such as lead, dilute hydrocarbon fuel content, aromatic content, naphthene content strictly proportional control, on the one hand to meet the high requirements of the catalyst, the other is to maximize the catalytic action of the catalyst to cause emissions to a minimum.

发明内容 SUMMARY

本发明的目的之一是通过调整催化剂制备的原材料并且改进催化剂的制备工艺等旨在一定程度上提高催化剂的各方面性能。 One object of the present invention to improve various aspects of performance of the catalyst material by adjusting the catalyst preparation and improve catalyst preparation process and the like are intended to some extent. 制备的催化剂从采用的原材料、制备工艺、贵金属的负载方法等多方面进行改进,使得催化剂在催化活性、耐高温性能、催化剂的空燃比操作窗口宽度、催化剂的低温起燃性能等方面得到了很大程度的改进。 The catalyst prepared from various raw materials to improve, manufacturing process, a method using a noble metal loading of the catalyst so obtained is in catalytic activity, high temperature performance, operating air-fuel ratio window width of the catalyst, a low temperature light-off performance of the catalyst improved large extent.

本发明制备的催化剂组成包括至少三种粒子分散在陶瓷基体上:负载有Pt族金属的热稳定或经过La、Ba稳定的氧化铝粒子;含Pt族金属起催化作用或不含Pt族金属起助剂作用的金属氧化物粒子,包括稀土复合氧化物,如Ce-Zr,或在其中加入La、Y、Nu、Pr、Ba等一种或两种以上形成的固熔体或复合氧化物材料;热稳定的惰性填充材料的粒子,包括高温非常稳定的α-氧化铝、钙钛矿、氧化钙、氧化钡、堇青石、莫来石、钛酸铝镁等。 The catalyst composition prepared by the present invention comprises at least three ceramic particles dispersed in the matrix: Pt loaded with thermally stable metal or through La, Ba stabilized alumina particles; Pt-containing or metal-free catalytic metal from Pt auxiliaries metal oxide particles, comprising a rare earth complex oxide, such as Ce-Zr, or added thereto La, Y, Nu, Pr, Ba, etc. One or a solid solution or a composite oxide of two or more materials formed ; particles of an inert thermally stable filler material comprises a high temperature very stable α- alumina, perovskite, calcium oxide, barium oxide, cordierite, mullite, aluminum magnesium titanate. 上述多种成分的成分混合及其结构复合,可以提供非常好的催化剂涂层材料,该材料既具有很好的耐高温性能,又能够与陶瓷蜂窝载体结合非常牢固,并且还能够在使用较低的贵金属量的同时,还达到很好的催化活性。 Above ingredients are mixed and a composite structure of a plurality of components, can provide very good catalyst coating material which has both a good high temperature performance, and capable of binding to a ceramic honeycomb carrier is very strong, and can also use a lower the amount of noble metal, it is also to achieve good catalytic activity.

本发明提供一种新的方法,即干混预研磨的方法,可以使得催化剂的各个组成部分能够达到很好的匹配,包括堇青石陶瓷蜂窝、氧化铝载体、稀土复合氧化物、各种添加剂等。 The present invention provides a new method, i.e., a pre-blended dry grinding method, such that the individual components of the catalyst can achieve a good match, comprising a cordierite ceramic honeycomb, an alumina carrier, rare earth complex oxide, various additives . 干态混合机械研磨是粉体加工的新技术,不仅可以改变粒子粒度减小,而且可以改善粒子特别是混合粒子的表面活性。 Hybrid mechanical polishing technology is a new dry powder processing, not only can change the particle size reduction, and can improve the surface active particles particularly mixing particles. 通过该方法,可以保证贵金属在载体表面的高度分散,为催化剂具有很好的催化表面活性创造了条件。 By this method, it is possible to ensure a highly dispersed noble metal surface of the carrier, the catalyst having good catalytic activity of the surface to create the conditions. 同时通过使用改进的氧化铝材料、稀土复合氧化物材料等,研磨后不仅使得催化剂的活性组分高度分散,而且由于粒度的减小和粒度的均匀而使耐高温性能得到提高,即使在1000℃以上的高温下,催化剂的活性组分都不会烧结。 By simultaneously using modified alumina material, rare earth complex oxide material and the like, such that only after grinding the active component of the catalyst is highly dispersed, and because a uniform particle size and reduce the size of the high temperature performance is improved, even at 1000 ℃ at temperatures above the active component of the catalyst are not sintered. 另外,本方法在催化剂制备过程中之还选择了一定量的惰性材料包括堇青石、莫来石、α-氧化铝等,关键就在于这些耐高温惰性材料,能够增加催化剂涂层与陶瓷蜂窝的结合强度。 Further, this method of catalyst preparation also during a selected quantity of inert materials include cordierite, mullite, alpha] alumina or the like, the key is that these high-temperature inert materials, can be increased and the coating of the ceramic honeycomb catalyst Bond strength.

已知有很多的催化剂制备方法,它们一般分为两种制备过程:在陶瓷蜂窝上预涂附高比表面的活性氧化铝涂层或含有氧化铝、稀土氧化物、其它添加物等组成的混合氧化物涂层,通过一定的热处理后再将贵金属活性组分负载到前述的含有高比表面涂层的陶瓷蜂窝载体上,再经过一定的热处理,或还原处理后制备成催化剂;另外一种制备过程是在陶瓷蜂窝上预涂附高比表面的活性氧化铝涂层或含有氧化铝、稀土氧化物、其它添加物等组成的混合氧化物涂层,通过一定的热处理后,再将含有贵金属活性组分的混合氧化物浆料涂附到前述的含有高比表面涂层的陶瓷蜂窝载体上,再经过一定的热处理,或还原处理后制备成催化剂。 There are many known catalyst preparation methods, which are generally divided into two kinds of preparation process: on a ceramic honeycomb attachment precoated active alumina coating layer containing a high specific surface or consisting of a mixture of alumina, rare earth oxides, other additives, etc. oxide coating, by heat treatment after certain noble metal active component supported on a carrier comprising a ceramic honeycomb washcoat aforementioned, then after a certain heat treatment, or after the reduction treatment to prepare a catalyst; another preparation process is pre-coated on the ceramic honeycomb attachment high specific surface activated alumina coating layer containing aluminum oxide or rare earth oxide, a mixed oxide coating composed of other additives and the like, by a certain heat treatment, and then the noble metal-containing active mixed oxides component slurry was coated onto a ceramic honeycomb carrier containing washcoat aforementioned, then after a certain heat treatment, or treating the reduced catalyst was prepared. 上述涂附过程可根据贵金属含量进行一次或多次。 The above-described process may be coated according to one or more precious metal content.

本发明与上述的催化剂制备过程有所不同,主要区别在于采用了经过模板法制备的现有的稀土基复合氧化物材料,高耐热性能的特种氧化铝载体,并经过干混预研磨特殊工艺过程制备催化剂的涂附用浆料。 The present invention relates to the above-described catalyst preparation process is different, the main difference is the use of a conventional rare earth-based composite oxide material is prepared through the template, the high heat resistance of specialty alumina carrier, and dry blending the pre-ground through a special process preparation of the catalyst coated with a slurry process. 该催化剂的涂附过程可一次或多次完成。 Coated process the catalyst may be one or more times to complete.

本发明为一种稀土基高性能三效催化剂的制备方法,其特征在于其一次涂附过程包括如下制备工艺过程:1.原料的选择:1) 选择合适的活性氧化铝载体,比表面一般为120~300m2/g,孔容大于0.3cm3/g,平均孔径为100以上,粒度为D90在25μm以下。 The present invention is a method for preparing a rare earth-based high-performance three-way catalyst, characterized in that it comprises a process for the preparation of coated following process: a choice of raw materials: 1) Select the appropriate activated alumina support, a specific surface generally 120 ~ 300m2 / g, a pore volume greater than 0.3cm3 / g, an average pore diameter 100 above, the D90 particle size of 25μm or less.

2) 选择合适的稀土基复合氧化物,比表面一般在65~150m2/g,孔容大于0.2cm3/g,平均孔径为110以上,粒度为D90在40μm以下。 2) Select the appropriate rare earth-based composite oxide, the specific surface area is generally 65 ~ 150m2 / g, a pore volume greater than 0.2cm3 / g, an average pore diameter 110 above, the D90 particle size of 40μm or less. 该稀土基复合氧化物中所含的铈和锆的量基本上对应于获得最终目的复合物所需的化学计量比,本发明中使用的铈/锆的原子比可以在1/9至9/1的范围内变化。 The amount of cerium and zirconium contained in the rare earth-based composite oxide substantially corresponding to obtain the desired final composite object stoichiometry, the atomic ratio of cerium in the present invention / zirconium may be in the 1/9 to 9 / varied in the range of 1. 同时,也添加了一定量的钇、镧、镨、钕中的一种或多种,含量在1%~15%范围之内。 At the same time, also add a certain amount or more of yttrium, lanthanum, praseodymium, neodymium, the content is in the range 1% to 15%.

3) 选择合适的贵金属盐溶液,包括硝酸铂、氯铂酸、六羟基铂酸、氯铂酸铵等的酸性或碱性溶液;硝酸铑、氯化铑溶液、氯铑酸盐;硝酸钯、氯化钯、氯钯酸等。 3) Select the appropriate noble metal salt solution, including platinum nitrate, chloroplatinic acid, hexahydroxoplatinic acid, ammonium chloroplatinate such as acidic or basic solution; rhodium nitrate, rhodium chloride solution, a rhodium chloride salt; palladium nitrate, palladium chloride, palladium chloride acid and the like.

4) 碳酸钡、氧化钡、乙酸钡、氢氧化钡、硫酸钡;碳酸钙、氧化钙、硫酸钙;硝酸氧锆、碳酸氧锆、氢氧化锆、乙酸氧锆、氯氧化锆;碳酸铈、硝酸铈;碳酸锶、硝酸锶;碳酸镁、硝酸镁;硝酸镧、碳酸镧;硝酸钇、碳酸钇等碱金属、碱土金属、稀土金属等盐类或氧化物。 4) barium carbonate, barium oxide, barium acetate, barium hydroxide, barium sulfate; calcium carbonate, calcium oxide, calcium sulfate; zirconyl nitrate, zirconyl carbonate, zirconium hydroxide, zirconyl acetate, zirconium oxychloride; cerium carbonate, cerium nitrate; strontium carbonate, strontium nitrate; magnesium carbonate, magnesium nitrate; lanthanum nitrate, lanthanum carbonate; yttrium nitrate, yttrium carbonate, alkali metals, alkaline earth metals, rare earth metal oxides or salts.

5) 惰性材料如α-氧化铝、钙钛矿、氧化钙、氧化钡、堇青石、莫来石、钛酸铝镁等。 5) α- inert materials such as alumina, perovskite, calcium oxide, barium oxide, cordierite, mullite, aluminum magnesium titanate. 上述粉末的比表面积一般在1~4m2/g之间,粉末的粒度在50μm以下。 Specific surface area of ​​the powder is generally between 1 ~ 4m2 / g, a particle size in the powder is 50μm or less.

6) 使用的酸性物质包括硝酸、醋酸等。 6) acidic substance used include nitric acid, acetic acid and the like. 上述酸性物质的杂质含量在1%以下。 Impurity content of the acidic substance is 1% or less.

7) 使用的碱性物质包括氨水、尿素、氢氧化钾等。 7) the basic substance include ammonia, urea, potassium hydroxide and the like. 上述碱性物质的杂质总含量不超过1%。 The total content of impurities of the alkaline substance is less than 1%.

8) 选择合适的堇青石陶瓷蜂窝基体,孔密度为300~600孔/平方英寸,正方形孔道。 8) Select the appropriate cordierite ceramic honeycomb substrate, a cell density of 300 to 600 cells / square inch, square tunnel. 该陶瓷蜂窝可以是国产的也可以是康宁公司的产品。 The ceramic honeycomb may be made in China can also be Corning's products. 一般的孔道密度是400孔/平方英寸,壁厚大约在0.1~0.22mm范围内,典型的国产陶瓷蜂窝的壁厚为0.16mm,康宁陶瓷蜂窝的壁厚为0.12mm。 Usually the cell density is 400 cells / square inch, a wall thickness in the range of about 0.1 ~ 0.22mm, the wall thickness of a typical ceramic honeycomb is made 0.16mm, the wall thickness of the ceramic honeycomb Corning 0.12mm.

9) 本发明制备的催化剂,含有的各种成分及含量为,活性氧化铝载体的含量为20~150克/升,稀土复合氧化物助剂的使用量一般为15~200克/升,各种填充材料如堇青石、莫来石、α-氧化铝等惰性粉末为10~100克/升,贵金属的含量一般为0.2~2克/升,Pt、Pd、Rh三种贵金属的比例一般控制在Pt/Rh=15∶1至2∶1,Pd/Rh=10∶1至2∶1,Pt/Pd/Rh=10∶0∶1至0∶10∶1。 9) The catalyst prepared in the present invention, and the contents of various components is contained, the content of active alumina support is 20 to 150 g / l, the amount of rare earth complex oxide additives is generally 15 to 200 g / liter, each ratio kinds of fillers such as cordierite, mullite, alpha] alumina or the like inert powder 10 to 100 g / l, the noble metal content is generally 0.2 to 2 g / l, Pt, Pd, Rh noble metals is generally controlled in the Pt / Rh = 15:1 to 2:1, Pd / Rh = 10:1 to 2:1, Pt / Pd / Rh = 10:0:1 to 0:10:1. 以La-Ba稳定氧化铝或稳定催化剂,其含量一般为氧化铝或催化剂涂层的0~5%。 In La-Ba stabilized alumina catalyst or stabilizer, the content thereof is generally 0 to 5% alumina or catalyst coating.

2.研磨及制备浆液:10) 将上述γ-氧化铝单独或混同稀上复合氧化物以及少量的碱金属、碱土金属等混合均匀后进行研磨至一定的粒度,一般为D90在3~15μm的范围之内。 2. Preparation of the slurry and polishing: 10) alone or the above-mentioned γ- alumina confused dilute the milled after mixing the composite oxide and a small amount of an alkali metal, alkaline earth metal or the like to a certain uniform particle size, typically a D90 of 3 ~ 15μm within range.

11) 将贵金属的单独或混合溶液浸渍在上述研磨后的粉末上,然后加入一定量的氨水或乙酸溶液,再进行混合研磨1~5小时,优选2~4小时,形成湿润性粉末混合物。 11) alone or in admixture of noble metal impregnation solution on the powder after the grinding, and then adding an amount of aqueous ammonia or acetic acid solution, and then mixed and ground for 1 to 5 hours, preferably 2 to 4 hours to form a wet powder mixture.

12) 将上述粉末在120~180℃温度下干燥1~5小时,400~600℃下煅烧1~5小时,优选2~3小时。 12) The above powder was dried for 1 to 5 hours at a temperature of 120 ~ 180 ℃, 1 to 5 hours, calcined at 400 ~ 600 ℃, preferably 2 to 3 hours.

13) 将湿润性粉末混合物或煅烧后的粉末,与适量的α-氧化铝、钙钛矿、氧化钙、氧化钡、堇青石、莫来石、钛酸铝镁等惰性物质的单独或混合物等充分混合。 Alone or in a mixture of 13) of the wet powder after firing or the powder mixture with a suitable amount of α- alumina, perovskite, calcium oxide, barium oxide, cordierite, mullite, aluminum magnesium titanate and other inerts mix well.

14) 在上述混合物中加入合适量的去离子水、乙酸、硝酸、适量的氨水等制成可流动的浆液。 14) adding a suitable amount of deionized water slurry made flowable, acetic acid, nitric acid, ammonia water and the like in a suitable amount of the above mixture.

15) 将上述浆液转移到数升大小的球磨罐中,加入适量的酸液或碱液调整浆液的pH值在2~5范围之内,加入少量的消泡剂,然后在球磨罐中进行球磨,时间在4~24小时,直至浆液的粒子粒度D90在10μm以下。 15) The slurry was transferred to a ball mill pot liters in size, to adjust the pH of the slurry was added an appropriate amount of acid or lye in a range of 2 to 5, a small amount of defoamer was added, followed by milling in a ball mill jar , at about 4 to 24 hours, until the slurry particles of 10μm or less in particle size D90.

16) 取出研磨后的浆液,加入酸、碱或去离子水等液态物质至固含量达到20%~45%。 16) the polishing slurry was taken out, the liquid substance was added to the solids content of the acid, base or deionized water, 20% to 45%.

3.涂附及煅烧活化: 3. Coated and calcinated:

17) 以陶瓷蜂窝基体或含有预涂层的陶瓷蜂窝基体浸入到上述浆液之中,10~40秒后取出,用压缩空气吹扫,放入干燥箱中100~250℃干燥5~20个小时,至脱水率达到75%以上。 17) to a ceramic honeycomb substrate or a ceramic honeycomb matrix comprising a precoat dipped into the slurry, taken after 10 to 40 sec, purged with compressed air, placed in a drying oven 100 ~ 250 ℃ 5 to 20 hours to dehydration rate of more than 75%. 干燥在空气下或惰性气氛下进行。 Drying under air or under an inert atmosphere.

18) 初步脱水后的催化剂毛坯放入马福炉中进行高温煅烧。 18) the catalyst after preliminary dewatering blank placed in a muffle furnace for high temperature calcination. 煅烧温度400~650℃,时间30分钟~5小时。 Calcination temperature 400 ~ 650 ℃, 30 minutes to 5 hours. 煅烧是在空气下或惰性气氛下进行。 Calcining is conducted in air or an inert atmosphere.

19) 煅烧之后,根据催化剂的本身需要和应用需要,在高温下对催化剂进行还原活化。 19) After calcination, the need and application needs, reducing the catalyst at a high temperature activation of the catalyst according to their own. 还原是在氢气气氛中或还原气氛下进行。 Reduction is carried out in a hydrogen atmosphere or in a reducing atmosphere.

本发明制备的稀土基三效催化剂,在制备过程中,可以根据需要,在陶瓷蜂窝基体上预涂附一种活性氧化铝载体,或直接进行催化剂涂层的涂附。 Preparing rare earth-based three-way catalyst of the present invention, during preparation, as needed, on a ceramic honeycomb substrate precoated attaching an activated alumina support, or directly coated catalyst coating. 但预涂附的活性氧化铝涂层必须添加氧化铝溶胶等物质使涂层结合的非常牢固。 But attachment precoated active alumina coating must be added to the coating material such as alumina sol bound very strong.

除了进行单层的涂附之外,可以依据实际应用的需要进行双层或多层的涂附。 In addition to a single layer coated, two or more layers may be coated according to the needs of practical application. 除了进行单层的涂附之外,可以依据实际应用的需要进行双层或多层的涂附。 In addition to a single layer coated, two or more layers may be coated according to the needs of practical application. 这种涂附过程可以是第一次涂附的简单重复,也可以是与第一次涂附有很大的不同。 This coated process can be a simple repetition of the first coated, may be coated with the first time with very different.

本发明作为一种稀土基高性能三效催化剂的制备方法,其另一特征在于其多层涂附过程包括如下制备工艺过程:1)第一层的浆液中含有至少一种的惰性材料包括α-氧化铝、钙钛矿、堇青石、莫来石、钛酸铝镁等,贵金属主要为Rh、Pd的单独或混合盐溶液,单独或共同负载到活性氧化铝载体上,该浆液涂附在陶瓷蜂窝载体上,经过压缩空气吹扫之后,烘箱中100~250℃干燥5~20个小时。 As the present invention is a method of preparing rare earth-based high-performance three-way catalyst, which is further characterized in that the process comprises the preparation of a multilayer coated process is as follows: a slurry of at least one inert material 1) comprises a first layer comprising α - alumina, perovskite, cordierite, mullite, aluminum magnesium titanate, mainly noble metal alone or mixed salt solution Rh, Pd, and loaded individually or jointly, the active alumina support, the slurry was coated to ceramic honeycomb carrier, after blowing compressed air, an oven dried 100 ~ 250 ℃ 5 ~ 20 hours.

2)第二层浆液可以含有Pt、Pd以及Rh的单独成分或混合成分,这些成分按照一定比例配制,分别或共同负载到活性氧化铝载体或稀土复合氧化物上。 2) a second layer slurry may contain Pt, Pd and Rh alone component or mixture of components, these components formulated in a certain proportion, respectively, to the common load or active rare earth complex oxide or alumina support. 该浆液不含有任何上述惰性材料。 The slurry does not contain any of the above inert material.

3)将已经涂附第一层贵金属陶瓷蜂窝载体浸入上述的浆液中,10~30秒后,取出压缩空气吹扫除去多余浆液,放入干燥箱中100~250℃干燥5~20个小时,至脱水率达到75%以上。 3) The layer of noble metal has been first coated ceramic honeycomb carrier was immersed in the slurry described above, after 10 to 30 seconds, remove the compressed air to remove excess slurry was purged, 100 ~ 250 ℃ placed in a drying oven 5 to 20 hours. to dehydration rate of more than 75%. 干燥在空气下或惰性气氛下进行。 Drying under air or under an inert atmosphere.

4)将上述催化剂的毛坯放入马福炉中进行煅烧,煅烧温度400~650℃,时间3~5小时。 4) the blank discharge the catalyst was calcined in a muffle furnace, firing temperature 400 ~ 650 ℃, for 3 to 5 hours. 煅烧是在空气或惰性气氛下进行。 Calcining is conducted in air or an inert atmosphere.

5)上述制备的催化剂也可以进行还原活化。 5) The catalyst prepared above reductive activation may be performed.

作为本发明的优选技术方案,其进一步特征在于其一次涂附过程包括如下制备工艺过程:1.原料的选择:1)优选合适的稀土基复合氧化物,该稀土基复合氧化物中使用的铈/锆的原子比可以在8-3∶1的范围内变化。 As a preferred aspect of the present invention, which is further characterized in that a coated preparation process comprising the following process: a choice of raw materials: 1) is preferably a suitable rare earth-based composite oxide, cerium oxide, rare earth-based composite for use atomic ratio / zirconium may vary within the scope of 8-3:1. 同时,添加的钇、镧、镨、钕中的一种或多种,含量在1%~10%范围之内。 Meanwhile, the added yttrium, lanthanum, praseodymium, neodymium, one or more, the content in the range of 1% to 10%.

2)优选合适的贵金属盐溶液,包括硝酸铂、氯铂酸等的酸性或碱性溶液;硝酸铑、氯化铑溶液;硝酸钯、氯化钯等。 2) a suitable noble metal salt solution preferably comprising platinum nitrate, chloroplatinic acid and the like acidic or basic solution; rhodium nitrate, rhodium chloride solution; palladium nitrate, palladium chloride and the like.

3)优选碳酸钡、氧化钡、乙酸钡;碳酸钙、氧化钙;硝酸氧锆、氢氧化锆、乙酸氧锆、氯氧化锆;硝酸铈;硝酸锶;硝酸镁;硝酸镧、碳酸镧;硝酸钇、碳酸钇等碱金属、碱土金属、稀土金属等盐类或氧化物。 3) preferably barium carbonate, barium oxide, barium acetate; calcium carbonate, calcium oxide; zirconyl nitrate, zirconium hydroxide, zirconyl acetate, zirconium oxychloride; cerium nitrate; strontium nitrate; magnesium nitrate; lanthanum nitrate, lanthanum carbonate; nitrate yttrium, yttrium carbonate, alkali metals, alkaline earth metals, rare earth metal oxides or salts.

4)本发明制备的催化剂,优选的各种成分及含量为,活性氧化铝载体的含量为20~120克/升,稀土复合氧化物助剂的使用量一般为15~150克/升,各种填充材料如堇青石、莫来石、α-氧化铝等惰性粉末为10~80克/升,贵金属的含量一般为0.2~1.5克/升,Pt、Pd、Rh三种贵金属的比例一般控制在Pt/Rh=10∶1至2∶1,Pd/Rh=8∶1至2∶1,Pt/Pd/Rh=8∶0∶1至0∶8∶1。 4) The catalyst prepared in the present invention, the preferred content of the various components and the content of active alumina support of 20 to 120 g / liter, the amount of rare earth complex oxide additives is generally 15 to 150 g / l, each kinds of fillers such as cordierite, mullite, alpha] inert alumina powder is 10 to 80 g / l, the noble metal content is generally 0.2 to 1.5 g / l, the proportion of Pt, Pd, Rh noble metals is generally controlled in the Pt / Rh = 10:1 to 2:1, Pd / Rh = 8:1 to 2:1, Pt / Pd / Rh = 8:0:1 to 0:8:1. 以La-Ba稳定氧化铝或稳定催化剂,其含量一般为氧化铝或催化剂涂层的0~3%。 In La-Ba stabilized alumina catalyst or stabilizer, the content thereof is generally 0 to 3% alumina or catalyst coating.

2.研磨及制备浆液:5)将贵金属的单独或混合溶液浸渍在上述研磨后的粉末上,然后加入一定量的氨水或乙酸溶液,再进行混合研磨优选为2~4小时,形成湿润性粉末混合物。 2. Preparation of the polishing slurry and: 5) mixed solution impregnating the noble metal alone or in the polishing powder, and then adding an amount of aqueous ammonia or acetic acid solution, and then mixed and ground preferably 2 to 4 hours to form a wet powder mixture.

6)将上述粉末在120~180℃温度下干燥1~5小时,优选的煅烧温度500~550℃,煅烧时间优选2~3小时。 6) The above powder was dried at a temperature of 120 ~ 180 ℃ 1 ~ 5 hours, and the calcination temperature is preferably 500 ~ 550 ℃, calcination time is preferably 2 to 3 hours.

3.涂附及煅烧活化:7)以陶瓷蜂窝基体或含有预涂层的陶瓷蜂窝基体浸入到上述浆液之中,10~40秒后取出,用压缩空气吹扫,放入干燥箱中100~250℃干燥5~12个小时。 3. Coated and calcinated: 7) to a ceramic honeycomb substrate or a ceramic honeycomb matrix comprising a precoat dipped into the slurry, taken after 10 to 40 sec, purged with compressed air, into the dry box 100 ~ 250 ℃ dried 5-12 hours.

8)初步脱水后的催化剂毛坯放入马福炉中进行高温煅烧。 8) the catalyst after preliminary dewatering blank placed in a muffle furnace for high temperature calcination. 煅烧温度500~550℃,时间30分钟~3小时。 Calcination temperature 500 ~ 550 ℃, 30 minutes to 3 hours.

具体实施方式 Detailed ways

实施例1--实施例5为一次涂附过程的实施例。 Example 5 was a coated according to the process of Example 1 - Fig.

实施例11000克γ-氧化铝粉末,比表面120平方米/克,700克(Ce/Zr=9∶1)稀土氧化物,比表面为65平方米/克,适量氧化钡、氧化锆、氧化铈等混合在一起,经球磨至一定的粒度范围后,再与20克Pd的氯化钯溶液,含有2克Rh的氯化铑溶液,适量碱液,进行混合研磨2小时,充分均匀后150℃干燥2小时,400℃空气下煅烧2小时。 Example 11000 g γ- alumina powder embodiments, specific surface 120 m2 / g, 700 g (Ce / Zr = 9:1) rare earth oxide, a specific surface area of ​​65 m2 / g, amount of barium oxide, zirconium oxide, cerium mixed together by ball milling to a particle size range, the palladium chloride solution and then with 20 g of Pd, rhodium chloride solution containing 2 g of Rh, an appropriate amount of alkali, and mixed ground for 2 hours, 150 sufficiently uniform ℃ dried for 2 hours and air calcined for 2 hours at 400 ℃. 将上述粉末与500克上述γ-氧化铝粉末、350克(Ce/Zr=1∶9)稀土氧化物、适量醋酸、适量去离子水、100克α-氧化铝粉末、50克堇青石粉末、50克氧化铝溶胶等混合进行球磨成浆液,然后用400单元的堇青石蜂窝基体浸入涂浆中,取出,用压缩空气吹扫过量涂浆,干燥去掉游离水,500℃煅烧150分钟。 The above powder with 500g of γ- alumina powder, 350 g (Ce / Zr = 1:9) a rare earth oxide, an appropriate amount of acetic acid, an appropriate amount of deionized water, 100 grams of α- alumina powder, 50 grams of cordierite powder, mixing 50 g of alumina sol or the like ball-milled slurry was then treated with 400 units cordierite honeycomb substrate is immersed in the coating slurry, removed with compressed air purging excess coating slurry, drying to remove free water and calcined 500 ℃ 150 min. 制备的催化剂含贵金属量为1.4克/升,钯/铑比为10∶1。 Amount of noble metal-containing catalyst prepared in 1.4 g / L, Pd / Rh ratio of 10.

实施例2800克γ-氧化铝粉末,比表面230平方米/克,560克(Ce/Zr/La=8∶1∶1)稀土氧化物,比表面为85平方米/克,适量碳酸钡、氢氧化锆、氧化钙等混合在一起,经球磨至一定的粒度范围后,再与18克Pt的氯铂酸溶液,含有1.2克Rh的氯铑酸铵溶液,进行混合研磨4小时,充分均匀后100℃干燥5小时,600℃空气下煅烧1小时。 Example 2800 g of alumina powder γ- embodiment, surface area 230 m2 / g, 560 g (Ce / Zr / La = 8:1:1) rare earth oxide, a specific surface area of ​​85 m2 / g, an appropriate amount of barium carbonate, zirconium hydroxide, calcium oxide were mixed together by ball milling to a particle size range after, and then 18 g of Pt solution of chloroplatinic acid, rhodium chloride ammonium solution containing 1.2 g of Rh, milled and mixed for 4 hours and sufficiently uniformly after 100 ℃ dried for 5 hours, calcined in air 600 ℃ 1 hour. 将上述粉末与400克上述γ-氧化铝粉末、280克上述Ce/Zr/La稀土氧化物、适量醋酸、适量去离子水、100克α-氧化铝粉末、50克堇青石粉末、50克氧化铝溶胶等混合进行球磨成浆液,然后用400单元的堇青石蜂窝基体浸入涂浆中,取出,用压缩空气吹扫过量涂浆,干燥去掉游离水,600℃煅烧60分钟。 The above powder and the above-mentioned γ- alumina powder 400 g 280 g of the Ce / Zr / La rare earth oxide, an appropriate amount of acetic acid, an appropriate amount of deionized water, 100 grams of α- alumina powder, cordierite powder 50 grams, 50 grams of oxide mixing alumina sol or the like ball-milled slurry was then treated with 400 units cordierite honeycomb substrate is immersed in the coating slurry, removed with compressed air purging excess coating slurry, drying to remove free water and calcined 600 ℃ 60 minutes. 制备的催化剂含贵金属量为0.5克/升,铂/铑比为15∶1。 Noble metal-containing catalyst prepared in an amount of 0.5 g / liter Pt / Rh ratio 15:1.

实施例31500克以3%铈、镧、2%钡改性的γ-氧化铝粉末,比表面180平方米/克,700克(Ce/Zr=1∶9)稀土氧化物,比表面为110平方米/克,适量氢氧化钡、碳酸锆、氧化镧等混合在一起,与含有10克Pd的硝酸钯溶液,含有5克Rh的硝酸铑溶液进行混合研磨约4小时后形成湿润性粉末,250℃干燥1小时,600℃空气下煅烧2小时。 31500 g at 3% of cerium, lanthanum, barium modified γ- 2% alumina powder, surface area 180 m2 / g, 700 g (Ce / Zr = 1:9) Example rare earth oxide, a specific surface of 110 m / g, an appropriate amount of barium hydroxide, zirconium carbonate, lanthanum oxide are mixed together, with a palladium nitrate solution containing 10 g of Pd, and rhodium nitrate solution containing 5 g of Rh were mixed and ground for about 4 hours after the formation of a wet powder, dried 250 ℃ 1 hour air calcination at 600 ℃ 2 hours. 将上述粉末与100克上述α-氧化铝粉末、350克上述Ce/Zr稀土氧化物、适量醋酸、适量去离子水、50克堇青石粉末、50克氧化铝溶胶等混合进行球磨成浆液,然后用400单元的堇青石蜂窝基体浸入涂浆中,取出,用压缩空气吹扫过量涂浆,干燥去掉游离水,400℃煅烧3小时。 The mixed powder was mixed with 100 g of the above-mentioned α- alumina powder 350 g of Ce / Zr rare earth oxide, an appropriate amount of acetic acid, an appropriate amount of deionized water, 50 grams of cordierite powder, 50 g alumina sol or the like ball-milled slurry was then cordierite honeycomb substrate with 400 cell was immersed in the coating slurry, removed with compressed air purging excess coating slurry, drying to remove free water, 400 deg.] C for 3 hrs. 制备的催化剂含贵金属量为2.4克/升,钯/铑比为2∶1。 Amount of noble metal-containing catalyst prepared in 2.4 g / L, Pd / Rh ratio of 2.

实施例41500克以3%镧、2%钡改性的γ-氧化铝粉末,比表面135平方米/克,500克(Ce/Zr/Y=3∶1∶1)稀土氧化物,比表面为96平方米/克,适量乙酸钡、乙酸锆、氧化铈等混合在一起,与含有10克Pt的硝酸铂溶液,含有5克Rh的硝酸铑溶液及适量的碱液进行混合研磨至一定粒度后形成湿润性粉末(D90小于15微米),将上述粉末与30克上述α-氧化铝粉末、150克上述Ce/Zr/La(Ce/Zr/La=8∶1∶1)稀土氧化物、适量醋酸、适量去离子水、50克堇青石粉末、50克氧化铝溶胶等混合进行球磨成浆液,然后用400单元的堇青石蜂窝基体浸入涂浆中,取出,用压缩空气吹扫过量涂浆,干燥去掉游离水,550℃煅烧30分钟。 3% Example 41,500 grams of lanthanum, barium 2% modified embodiment of γ- alumina powder, surface area 135 m2 / g, 500 g (Ce / Zr / Y = 3:1:1) a rare earth oxide, specific surface nitric acid mixed 96 m2 / g, an appropriate amount of barium acetate, zirconium acetate, and cerium oxide together, with platinum nitrate solution containing 10 g of Pt, and rhodium Rh containing 5 grams of the solution were mixed and the amount of lye ground to a certain size after forming the wet powder (D90 less than 15 microns), the above powder with 30 g alumina powder α- above 150 g of the Ce / Zr / La (Ce / Zr / La = 8:1:1) a rare earth oxide, mixing an appropriate amount of acetic acid, an appropriate amount of deionized water, 50 grams of cordierite powder, 50 g alumina sol or the like ball-milled slurry was then treated with 400 units cordierite honeycomb substrate is immersed in the coating slurry, removed, an excess of blowing compressed air pasted , dried to remove free water and calcined 550 ℃ 30 minutes. 制备的催化剂含贵金属量为0.65克/升,铂/铑比为2∶1。 Amount of noble metal-containing catalyst prepared was 0.65 g / L, Pt / Rh ratio of 2.

实施例51000克1%氧化钡稳定γ-氧化铝粉末,比表面160平方米/克,浸渍到含有15克Pt的H2Pt(OH)6氨水溶液中,500克3%镧稳定的γ-氧化铝粉末,比表面积为135平方米/克,浸渍到含3克Rh的硝酸铑溶液中,500克1%氧化钡稳定的γ-氧化铝粉末,比表面积为160平方米/克,浸渍到含3克Pd的氯化钯的溶液中,上述粉末与乙酸钡、氢氧化锆、氧化铈等混合在一起,进行球磨3小时至粒度D90小于15微米,再加100克α-氧化铝粉末、20克堇青石粉末、30克氧化铝溶胶、1000克稀土复合氧化物(60%La203,10%CeO2,22%Nd2O3,8%Pr6O11)和水及乙酸等球磨成浆液,400单元的堇青石蜂窝基体浸入涂浆中,取出,用压缩空气吹扫过量涂浆,干燥去掉游离水,500℃煅烧30分钟。 1% Example 51,000 grams of barium oxide stabilized alumina powder γ- embodiment, surface area 160 m2 / g, immersed H2Pt (OH) 6, Pt containing 15 g of aqueous ammonia solution, 500 g of 3% lanthanum stabilized alumina γ- powder, the specific surface area of ​​135 m2 / g, to a solution of 3 g of Rh impregnating rhodium nitrate solution and 500 grams of 1% of barium oxide stabilized γ- alumina powder, a specific surface area of ​​160 m2 / g, is impregnated with 3 to g of palladium Pd chloride solution, and mixing the powder of barium acetate, zirconium hydroxide, cerium oxide together, ball milled for three hours to a particle size D90 less than 15 microns, α- plus 100 g alumina powder, 20 g cordierite powder, 30 g of alumina sol, rare earth complex oxide 1000 g (60% La203,10% CeO2,22% Nd2O3,8% Pr6O11), and acetic acid, and water slurry was ball-milled, cordierite honeycomb substrate is immersed in 400 cells coating the slurry, removed, blowing compressed air excess coating slurry, dried to remove free water and calcined 30 minutes 500 ℃. 制备的催化剂含贵金属量为0.9克/升,铂/铑/钯比为5∶1∶1。 Amount of noble metal-containing catalyst prepared in 0.9 g / l, platinum / rhodium / palladium ratio 5:1:1.

实施例6本例作为多层涂附工艺过程的实施例。 EXAMPLE 6 This Example embodiments of a multilayer coated according to the process.

第一层浆液:1260克γ-氧化铝粉末,比表面130平方米/克,浸渍含有15克Pd的氯化钯溶液,再浸渍含有2.5克Rh的氯化铑溶液,与850克Ce/Zr/La(Ce/Zr/La=8∶1∶1)稀土氧化物,比表面为75平方米/克,适量氧化钡、氧化锆、α-氧化铝粉末、适量醋酸、适量去离子水、堇青石粉末、氧化铝溶胶等混合进行球磨成浆液。 The slurry of the first layer: 1260 g γ- alumina powder, surface area 130 m2 / g, was impregnated with 15 g of palladium chloride, Pd, and then impregnated with a rhodium chloride solution 2.5 g of Rh, and 850 g Ce / Zr / La (Ce / Zr / La = 8:1:1) rare earth oxide, a specific surface area of ​​75 m2 / g, amount of barium oxide, zirconium oxide, alpha] alumina powder, an appropriate amount of acetic acid, an appropriate amount of deionized water, Viola bluestone mixed powder, an alumina sol or the like ball-milled slurry.

第二层浆液:1000克以3~5%铈、镧、2%钡改性的γ-氧化铝粉末,比表面130平方米/克,与含有10克Pt的硝酸铂溶液,含有2.5克Rh的硝酸铑溶液,进行混合研磨形成充分分散的湿润性粉末,再与Ce/Zr/La/Y稀土氧化物(比表面为72平方米/克)适量醋酸、去离子水等混合进行球磨成浆液。 The second layer slurry: 1000 grams of 3 to 5% of cerium, lanthanum, barium modified γ- 2% alumina powder, surface area 130 m2 / g, and a platinum nitrate solution containing 10 g of Pt, and containing 2.5 g of Rh the rhodium nitrate solution, mixed wet ground to form well-dispersed powder, and then the ball Ce / Zr / La / Y rare earth oxide (specific surface area 72 m2 / g) amount of acetic acid, deionized water, mixing ground slurry .

然后用400单元的堇青石蜂窝基体浸入第一层浆液中,压缩空气吹扫过量涂浆,干燥去掉游离水,500℃煅烧30分钟。 Then treated with 400 units cordierite honeycomb substrate is immersed in a first slurry layer, coating the compressed air purging excess slurry, drying to remove free water and calcined 500 ℃ 30 minutes. 再浸入第二层浆液中,压缩空气吹扫过量涂浆,干燥去掉游离水,500℃煅烧60分钟。 The second layer is then immersed in the slurry, blowing compressed air excess coating slurry, drying to remove free water and calcined 60 minutes 500 ℃. 制备的催化剂含贵金属量为20克/立方英尺,钯//铂铑比为3∶2∶1。 Amount of noble metal-containing catalyst prepared 20 g / ft, palladium, platinum and rhodium ratio 3:2:1 //.

比较例1先将氧化铝和氧化铈混合物的涂浆液浸到蜂窝载体上,然后再将活性组分负载到有涂层的蜂窝载体上。 Comparative Example 1 The slurry coated first mixture of alumina and cerium oxide on the honeycomb carrier is immersed, and then loaded with an active component to the coated honeycomb carrier. 球磨由1000g氧化铝(90wt%)和氧化铈(10wt%)的混合物粉末(比表面积为110m2/g),75mlHNO3和965mlH2O组成的混合液,浆液经过16.5小时的研磨后稀释,将横截面上每平方英寸有264个孔道的堇青石蜂窝载体浸入此浆液中,直至蜂窝载体中涂层的含量达到1.42g/in3。 1000g of milled alumina (90wt%) and cerium oxide (10wt%) mixture powder (specific surface area 110m2 / g), 75mlHNO3 composition and 965mlH2O mixture was milled slurry was 16.5 hours after dilution, each of the cross-section channels 264 square inch cordierite honeycomb carrier was immersed in this slurry, a honeycomb carrier until the content of the coating reached 1.42g / in3. 将此有涂层的蜂窝载体浸入由H2PtCl6和Na2PdCl6组成的溶液中(含0.337%Pt和0.142%Pd),一定时间后将载体取出,用压缩空气吹走多余液体。 This honeycomb carrier was immersed in a coating solution consisting of H2PtCl6 and consisting of Na2PdCl6 (containing 0.337% Pt and 0.142% Pd), remove the carrier after a certain time, the excess fluid blown off with compressed air. 通入H2S15分钟,用去离子水洗涤,120℃干燥,500℃锻烧,制备的催化剂含0.91g.Pt/升和0.488g.Pd升。 Into H2S15 minutes, washed with deionized water, dried 120 deg.] C, 500 deg.] C calcined catalyst prepared containing 0.91g.Pt/ 0.488g.Pd liters and liters.

比较例21000g氧化铝粉末(含95%氧化铝和5%的氧化铈),浸渍在含有383gNi(CHO2)2·2H2O的氨的溶液中。 Comparative Example 21000g alumina powder (containing 95% alumina and 5% of cerium oxide), was immersed in a solution containing ammonia 383gNi (CHO2) 2 · 2H2O in the. 粉末在炉中200℃烘干,650℃烧2小时。 Powder is dried in an oven 200 ℃, burning 650 ℃ 2 hours. 用含有11.5gPt的六羟基铂酸的碱式水溶液浸渍中,然后再浸渍在含有1.65gRh的Rh(NO3)3和120ml冰醋酸的水溶液中。 Impregnated with an aqueous solution of alkaline hexahydroxoplatinic acid containing 11.5gPt in, and then impregnated with an aqueous solution of 120ml of glacial acetic acid containing 3 1.65gRh of Rh (NO3) in. 得到的粉末和450mlH2O混合后球磨。 450mlH2O mixed powder obtained after milling. 球磨19小时后,将总比表面不超过1m2/g孔道密度为400孔的堇青石蜂窝载体浸入到上述浆液中,直至涂层达到122g/升,取出吹走多余浆液,干燥并在500℃烧。 After 19 hours milling, the surface is better than no more than 1m2 / g cell density of 400 cells cordierite honeycomb carrier is immersed in the slurry, until the coating reaches 122g / liter, the excess slurry was blown away removed, dried and fired at 500 ℃ . 最后得到的催化剂含有1.24g.Pt/升,0.177g.Rh/升,和18.31g.NiO/升。 The resulting catalyst contained 1.24g.Pt/ l, 0.177g.Rh / liter, and 18.31g.NiO / liter.

比较例3第一涂层制备:1750g比表面积为150m2/g的氧化铝载体(负载10%其它氧化物,比例为10CeO2∶88ZrO2∶2CaO),放置在球磨机中与含15.43gPt的H2Pt(OH)6单乙胺水溶液,混合20分钟,再加入2克冰乙酸,球磨至90%以上的粒径小于10μ。 The first coating preparation Comparative Example 3: 1750g specific surface area of ​​150m2 / g of alumina support (loading 10% other oxides, the proportion of 10CeO2:88ZrO2:2CaO), placed in a ball mill containing H2Pt (OH) 15.43gPt of 6 monoethylamine solution, mixing for 20 minutes, then 2 g of glacial acetic acid, 90% or more milling to a particle size of less than 10μ. 200克比表面积为100m2/g的氧化铈混合20分钟成一浆液,其固含量为44%。 200 g specific surface area of ​​100m2 / g ceria mixed for 20 minutes into a slurry having a solids content of 44%. 400单元的蜂窝基体浸入第一涂浆中,吹扫,110℃干燥过夜,500℃煅烧1小时,至负载量为109g/升。 Honeycomb substrate is immersed in a first coating unit 400 slurry, a purge, dried overnight at 110 deg.] C, 500 deg.] C was calcined for 1 hour to a loading of 109g / liter.

第二涂层制备:660克比表面积为150m2/g的氧化铝及660克去离子水在另一球磨机中混合5分钟,加入含4.65gPt的H2Pt(OH)6的单乙胺水溶液,混合20分钟。 The second coating was prepared: 660 grams 150m2 / g of alumina and 660 g of deionized water were mixed in a ball mill for another 5 minutes, an aqueous solution of monoethylamine were added 4.65gPt of H2Pt (OH) 6, the mixing specific surface area of ​​20 minute. 然后将10.22g硝酸钡晶体加入混合20分钟,再加入13克冰乙酸,球磨至90%以上粒径小于10μ。 Barium nitrate crystals is then added 10.22g mixed for 20 minutes, then add 13 g of glacial acetic acid, 90% or more milling to a particle size of less than 10μ.

800g含有12%氧化铈及88%氧化锆的复合氧化物,比表面为52m2/g,加入含有5.4gRh的硝酸铑溶液及含0.812gPd的硝酸钯溶液,两溶液的总量为140克,pH小于1.0,即在1.5小时内向共形成粉末中慢慢加入Rh-Pd溶液,再混合1.5小时。 800g containing 12% ceria and 88% zirconia composite oxide, a specific surface area of ​​52m2 / g, was added a solution containing rhodium nitrate and palladium nitrate solution 5.4gRh containing 0.812gPd total amount 140 g of the two solutions, pH less than 1.0, i.e., co-formed powder was slowly added a solution of Rh-Pd, and then mixed for 1.5 hours over 1.5 hours. 120℃干燥湿粉,空气中500℃煅烧。 120 ℃ wet powder was dried, calcined in air 500 ℃. 然后将该粉末与上述浆液,去离子水,冰醋酸等混合,球磨至90%以上粒径小于10μ。 The powder is then mixed with the slurry, deionized water, glacial acetic acid, 90% or milling to a particle size of less than 10μ.

将涂有第一涂层的蜂窝基体分别浸入第二涂浆中(固含量均为33%),100℃干燥,500℃煅烧,得到的贵金属含量为0.7g/升,上述催化剂分别进行老化前后的起燃温度评价。 Coated with a first coating layer of the second honeycomb substrates were immersed in the coating slurry (solids content of 33%), dried 100 ℃, 500 ℃ calcination, the noble metal content is obtained 0.7g / liter, respectively, before and after aging of the catalyst evaluation of light-off temperature. 数据见表1-本发明方法实施比较例老化前后的起燃温度评价数据表。 Data are shown in Table embodiment ignition temperature before and after aging of Comparative Example Data Sheet Evaluation Method 1 of the present invention.

评价条件为:φ25×50催化剂,空速50000h-1,标准混合气的组成为:O22.5%、H2O 10%、H20.4~0.8%、SO20.02%、HC(C3H6∶C3H8=2∶1)0.15%、CO 1.5%、NO 0.1%。 Evaluation conditions: φ25 × 50 catalyst composition, space velocity of 50000h-1, the standard gas mixture was: O22.5%, H2O 10%, H20.4 ~ 0.8%, SO20.02%, HC (C3H6:C3H8 = 2 :1) 0.15%, CO 1.5%, 0.1% NO.

老化条件为:1050℃下空气中煅烧50小时。 Aging conditions: 1050 ℃ calcined in air for 50 hours.

表1-本发明方法实施比较例老化前后的起燃温度评价数据表 Method 1 Table embodiment of the present invention the ignition temperature before and after aging of Comparative Example evaluation data table

从表中可以看出,本发明实施例1、2、3中新鲜催化剂对三种污染物的起燃温度与比较例中的起燃温度相当,但老化后对三种污染物的起燃温度要低于比较例催化剂的起燃温度,表明实施例的1、2、3的催化剂耐高温性能要好于比较例。 As can be seen from the table, light off temperature light-off temperature in Comparative Example 1, 2 of the three pollutants in the fresh catalyst in the embodiment of the present invention considerably, but the light-off temperature for the aging of the three pollutants Comparative Example lower than the ignition temperature of the catalyst, the catalyst showed high temperature performance of the embodiment is better than Comparative Examples 1, 2,. 而对实施例4、5、6,新鲜催化剂和老化之后的催化剂对三种污染物的起燃温度均要低于比较例,表明该实施例催化剂的活性和耐高温性能均要好于比较例催化剂。 While Examples 4 embodiment, fresh catalyst and catalyst light-off temperature after aging for three pollutants are lower than Comparative Example shows that the activity and heat resistance of the catalyst of this embodiment are better than Comparative Example Catalyst .

Claims (2)

1.一种稀土基三效催化剂的制备方法,其特征在于其一次涂附过程包括如下制备工艺过程:(1).原料的选择:1)选择活性氧化铝载体,比表面为120~300m2/g,孔容大于0.3cm3/g,平均孔径为100以上,粒度为D90在25μm以下;2)选择稀土基复合氧化物,比表面在65~150m2/g,孔容大于0.2cm3/g,平均孔径为110以上,粒度为D90在40μm以下,使用的铈/锆的原子比在1/9至9/1的范围内变化,同时,添加了钇、镧、镨、钕中的一种或多种,含量在1%~15%范围之内;3)选择贵金属盐溶液,包括硝酸铂、氯铂酸、六羟基铂酸、氯铂酸铵的酸性或碱性溶液;硝酸铑、氯化铑、氯铑酸盐;硝酸钯、氯化钯、氯钯酸;4)选择碱金属、碱土金属、稀土金属的盐或氧化物,所述碱金属、碱土金属、稀土金属的盐或氧化物是碳酸钡、氧化钡、乙酸钡、氢氧化钡、硫酸钡;碳酸钙、氧化钙、 1. A method for preparing a rare earth-based three-way catalyst, characterized in that it comprises a coated preparation procedure follows the process: (1) material selection: 1) Select the activated alumina support, a specific surface area of ​​120 ~ 300m2 / g, a pore volume greater than 0.3cm3 / g, an average pore diameter 100 above, in the D90 particle size of 25μm or less; 2) select the rare earth-based composite oxide in the surface area 65 ~ 150m2 / g, a pore volume greater than 0.2cm3 / g, 110 average pore diameter above D90 in the particle size of 40μm or less, and the cerium / zirconium atomic ratio varies in the range of 1/9 to 9/1, while the addition of yttrium, lanthanum, praseodymium, neodymium in or more, the content in the range of 1% to 15%; 3) select the noble metal salt solution, including platinum nitrate, chloroplatinic acid, hexahydroxoplatinic acid, ammonium chloroplatinate acidic or basic solution; rhodium nitrate, chloride rhodium, rhodium chloride salt; palladium nitrate, palladium chloride, palladium chloride acid; 4) selecting an alkali metal, alkaline earth metal, rare earth metal oxides or salts, the alkali metal, alkaline earth metal, a rare earth metal salt or oxide material is barium carbonate, barium oxide, barium acetate, barium hydroxide, barium sulfate; calcium carbonate, calcium oxide, 酸钙;硝酸氧锆、碳酸氧锆、氢氧化锆、乙酸氧锆、氯氧化锆;碳酸铈、硝酸铈;碳酸锶、硝酸锶;碳酸镁、硝酸镁;硝酸镧、碳酸镧;硝酸钇、碳酸钇;5)填充材料α-氧化铝、钙钛矿、氧化钙、氧化钡、堇青石、莫来石、钛酸铝镁,填充材料粉末的比表面积在1~4m2/g之间,填充材料粉末的粒度在50μm以下;6)使用的酸性物质包括硝酸、醋酸,上述酸性物质的杂质含量在1%以下;7)使用的碱性物质包括氨水、尿素、氢氧化钾,上述碱性物质的杂质总含量不超过1%;8)选择堇青石陶瓷蜂窝基体,孔密度为300~600孔/平方英寸,正方形孔道,壁厚在0.1~0.22mm范围内;9)制得的催化剂含有的各种成分及含量为,活性氧化铝载体的含量为20~150克/升,稀土基复合氧化物助剂的使用量为15~200克/升,填充材料为10~100克/升,贵金属的含量为0.2~2克/升,Pt、Pd、Rh Calcium; zirconyl nitrate, zirconyl carbonate, zirconium hydroxide, zirconyl acetate, zirconium oxychloride; cerium carbonate, cerium nitrate; strontium carbonate, strontium nitrate; magnesium carbonate, magnesium nitrate; lanthanum nitrate, lanthanum carbonate; yttrium nitrate, yttrium carbonate; 5) filler α- alumina, perovskite, calcium oxide, barium oxide, cordierite, mullite, magnesium titanate, than the surface area of ​​the filler material powder is between 1 ~ 4m2 / g, filled particle size of the material powder is 50μm or less; 6) acidic substance used include nitric acid, acetic acid, the impurity content of the acidic substance is 1% or less; 7) the basic substance include ammonia, urea, potassium, said alkaline substance the total content of impurities not exceeding 1%; 8) select cordierite ceramic honeycomb substrate, a cell density of 300 to 600 cells / square inch, square pore wall thickness in the range of 0.1 ~ 0.22mm; 9) contained in the catalyst prepared and the content of the various components, the content of active alumina support of 20 to 150 g / l, the amount of rare earth-based composite oxide additives is 15 to 200 grams / liter, the filler material is 10 to 100 g / l, the noble metal in an amount of 0.2 to 2 g / l, Pt, Pd, Rh 三种贵金属的比例控制在Pt/Rh=15∶1至2∶1,Pd/Rh=10∶1至2∶1,Pt/Pd/Rh=10∶0∶1至0∶10∶1,以La-Ba稳定氧化铝或稳定催化剂,其含量为氧化铝或催化剂涂层的0~5%;(2).研磨及制备浆液:10)将上述活性氧化铝单独或混同稀土基复合氧化物以及少量的碱金属、碱土金属、稀土金属的盐或氧化物混合均匀后进行研磨至粒度为D90在3~15μm;11)将贵金属的单独或混合溶液浸渍在上述研磨后的粉末上,然后加入一定量的氨水或乙酸溶液,再进行混合研磨1~5小时,形成湿润性粉末混合物;12)将上述粉末在120~180℃温度下干燥1~5小时,400~600℃下煅烧30分钟~5小时;13)将湿润性粉末混合物或煅烧后的粉末,与适量的α-氧化铝、钙钛矿、氧化钙、氧化钡、堇青石、莫来石、钛酸铝镁的单独或混合物充分混合;14)在上述混合物中加入合适量的去离子水、乙酸、硝酸 Noble metals proportional control in Pt / Rh = 15:1 to 2:1, Pd / Rh = 10:1 to 2:1, Pt / Pd / Rh = 10:0:1 to 0:10:1 to la-Ba stabilized alumina catalyst or stabilizer in an amount of 0 to 5% alumina or catalyst coating; (2) grinding and preparing a slurry: 10) alone or the above-mentioned active alumina based composite oxide and rare earth confused. small amounts of alkali metals, alkaline earth metals, rare earth metal salts or oxides mixed after grinding to a particle size D90 is at 3 ~ 15μm; 11) alone or in admixture of noble metal impregnation solution on the powder after the grinding, then adding some the amount of aqueous ammonia or acetic acid solution, and then mixed and ground for 1-5 hours to form a wet powder mixture; 12) the above powder at a temperature of 120 ~ 180 ℃ dried for 1 to 5 hours, calcined from 30 minutes to 5 at 400 ~ 600 ℃ hours; alone or in a mixture of 13) after the wet powder mixture or calcined powder with a suitable amount of α- alumina, perovskite, calcium oxide, barium oxide, cordierite, mullite, magnesium aluminum titanate mixed ; 14) is added in a suitable amount of the above mixture of deionized water, acetic acid, nitric 适量的氨水制成可流动的浆液;15)将上述浆液转移到数升大小的球磨罐中,加入适量的酸液或碱液调整浆液的pH值在2~5范围之内,加入少量的消泡剂,然后在球磨罐中进行球磨,时间在1~24小时,直至浆液的粒子粒度D90在10μm以下;16)取出研磨后的浆液,加入液态物质至固含量达到20%~45%,所述的液态物质是酸、碱或去离子水;(3).涂附及煅烧活化:17)以陶瓷蜂窝基体或含有预涂层的陶瓷蜂窝基体浸入到上述浆液之中,10~40秒后取出,用压缩空气吹扫,放入干燥箱中100~250℃干燥5~20个小时,至脱水率达到75%以上,干燥在空气下或惰性气氛下进行,18)初步脱水后的催化剂毛坯放入马福炉中进行高温煅烧,煅烧温度400~650℃,时间30分钟~5小时,煅烧是在空气下或惰性气氛下进行,19)煅烧之后,根据催化剂的本身需要和应用需要,在高温下对催 The amount of ammonia slurried flowable; 15) transferring the slurry to a few liter mill pot size, adjust the pH of the slurry was added an appropriate amount of acid or lye in a range of 2 to 5, adding a small amount of consumption foaming agent, and then milling in a ball mill jar, time 1 to 24 hours, until the slurry particle size D90 in 10μm or less; 16) slurry was taken out grinding, addition of a liquid substance to a solids content of 20% to 45%, of the liquid substance described below is an acid, base or deionized water; (3) coated and calcinated: 17) to a ceramic honeycomb substrate or a ceramic honeycomb matrix comprising a pre-coat was immersed into the slurry, after 10 to 40 sec. removed by blowing compressed air, placed in a drying oven 100 ~ 250 ℃ 5 to 20 hours until dehydration rate reaches 75% or more, drying in air or an inert atmosphere, 18) after the preliminary dehydration catalyst blank after discharge muffle furnace for high temperature calcination, the calcination temperature is 400 ~ 650 ℃, 30 minutes to 5 hours, firing is carried out in the air or an inert atmosphere, 19) calcining the catalyst according to the own needs and application needs, at a high temperature for reminders 化剂进行还原活化,还原是在还原气氛下进行。 Activation reduction agent, the reduction is carried out in a reducing atmosphere.
2.按照权利要求1所述的方法,其特征在于其一次涂附过程包括如下制备工艺过程:(1).原料的选择:1)稀土基复合氧化物,使用的铈/锆的原子比在8-3∶1,同时,添加的钇、镧、镨、钕中的一种或多种,含量在1%~10%范围之内,2)贵金属盐溶液,包括硝酸铂、氯铂酸的酸性或碱性溶液;硝酸铑、氯化铑;硝酸钯、氯化钯,3)所述碱金属、碱土金属、稀土金属的盐或氧化物是碳酸钡、氧化钡、乙酸钡;碳酸钙、氧化钙;硝酸氧锆、氢氧化锆、乙酸氧锆、氯氧化锆;硝酸铈;硝酸锶;硝酸镁;硝酸镧、碳酸镧;硝酸钇、碳酸钇;4)制备的催化剂的各种成分及含量为,活性氧化铝载体的含量为20~120克/升,稀土基复合氧化物助剂的使用量为15~150克/升,填充材料为10~80克/升,贵金属的含量为0.2~1.5克/升,Pt、Pd、Rh三种贵金属的比例控制在Pt/Rh=10∶1至2∶1 2. The method according to claim 1, characterized by the following process comprising preparing a coated procedure in that: (1) material selection: 1) The rare earth-based composite oxide, the cerium / zirconium atomic ratio 8-3:1, while adding yttrium, lanthanum, praseodymium, neodymium, one or more, the content in the range of 1% to 10%, 2) a noble metal salt solution, including platinum nitrate, chloroplatinic acid acidic or basic solution; rhodium nitrate, rhodium chloride; palladium nitrate, palladium chloride, 3) the alkali metal, alkaline earth metal, rare earth metal oxides or salts are barium carbonate, barium oxide, barium acetate; calcium carbonate, calcium oxide; zirconyl nitrate, zirconium hydroxide, zirconyl acetate, zirconium oxychloride; cerium nitrate; strontium nitrate; magnesium nitrate; lanthanum nitrate, lanthanum carbonate; yttrium nitrate, yttrium carbonate; various components of the catalyst 4) preparation of and content, content of the active alumina support is from 20 to 120 g / liter, the amount of rare earth-based composite oxide additives is 15 to 150 grams / liter, the filler material is 10 to 80 g / l, the noble metal content of 0.2 to 1.5 g / l, Pt, Pd, Rh ratio is controlled noble metals Pt / Rh = 10:1 to 2:1 Pd/Rh=8∶1至2∶1,Pt/Pd/Rh=8∶0∶1至0∶8∶1,以La-Ba稳定氧化铝或稳定催化剂,其含量为氧化铝或催化剂涂层的0~3%;(2).研磨及制备浆液:5)将贵金属的单独或混合溶液浸渍在上述研磨后的粉末上,然后加入一定量的氨水或乙酸溶液,再进行混合研磨2~4小时,形成湿润性粉末混合物;6)将上述粉末在120~180℃温度下干燥1~5小时,煅烧温度500~550℃,煅烧时间1~3小时;(3).涂附及煅烧活化:7)以陶瓷蜂窝基体或含有预涂层的陶瓷蜂窝基体浸入到上述浆液之中,10~40秒后取出,用压缩空气吹扫,放入干燥箱中100~250℃干燥5~12个小时;8)初步脱水后的催化剂毛坯放入马福炉中进行高温煅烧,煅烧温度500~550℃,时间30分钟~3小时。 Pd / Rh = 8:1 to 2:1, Pt / Pd / Rh = 8:0:1 to 0:8:1 to La-Ba stabilized alumina catalyst or stabilizer in an amount of alumina or catalyst coating 0 to 3%; (2) grinding and preparing a slurry: 5), alone or in a mixed impregnation solution the noble metal on the powder after the grinding, and then adding an amount of aqueous ammonia or acetic acid solution, and then mixing and grinding 2 to 4 hours to form a wet powder mixture; 6) the above powder at a temperature of 120 ~ 180 ℃ dried for 1 to 5 hours, firing temperature 500 ~ 550 ℃, the calcination time is 1-3 hours; (3) coated and calcinated: 7) a ceramic honeycomb substrate or a ceramic honeycomb matrix containing precoat dipped into the slurry, taken after 10 to 40 sec, purged with compressed air, placed in a drying oven 100 ~ 250 ℃ 5 to 12 hours ; 8) the catalyst after preliminary dewatering blank placed in a muffle furnace for high temperature calcination, the calcination temperature is 500 ~ 550 ℃, 30 minutes to 3 hours.
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