CN102861565A - Aluminum oxide-loaded cerium oxide catalyst and preparation method and application thereof - Google Patents

Aluminum oxide-loaded cerium oxide catalyst and preparation method and application thereof Download PDF

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CN102861565A
CN102861565A CN 201210339709 CN201210339709A CN102861565A CN 102861565 A CN102861565 A CN 102861565A CN 201210339709 CN201210339709 CN 201210339709 CN 201210339709 A CN201210339709 A CN 201210339709A CN 102861565 A CN102861565 A CN 102861565A
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alumina
catalyst
ceria
supported
cerium
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CN 201210339709
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Chinese (zh)
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潘卫国
周曰
郭瑞堂
徐宏建
于月良
何明福
闻雪平
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上海电力学院
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Abstract

The invention discloses an aluminum oxide-loaded cerium oxide catalyst and a preparation method and application thereof. Calculated by mass ratio, the mass ratio of aluminum oxide to cerium oxide in the aluminum oxide-loaded cerium oxide catalyst is 85:15. The preparation method for the aluminum oxide-loaded cerium oxide catalyst is characterized in that by adopting an equivalent-volume impregnation method, a coprecipitation method or a sol-gel method, the finally obtained aluminum oxide-loaded cerium oxide catalyst is higher in denitration activity at the lower reaction temperature of 200 DEG C when being used in a selective catalytic reduction flue gas denitration process, and the denitration efficiency can reach at least 90 percent, and thereby, the abuse that the reaction temperature of a traditional catalyst is high is overcome.

Description

一种氧化铝负载氧化铈催化剂及其制备方法和应用 An alumina ceria supported catalyst and preparation method and application

技术领域 FIELD

[0001] 本发明涉及到烟气脱硝催化剂技术领域,具体涉及ー种氧化铝负载氧化铈催化剂及其制备方法和应用。 [0001] The present invention relates to the technical field of flue gas denitration catalyst, particularly to seed ー alumina supported ceria catalyst and preparation method and application.

背景技术 Background technique

[0002] 氮氧化物NOx是世界各国公认的主要大气污染物之一。 [0002] nitrogen oxides NOx is one of the major air pollutants recognized around the world. 它破坏臭氧层,形成酸雨和光化学烟雾,影响生态环境,危害人类健康,目前氮氧化物的减排已受到人们极大的关注。 It destroys the ozone layer, acid rain and photochemical smog, ecological impacts, harm to human health, the current emissions of nitrogen oxides has been of great concern. 我国是以燃煤为主的发展中国家,燃煤排放的氮氧化物是造成氮氧化物环境污染的主要人为来源。 Our country is developing coal-based, nitrogen oxide emissions from coal burning is caused by nitrogen oxides major anthropogenic sources of environmental pollution. 2009年我国火电厂氮氧化物排放总量达到1860万吨我国国民经济的快速发展,使得我国燃煤发电装机容量迅速増加,有专家预测:如果不进一步采取有效的措施来控制氮氧化物的排放,我国氮氧化物排放量将继续增长,2020年将达到2900万吨左右。 In 2009 the total amount of nitrogen oxide emissions thermal power plants in China reached 18.6 million tons the rapid development of China's national economy, making China's coal-fired power generation capacity quickly be increased, in some experts predict: If you do not take further effective measures to control emissions of nitrogen oxides nitrogen oxide emissions our country will continue to grow in 2020 will reach about 29 million tons. 随着我国环保要求的日益严格,执法力度的加严,选择性催化还原(Selective CatalyticReduction, SCR)烟气脱硝技术因其脱硝率高(可达90%以上)、技术成熟成为燃煤电站锅炉控制NOx排放的首选。 With our country's increasingly stringent environmental requirements, tightened enforcement, and selective catalytic reduction (Selective CatalyticReduction, SCR) flue gas denitrification technology because of its high rate of denitrification (up to 90%), technology has become mature coal-fired utility boiler control the preferred NOx emissions.

[0003] 催化剂是SCR烟气脱硝技术的核心,其配方、结构和表面积对脱除NOx的效果有很大影响。 [0003] SCR catalysts are the core of flue gas denitrification technique, its formula, structure and surface area have a great influence on the effect of the removal of NOx. 在SCR系统运行的过程中,催化剂会因为各种物理化学作用(中毒、磨损、热烧结、堵塞/沾污等)而失效,这些都与锅炉的燃料特性密切相关。 During operation of the SCR system, catalyst because of various physical and chemical effects (poisoning, wear, thermal sintering, plugging / fouling, etc.) failure, these properties are closely related to the fuel boiler. 由于受我国煤炭资源和燃料供应政策的制约,我国火电厂燃煤的品质通常较差,而且近年来由于我国煤炭市场供求关系紧张,发电用煤质量近几年来一直呈下降趋势,煤炭中的灰份和硫份上升。 Due to the constraints of China's coal resources and fuel supply policy, the quality of coal-fired thermal power plant is usually poor, but in recent years due to the coal market supply and demand of tension, the quality of coal for power generation has been declining in recent years, coal ash parts of sulfur rise. 我国动カ用煤与世界发达国家相比,质量处于较低水平,国际上动力用煤的灰分小于15%,按此衡量,我国只有20%的动カ用煤产品质量能达到标准。 Our dynamic grades of coal, compared with developed countries, the quality at a lower level, the international power coal ash is less than 15%, the measure of its size, China is only 20% of the move ka coal product quality to meet the standard. 这样造成我国火电厂用煤种类复杂、多祥,特别是燃用劣质煤和运行煤种频繁变化,使得火电厂燃煤持续偏离设计煤种和校核煤种,此外,我国燃煤的成分极其复杂,元素在煤中的富存状态多种多祥。 Such species cause coal in thermal power plant complex, multi-cheung, especially those burning low quality coal and coal run frequently change, making coal-fired power plants continue to deviate from the design of coal and coal checking, in addition, the composition of our coal is extremely complex elements in the coal-rich states exist in a variety of multi-cheung. 因此急需探索火电厂煤质变化对SCR催化剂活性的影响,研究煤中不同组分单独以及多种组分叠加对SCR催化剂的作用机理,认识催化剂的失活规律,这对降低催化剂活性衰减速率、延长催化剂使用寿命、降低火电厂脱硝成本、促进烟气脱硝技术的推广应用具有重要的现实意义,为SCR的运行提供理论指导依据。 Therefore an urgent need to explore changes in coal thermal power plant on the SCR catalyst activity, research and a variety of individual components superimposed on the mechanism of action of different components of SCR catalyst in coal, catalyst deactivation understanding of the law, which reduce the catalyst activity decay rate, extended catalyst life, has important practical significance to reduce the thermal power plant denitration costs and promote the popularization and application of flue gas denitrification technology to provide theoretical guidance for operation of the SCR. 由于纳米CeO2的比表面积大、化学活性高、热稳定性好、良好的储氧和释氧能力,可改变催化剂中活性组分在载体上的分散情况,明显提高其催化性能,井能提高载体的高温热稳定性能、机械性能和抗高温氧化性能。 Due to the large ratio of surface area of ​​CeO2, high chemical activity, good thermal stability, good oxygen storage capacity and oxygen release, may change the dispersion of the active catalyst component on the carrier, increasing their catalytic performance, the support shaft can be improved high temperature thermal stability, mechanical properties, and high temperature oxidation resistance. 另外,CeO2还在贵金属气氛中起稳定作用,提高NOx的转化率,并使催化剂保持较好的抗毒性及较高的催化活性。 Further, the noble metal is still an atmosphere of CeO2 stabilizing effect, increase the conversion rate of NOx, and the catalyst maintained good anti-toxicity and high catalytic activity. 而关于负载氧化铈催化剂应用于催化氢氧化物的NH3-SCR反应目前尚未见文献报道。 While supported on cerium oxide catalyst for the catalytic reaction of NH3-SCR hydroxide present has not been reported.

发明内容 SUMMARY

[0004] 本发明的目的在于为了提高催化剂的高温热稳定性能、机械性能和抗高温氧化性能,使得其在较低的温度区间拥有较高的脱硝活性这ー技术问题而提供ー种氧化铝负载氧化铈催化剂及其制备方法。 [0004] The object of the present invention is to improve the high temperature thermal stability of the catalyst, the mechanical properties, and high temperature oxidation resistance, so that it has a high denitration activity in a low temperature range of this technical problem is provided ー ー alumina supported species cerium oxide catalyst and preparation method. 该氧化铝负载氧化铈催化剂具有操作间断,活性组分抑郁分散在载体表面,增大表面积,能在较低的温度窗ロ拥有较高的脱硝活性的优点。 The alumina-supported catalyst having cerium oxide intermittent operation, the active ingredient dispersed in a depression surface of the carrier, a large surface area, can have the advantage of a higher ro denitration activity in a low temperature window.

[0005] 本发明的技术方案 [0005] aspect of the present invention.

一种氧化铝负载氧化铈催化剂,按质量比计算,即氧化铝:氧化铈为85 :15。 An alumina ceria supported catalyst, the mass ratio is calculated, i.e., alumina: ceria is 85: 15.

[0006] 上述的一种氧化铝负载氧化铈催化剂的制备方法,可以采用常规的等体积浸溃法,共沉淀法,溶胶凝胶法或柠檬酸法等,本发明仅以等体积浸溃法,共沉淀法和溶胶凝胶法进行举例,具体如下: Preparation of [0006] the above-described method of an alumina ceria supported catalyst, an equal volume of a conventional dipping method, a coprecipitation method, a sol-gel method or citric acid method, the present invention is only equal volume impregnation method , co-precipitation method and sol-gel method for example, as follows:

等体积浸溃法制备氧化铝负载氧化铈催化剂,步骤如下: Preparation of an equal volume of alumina impregnated ceria supported catalyst, the following steps:

将伽马氧化铝与硝酸铈或醋酸铈进行混合后溶于去离子水中,并使其完全浸溃刚好饱和,20-100°C下采用聚四氟こ烯搅拌桨,控制搅拌速率为200-600rpm搅拌0. 5_3h,而后在80-110°C下干燥4-12h,然后在300ml/min的N2气氛、600°C在管式炉中焙烧l_12h,硝酸铈或醋酸铈高温完全分解为氧化铈,伽马氧化铝不变,再冷却至室温得到氧化铝负载氧化铈催化剂。 After the gamma alumina is mixed with the cerium acetate or cerium nitrate dissolved in deionized water, dipping immediately and completely saturated, using PTFE ko alkenyl paddles at 20-100 ° C, 200 to control the stirring rate 600rpm stirring 0. 5_3h, and then dried at 80-110 ° C 4-12h, and then in an N2 atmosphere 300ml / min of, 600 ° C in a tube furnace and fired l_12h, cerium acetate, cerium nitrate or cerium oxide completely decomposed temperature , constant gamma alumina, cooled to room temperature to obtain an alumina ceria supported catalyst.

[0007] 共沉淀法制备氧化铝负载氧化铈催化剂,步骤如下: [0007] Preparation of Alumina coprecipitated ceria supported catalyst, the following steps:

将硝酸铈与硝酸铝溶于去离子水中,在室温下采用聚四氟こ烯搅拌桨以200-600rpm的速率搅拌溶解,而后向里面加入3mol/L的氨水调pH为5-11后搅拌l_3h进行静止沉定,将所得的沉淀过滤并用去离子水冲洗干净后再次过滤; Cerium nitrate and aluminum nitrate in deionized water, using PTFE ko alkenyl paddle stirring rate 200-600rpm dissolved at room temperature, followed by addition of 3mol / L aqueous ammonia to pH 5-11 l_3h after which stirring Shen a still set, the resulting precipitate was filtered and washed with deionized water and filtered again after cleaning;

再次过滤后将所得沉淀在80-100°C下干燥6-12h,然后在lL/min的N2气氛、600°C在管式炉中焙烧5-12h,硝酸铺或醋酸铺高温完全分解为氧化铺,硝酸招高温完全分解为氧化铝,再冷却至室温得到氧化铝负载氧化铈催化剂。 After the resulting precipitate was filtered again and dried at 80-100 ° C 6-12h, and then in an N2 atmosphere lL / min to, 600 ° C in a tube furnace and fired 5-12h, nitric acid, acetic acid, or spread plated high temperature oxide completely decomposed Shop, nitric move completely decomposed alumina temperature, cooled to room temperature to obtain an alumina ceria supported catalyst.

[0008] 溶胶凝胶法制备氧化铝负载氧化铈催化剂,步骤如下: [0008] The sol gel process alumina, ceria supported catalyst, the following steps:

将异丙醇铝与硝酸铈或醋酸铈进行混合后溶于去离子水中配制成溶液,在室温下采用聚四氟こ烯搅拌桨搅拌控制搅拌速率为100-600rpm,向其中加入硝酸,使总金属离子摩尔浓度与硝酸的摩尔比0. 05-0. I,制得溶胶; After the formulation was dissolved in deionized aluminum isopropoxide was mixed with a cerium nitrate or cerium acetate in water into a solution, using PTFE ko alkenyl propeller agitation stirring rate controls the range of 100-600rpm, nitric acid was added thereto at room temperature, total molar ratio of the metal ion molar concentration of nitric acid 0. 05-0 I, prepared by sol;

而后将制得的溶胶在80-100°C下干燥12h制得干凝胶,最后将制得的干凝胶在300ml/min的N2气氛、600°C在管式炉中焙烧3_12h,硝酸铺或醋酸铺高温完全分解为氧化铺,异丙醇铝高温完全分解为氧化铝,再冷却至室温得到氧化铝负载氧化铈催化剂。 After the prepared sol was dried at 80-100 ° C to obtain xerogel 12h, and finally the obtained calcined xerogel 3_12h, laid in an N2 atmosphere 300ml / min of, 600 ° C in a tube furnace nitrate acetic acid or plated high temperature oxide shop completely decomposed, the complete decomposition temperature of aluminum isopropoxide as aluminum, cooled to room temperature to obtain an alumina ceria supported catalyst.

[0009] 上述所得的一种氧化铝负载氧化铈催化剂在脱硝过程中的应用,步骤如下: [0009] A ceria-alumina supported catalyst obtained in the above-described denitration process of the application, the following steps:

脱硝开始前先用模拟烟气中的NO通入固定床反应器约l_2h,让氧化铝负载氧化铈催化剂吸附NO达到饱和,避免因氧化招负载氧化铺催化剂的吸附引起NO的减少;氧化招负载氧化铈催化剂吸附NO达到饱和后,将待脱硝的烟气通入固定床反应器控制反应温度在200-400°C,流速为500ml/min,空间速度10000-3000(¾'在氧化铝负载氧化铈催化剂的作用下,烟气中的NH3将NO还原为N2气体,反应后的混合气经磷酸溶液吸收未反应的NH3后经排气管排入大气,从而达到烟气脱硝的目的; Denitration before the start first with the simulated flue gas into a fixed bed reactor NO about l_2h, ceria alumina-supported catalyst so that adsorption of NO saturated adsorption avoid laying oxide oxidation catalyst supported strokes due to reduction of NO; ​​load strokes oxide cerium oxide catalyst after adsorption of NO saturated denitration of flue gas to be passed into a fixed bed reactor to control the reaction temperature at 200-400 ° C, a flow rate of 500ml / min, space velocity 10000-3000 (¾ 'oxide supported on alumina under the action of the cerium catalyst, the NO in the flue gas is reduced to N2 NH3 gas, the mixed gas by the reaction of phosphoric acid solution after absorption of unreacted NH3 into the atmosphere through the exhaust pipe, so as to achieve the purpose of denitrification of flue gas;

所述的模拟烟气组成:N0200-600ppm,NH3200_600ppm以及O2为0_5%,其余气体N2作为平衡气。 Said simulated flue gas composition: N0200-600ppm, NH3200_600ppm 0_5% O2, and the remainder N2 gas as a ballast gas.

[0010] 本发明的有益效果 [0010] Advantageous effects of the present invention.

本发明的一种氧化铝负载氧化铈催化剂,由于在多孔状材料中,伽马氧化铝是最常用的催化吸附剂载体的晶体材料之一。 An alumina ceria supported catalyst of the present invention, since the porous material, the gamma alumina is one of the most commonly used catalytic material is crystalline adsorbent support. 氧化铝由于其优良的机械特征和理想的孔结构特征对催化吸附剂的改进起到重要作用。 Alumina because of its excellent mechanical and structural features of the pores play an important role for the desired improved catalytic adsorbent. 由于纳米CeO2的比表面积大、化学活性高、热稳定性好、良好的储氧和释氧能力,可改变催化剂中活性组分在载体上的分散情况,明显提高其催化性能,并能提高载体的高温热稳定性能、机械性能和抗高温氧化性能,CeO2还在贵金属气氛中起稳定作用,提高COXH4及NOx的转化率,因此使最終形成的氧化铝负载氧化铈催化剂保持较好的抗毒性及较高的催化活性。 Due to the large ratio of surface area of ​​CeO2, high chemical activity, good thermal stability, good oxygen storage capacity and oxygen release, may change the dispersion of the active catalyst component on the carrier, increasing their catalytic performance, and can improve the carrier high temperature thermal stability, mechanical properties and high temperature oxidation resistance, noble atmosphere of CeO2 also a stabilizing effect, and improve the conversion rate of NOx COXH4, thus finally formed cerium oxide supported on alumina catalyst poisoning resistance and maintain good higher catalytic activity.

[0011] 等体积浸溃方法制备氧化铝负载氧化铈催化剂,因其操作简单,可控性强的优点,在实际脱硝活性实验中取得较高的脱硝活性,在200°c的低温窗ロ都能保持在88%以上。 [0011] The method of preparing an equal volume of the impregnated ceria-alumina supported catalyst, because of its simple operation, strong controllability advantages achieved high denitration activity in a practical experiment denitration activity in a low temperature of 200 ° c ro window are can be maintained at 88% or more.

[0012] 共沉淀法是最有效的ー种方法制备氧化铝负载氧化铈的方法,得到均匀分散的、纳米级的铈粒子,共沉淀法虽然操作简单,但比较难以控制。 [0012] The coprecipitation method is the most effective method for preparing cerium oxide, alumina-supported ー method, to obtain a uniform dispersion of nano-sized cerium oxide particles, although the coprecipitation method is simple, but more difficult to control. 在制各过程中,有很多因素需要考虑,比如混合的程度、沉淀温度、沉淀时溶液的pH值、老化时间、过滤洗涤、各种前身化合物的添加顺序以及加入方式的不同等等,都可能对实验结果产生很明显的影响。 In each process system, there are many factors to consider, such as the degree of mixing, the precipitation temperature, pH value of the solution during the precipitation, the aging time, filtered and washed, etc. The order of addition of various different compounds as well as the predecessor added embodiment, may have a very significant impact on results. 所以本发明进一歩的确定了以上參数,取得最优值,制备出高效的氧化铝负载氧化铈催化剂,同样在200°C低温窗ロ时能达到脱硝率90%以上。 Therefore, according to the present invention into a ho determine the above parameters, to obtain the optimum value, the efficient preparation of cerium oxide supported on alumina catalyst can achieve the same denitration rate at 200 ° C ro when low temperature window above 90%.

[0013] 溶胶凝胶法制备氧化铝负载氧化铈催化剂,通过确定实验条件,确定铈源与载体,得出高效的低温SCR催化剂,在200°C低温窗ロ铈能达到脱硝率92%以上。 [0013] sol - gel process alumina, ceria supported catalyst, the experimental conditions determined by determining a cerium source and a carrier, the low temperature SCR catalyst efficiency results in low window 200 ° C ro cerium denitration rate can reach 92%.

具体实施方式 Detailed ways

[0014] 下面通过具体实施例对本发明进ー步阐述,但并不限制本发明。 [0014] The following further into ー present invention is illustrated by way of specific examples, but not limit the invention.

[0015] 本发明的实施例中的所用催化反应器采用内径为14_的固定床反应器,原料气经过预热进入固定床反应器,反应温度在20(T400°C,流速为500ml/min,空间速度230001^,氧化铝负载氧化铈催化剂5g。 [0015] Example embodiments of the present invention employed with an inner diameter of 14_ catalytic reactor of a fixed bed reactor, the preheated feed gas enters the fixed bed reactor, the reaction temperature is 20 (T400 ° C, a flow rate of 500ml / min The space velocity ^ 230001, ceria alumina-supported catalyst 5g.

[0016] 模拟烟气组成:N0600ppm,NH3600ppm以及O2为5%,其余气体N2作为平衡气,气体流量由质量流量计CS200控制。 [0016] The simulated flue gas composition: N0600ppm, NH3600ppm and 5% O2, N2 gas as the remaining gas balance, the gas flow rate controlled by a mass flow meter CS200.

[0017] 本发明所用的各种原料的规格及生产厂家的信息请补充。 Information of the various starting materials used in the [0017] present invention, specifications and manufacturers please add.

[0018] [0018]

Figure CN102861565AD00051

[0019] 上述的一种氧化铝负载氧化铈催化剂的制备方法,按等体积浸溃法进行制备,步骤如下: [0019] A method for preparing the cerium oxide supported on alumina catalyst, prepared by an equal volume impregnation method, the following steps:

将两份0. 85g伽马氧化铝分别浸溃于配制好的0. 15g硝酸铈和0. 15g醋酸铈溶液中,分别于50°C下采用聚四氟こ烯搅拌桨搅拌,搅拌过程控制搅拌速率为200rpm,时间lh,而后分别在110°C下干燥12h,然后分别在300ml/min的N2气氛、600°C在管式炉中焙烧5h,再分别冷却至室温得到CeO2的负载量为15%的氧化铝负载氧化铈催化剂A及B。 The two gamma-alumina 0. 85g are impregnated in the formulated 0. 15g 0. 15g of cerium nitrate and cerium acetate solution, respectively ko alkenyl PTFE paddle stirred at 50 ° C, stirred for process control stirring rate at 200 rpm, the time LH, then were dried 12h at 110 ° C, and then respectively in an N2 atmosphere 300ml / min of, 600 ° C calcining 5h in a tube furnace, and then were cooled to obtain a loading of CeO2 was room temperature 15% of alumina, ceria supported catalyst a and B.

[0020] 实施例2 [0020] Example 2

一种氧化铝负载氧化铈催化剂,按质量百分比计算,即氧化铝:氧化铈为85 :15。 An alumina ceria supported catalyst, by mass percentage, i.e., alumina: ceria is 85: 15.

[0021] 上述的一种氧化铝负载氧化铈催化剂的制备方法,按共沉淀法进行制备,步骤如下: [0021] A method for preparing the cerium oxide supported on alumina catalyst, prepared by the coprecipitation method, the following steps:

将0. 15g硝酸铈和0. 15g醋酸铈分别与6. 255g硝酸铝溶于去离子水中,在室温下采用聚四氟こ烯搅拌桨,以200rpm的速率搅拌溶解,而后分别加入3mol/L的氨水调pH为11,搅拌3h后,将沉淀过滤并用去离子水冲洗干净; To 0. 15g 0. 15g of cerium nitrate and cerium acetate respectively 6. 255g of aluminum nitrate dissolved in deionized water, using PTFE ko alkenyl paddles at room temperature, dissolved with stirring at a rate of 200rpm, and then were added 3mol / L aqueous ammonia to pH 11. after stirring for 3h, the precipitate was filtered and rinsed with deionized water;

而后将所得沉淀分别在100°C下干燥12h,然后分别在lL/min的N2气氛、600°C在管式炉中焙烧5h,再分别冷却至室温得到CeO2的负载量为15%的氧化铝负载氧化铈催化剂C及D0 After the resulting precipitate was dried and 12h, respectively, at 100 ° C, respectively in an N2 atmosphere and then lL / min of, 600 ° C for 5h calcined in a tube furnace, and then were cooled to room temperature to give loading of CeO2 is 15% alumina ceria supported catalyst C and D0

[0022] 实施例3 [0022] Example 3

一种氧化铝负载氧化铈催化剂,按质量百分比计算,即氧化铝:氧化铈为85 :15。 An alumina ceria supported catalyst, by mass percentage, i.e., alumina: ceria is 85: 15.

[0023] 上述的一种氧化铝负载氧化铈催化剂的制备方法,按溶胶凝胶法进行制备,步骤如下: [0023] A method for preparing the cerium oxide supported on alumina catalyst, prepared by the sol-gel method, the following steps:

称3. 405g异丙醇铝分别与0. 15g硝酸铈和0. 15g醋酸铈溶于配制成溶液,在室温下采用聚四氟こ烯搅拌桨,控制搅拌速率为200rpm,并向其中分别加入I. 2ml的0. lmol/L的硝酸作为胶溶剂,制得溶胶; Said aluminum isopropoxide 3. 405g 0. 15g respectively cerium nitrate and cerium acetate was dissolved in 0. 15g formulated as a solution, using paddle PTFE alkenyl ko at room temperature, stirring rate is controlled at 200 rpm, and thereto were added I. 2ml of 0. lmol / L of nitric acid as a peptizing agent, to obtain a sol;

而后将制得的溶胶分别在80°C下干燥12h制得干凝胶,最后将制得的干凝胶分别在300ml/min的N2气氛、600°C在管式炉中焙烧5h,再分别冷却至室温得到CeO2的负载量为15%的氧化铝负载氧化铈催化剂E及F。 After the sol obtained are dried at 80 ° C for 12h to obtain a xerogel, and finally resulting in an N2 atmosphere xerogels were 300ml / min of, 600 ° C for 5h calcined in a tube furnace, and then were E ceria-alumina supported catalyst obtained was cooled to room temperature CeO2 loading of 15% and F.

[0024] 应用实施例I [0024] Application Example I

利用实施例I、实施例2及实施例3所得的铈基的负载量分别为15%的氧化铝负载氧化铈催化剂A、B、C、D、E、F及普通催化剂(美国的Cormetech氧化钛基SCR催化剂)分别进行脱硝活性实验 Using Example I, Example 2 and Example 3 are loading cerium-based embodiment 15%, respectively, of cerium oxide supported on alumina catalysts A, B, C, D, E, F, and conventional catalysts (US Cormetech dioxide based SCR catalyst) were denitration activity tests

实验测试开始前先用模拟烟气中的NO通入固定床反应器约lh,让氧化铝负载氧化铈催化剂吸附NO饱和,主要是为了避免因氧化铝负载氧化铈催化剂的吸附引起NO的減少;模拟烟气的各组分在混气箱中混合后,然后通入固定床反应器在氧化铝负载氧化铈催化剂的作用下,NH3将NO还原为N2,反应后的混合气经磷酸溶液吸收未反应的NH3后经排气管排入大气,NO浓度采用美国热电的Model60I烟气分析仪检测,其脱硝的结果见下表: Experiment before starting the test with simulated flue gas is passed through a fixed bed reactor NO about LH, ceria alumina-supported catalyst so that adsorption of NO saturated, mainly to avoid adsorption of cerium oxide supported on alumina catalyst causes reduction of NO; simulation of the components in the flue gas after the aeration mixing tank, and then introduced into a fixed bed reactor under the effect of cerium oxide supported on alumina catalyst, NH3 to NO was reduced to N2, a mixed gas phosphoric acid solution after the reaction was not absorbed after the reaction NH3 into the atmosphere through the exhaust pipe, the flue gas NO concentration using Model60I analyzer Thermo, the denitration results as follows:

Figure CN102861565AD00061

从上表中可以看出,本发明中所述的氧化铝负载氧化铈脱硝催化剂相比于现有技术中 As can be seen from the table, according to the present invention, the alumina-supported ceria denitration catalyst as compared to the prior art

的普通催化剂(美国的Cormetech氧化钛基SCR催化剂),在低温区域具有更高的脱硝活性, The conventional catalysts (US Cormetech titania-based SCR catalyst), has higher denitration activity in a low temperature region,

同时本发明中的氧化铝负载氧化铈催化剂应用后,其脱硝率最低都大于87%,最高都达到 While the rear ceria alumina-supported catalyst of the present invention is applied, its denitration rate is greater than the lowest 87%, have reached the highest

96%以上,可见本发明的氧化铝负载氧化铈催化剂具有很高的催化氧化性,对于氮氧化物有 More than 96%, showing that the cerium oxide supported on alumina catalyst of the invention has a high catalytic oxidation, for nitrogen oxides have

很高的脱除活性。 High removal activity. 并且制作エ艺简单,方便操作,可调控性能强,可以改变负载量及相应载 Ester Production and simple process, easy to operate, can be strong regulation properties, be varied and the corresponding load carrier

体来调整活性。 Active body is adjusted.

[0025] 以上所述内容仅为本发明构思下的基本说明,而根据本发明的技术方案所做的任何等效变换,均属于本发明保护的范围。 [0025] The above description is provided only for the basic concept of the present invention, according to any aspect of the present invention made equivalent transformation, all fall within the scope of the present invention.

Claims (5)

  1. 1. 一种氧化铝负载氧化铈催化剂,其特征在于所述的氧化铝负载氧化铈催化剂按质量百分比计算,即氧化铝:氧化铈为85:15。 A cerium oxide supported on alumina catalyst, wherein said catalyst is an alumina supported ceria by mass percentage, i.e., alumina: ceria 85:15.
  2. 2.如权利要求I所述的ー种氧化铝负载氧化铈催化剂的制备方法,其特征在于步骤如下: 首先将伽马氧化铝与硝酸铈或醋酸铈混合溶于去离子水中,使其完全浸溃刚好饱和,20-100°C下控制搅拌速率为200-600rpm搅拌0. 5_3h,而后在80_110°C下干燥4_12h,然后在300ml/min的N2气氛、600°C在管式炉中焙烧l_12h后冷却至室温得到氧化铝负载氧化铈催化剂。 2. The method as claimed in claim I ー species ceria alumina-supported catalyst, characterized by the following steps: First, gamma-alumina and cerium nitrate or cerium acetate mixed in deionized water, and completely immersed collapse just saturated, controlling the stirring rate at 20-100 ° C is stirred 200-600rpm 0. 5_3h, and then dried at 4_12h 80_110 ° C, and then in an N2 atmosphere 300ml / min of, 600 ° C calcined in a tube furnace l_12h after cooling to room temperature to obtain an alumina ceria supported catalyst.
  3. 3.如权利要求I所述的ー种氧化铝负载氧化铈催化剂的制备方法,其特征在于步骤如下: 将硝酸铈与硝酸铝溶于去离子水中,在室温下控制搅拌转速为200-600rpm进行溶解,而后向里面加入3mol/L的氨水调pH为5-11后搅拌l_3h进行静止沉定,将所得的沉淀过滤并用去离子水冲洗干净再次过滤; 再次过滤后将所得沉淀在80-100°C下干燥6-12h,然后在lL/min的N2气氛、600°C在管式炉中焙烧5-12h后冷却至室温得到氧化铝负载氧化铈催化剂。 3. The method as claimed in claim I ー species ceria alumina-supported catalyst, characterized by the steps of: cerium nitrate and aluminum nitrate in deionized water, stirring speed controlled at room temperature for 200-600rpm dissolved, then added to the inside 3mol / L aqueous ammonia to pH 5-11 with stirring l_3h sink after a still set, the resulting precipitate was filtered and rinsed with deionized water and filtered again; after the resulting precipitate was filtered at 80-100 ° again C was dried at 6-12h, and then in an N2 atmosphere lL / min to, 600 ° C in 5-12h cooling after firing tube furnace to room temperature to obtain an alumina ceria supported catalyst.
  4. 4.如权利要求I所述的ー种氧化铝负载氧化铈催化剂的制备方法,其特征在于步骤如下: 将异丙醇铝与硝酸铈或醋酸铈溶于去离子水中配制成溶液,在室温下控制搅拌速率为100-600rpm搅拌,向其中加入硝酸,使总金属铝与铈离子的摩尔浓度与硝酸的摩尔比为0. 05-0. I :1,制得溶胶; 而后将制得的溶胶在80-100°C下干燥12h制得干凝胶; 最后将制得的干凝胶在300ml/min的N2气氛、600°C在管式炉中焙烧3_12h后冷却至室温得到氧化铝负载氧化铈催化剂。 4. The method as claimed in claim I ー species ceria alumina-supported catalyst, characterized by the steps of: aluminum isopropoxide and cerium acetate or cerium nitrate dissolved in deionized water and formulated into a solution, at room temperature controlled stirring rate 100-600rpm agitation, nitric acid was added thereto to make the total molar concentration of nitrate ions to cerium aluminum molar ratio of 0. 05-0 I: 1, to obtain a sol; obtained after the sol. at 80-100 ° C 12h and dried to obtain a xerogel; finally obtained xerogel in an N2 atmosphere 300ml / min of, 600 ° C after firing 3_12h cooled in a tube furnace to room temperature to obtain an alumina supported oxide cerium catalyst.
  5. 5.如权利要求I所述的ー种氧化铝负载氧化铈催化剂在脱硝过程中的应用,其特征在于步骤如下: 脱硝开始前先用模拟烟气中的NO通入固定床反应器约l_2h,让氧化铝负载氧化铈催化剂吸附NO达到饱和,氧化铝负载氧化铈催化剂吸附NO达到饱和后,将待脱硝的烟气通入固定床反应器控制反应温度在200-400°C,流速为500ml/min,空间速度10000-3000(¾'在氧化铝负载氧化铈催化剂的作用下,烟气中的NH3将NO还原为N2气体,反应后的混合气经磷酸溶液吸收未反应的NH3后经排气管排入大气,从而达到烟气脱硝的目的; 所述的模拟烟气组成:N0200-600ppm,NH3200_600ppm以及O2为0_5%,其余气体N2作为平衡气。 5. Application ー ceria-alumina supported catalyst species I in the denitration process as claimed in claim, wherein the steps of: before the start of the first denitration of flue gas NO analog into a fixed bed reactor for about l_2h, let alumina-supported catalyst adsorbed NO ceria saturated, cerium oxide supported on alumina catalyst after adsorption of NO saturated denitration of flue gas to be passed into a fixed bed reactor to control the reaction temperature at 200-400 ° C, a flow rate of 500ml / after min, space velocity 10000-3000 (¾ 'under the effect of cerium oxide supported on alumina catalyst, the NO in the flue gas is reduced to N2 NH3 gas, a mixed gas phosphoric acid solution after the reaction by absorption through the exhaust unreacted NH3 tube into the atmosphere, so as to achieve the purpose of flue gas denitrification; said simulated flue gas composition: N0200-600ppm, NH3200_600ppm 0_5% O2, and the remainder N2 gas as a ballast gas.
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CN104096574A (en) * 2013-04-12 2014-10-15 财团法人工业技术研究院 Catalytic agent used for oxidation of ammonia gas, and method for removing ammonia gas in gas
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CN104190394A (en) * 2014-09-19 2014-12-10 西南化工研究设计院有限公司 Honeycombed denitration catalyst taking titanium aluminum composite oxide as carrier and preparation method thereof
CN105498474A (en) * 2015-11-28 2016-04-20 成都德善能科技有限公司 Air purification method
CN105797577A (en) * 2016-04-27 2016-07-27 华北电力大学 Process and catalyst for catalytically reducing NOX by using methane

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