CN104475152B - The choice of catalyst for the nitrogen oxide and hydrogen in the catalytic reduction - Google Patents

The choice of catalyst for the nitrogen oxide and hydrogen in the catalytic reduction Download PDF

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CN104475152B
CN104475152B CN201410527706.3A CN201410527706A CN104475152B CN 104475152 B CN104475152 B CN 104475152B CN 201410527706 A CN201410527706 A CN 201410527706A CN 104475152 B CN104475152 B CN 104475152B
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CN104475152A (en
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李兰冬
关乃佳
武光军
戴卫理
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南开大学
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Abstract

本发明涉及一种氮氧化物氢气选择催化还原的催化剂及其应用。 The present invention relates to a catalyst and a nitrogen oxide selected hydrogen in the catalytic reduction. 催化剂组成是以贵金属活性组分Pt,稀土元素助剂(La,Ce,Sm等)以及分子筛载体(MFI,BEA,CHA,FER,MOR等)。 The catalyst composition of the noble metal active component is Pt, a rare earth element aids (La, Ce, Sm, etc.) and the molecular sieve support (MFI, BEA, CHA, FER, MOR, etc.). 以氢气作为还原剂,使用上述催化剂可以在富氧条件下将氮氧化物转化为无害的氮气。 Hydrogen as a reducing agent, the catalyst can be used under oxygen-rich conditions the nitrogen oxides into harmless nitrogen gas. 所述反应的条件为,反应温度为100‑400℃,氮氧化物浓度为100‑2000ppm,氢气/氮氧化物比例为2‑6,反应的体积空速(GHSV)为1000‑60000h‑1。 The reaction conditions for the reaction temperature is 100-400 deg.] C, at a concentration of 100 to 2000 ppm of nitrogen oxides, hydrogen / nitrogen oxide ratio of 2-6, a volume space velocity of the reaction (a GHSV) of 1000-60000h-1. 本发明提供了一种高性能净化氮氧化物催化剂,可达到较高的氮氧化物转化率,并且工艺流程简单、绿色节能,适于大规模工业化推广应用。 The present invention provides a nitrogen oxide purification catalyst of high performance, can achieve a high conversion rate of nitrogen oxides, and the process is simple, green energy, suitable for large scale industrial application.

Description

用于氮氧化物氢气选择催化还原的催化剂及其应用 The choice of catalyst for the nitrogen oxide and hydrogen in the catalytic reduction

技术领域 FIELD

[0001] 本发明涉及一种氮氧化物氢气选择催化还原的催化剂及其应用。 [0001] The present invention relates to a catalyst and a nitrogen oxide selected hydrogen in the catalytic reduction.

背景技术 Background technique

[0002] 氮氧化物(N0X)是一类主要的大气污染物,主要包括一氧化氮(N0)和二氧化氮(n〇2)。 [0002] nitrogen oxides (NOx) are a major class of air pollutants, including nitric oxide (N0) and nitrogen dioxide (n〇2). 氮氧化物对生态环境造成严重的危害,它是引发酸雨和光化学烟雾的主要物种,可导致人眼红肿,视力减退,呼吸急促,头痛,肺水肿等疾病,甚至威胁人类生命。 Nitrogen oxides cause serious harm to the ecological environment, which is the main species caused by acid rain and photochemical smog, can cause eye irritation, vision loss, shortness of breath, headache, pulmonary edema and other diseases, and even threaten human life. 氮氧化物由于其危害大,难消除等特点已经受到全世界范围的广泛关注。 Nitrogen oxides due to their great harm, and so difficult to eliminate already received extensive attention worldwide. 催化还原法是氮氧化物净化的主要方法,在特定催化剂作用下,氮氧化物可以被还原为无害的氮气。 Catalytic reduction method is the primary method of purifying nitrogen oxide, at a specific catalyst, the nitrogen oxides can be reduced to harmless nitrogen. 以氨为还原剂,选择催化还原NOx的技术(NH3-SCR)是1957年由Engelhard公司开发并申请专利。 Ammonia as a reducing agent, the NOx selective catalytic reduction technologies (NH3-SCR) in 1957 developed and patented by the company Engelhard. 后来日本在该国环保政策驱动下,成功研制出了现今被广泛使用的V205/Ti02催化剂,并分别于1977年和1979年在燃油和燃煤锅炉上成功投入商业运用。 Later in Japan under the country's environmental policy-driven, successful production of the V205 / Ti02 catalyst now widely used, respectively in 1977 and 1979 successfully put into commercial use in the oil and coal-fired boilers. SCR法目前已成为世界上应用最多、最为成熟且最有成效的一种烟气脱硝技术,其主要反应为4NH3+4NO+〇2—4N2+6H2〇。 SCR method has become the most widely used in the world, the most mature and most effective kind of flue gas denitrification technology, the main reaction 4NH3 + 4NO + 〇2-4N2 + 6H2〇. 科研人员围绕NH3-SCR进行了大量的研宄工作,很多新催化剂体系可见专利报道(US5 198403; US2012184429)。 Researchers around the NH3-SCR traitor done a lot of research work, a lot of new catalyst systems visible patent reports (US5 198403; US2012184429). 然而,NH3-SCR尚存在一些缺点和瓶颈,还原剂NH3具有很强的腐蚀性,对管路和设备的要求非常高,造价昂贵;还原剂NH3的加入比例要求精确控制,不足量的NH3无法达到预想的净化效果,而过量的NH3又会对环境造成二次污染。 However, NH3-SCR, there are still some shortcomings and bottlenecks, reducing NH3 highly corrosive, piping and equipment requirements are very high, expensive; NH3 added in a proportion of fine control of the reducing agent, an insufficient amount of NH3 can not be achieve the desired purification effect, and excess NH3 in turn will cause secondary pollution to the environment.

[0003] 与NH3-SCR比较,以氢气作为还原剂的选择催化还原反应(H2-SCR)具有明显的优势:H2-SCR反应发生的温度(一般<l5〇°C)远远低于NH3-SCR反应(300-400°C),在实际应用过程中可以节约大量的能源消耗,同时降低了对设备的要求;氢是廉价易得的清洁还原剂, 它比NH3要便宜的多,并且没有NH3的腐蚀性,避免了NH3储藏运输过程中种种问题,大大增加了氮氧化物消除反应的经济性和可操作性。 [0003] compared to NH3-SCR, hydrogen as a reducing agent in selective catalytic reduction (H2-SCR) has obvious advantages: temperature (typically <l5〇 ° C) H2-SCR reaction occurs far below the NH3- SCR reaction (300-400 ° C), in the actual application process can save a lot of energy consumption, while reducing equipment requirements; hydrogen is readily available and inexpensive clean reducing agents, it is much cheaper than NH3, and no NH3 corrosion, avoiding the process of NH3 storage transport problems, greatly increasing the nitrogen oxide eliminate the economic and operational response. H2-SCR脱硝反应是一条清洁高效的环保路线, 能有效避免己经工业化的NH3-SCR路线中的诸多缺点,具有重大的经济和社会效应。 H2-SCR denitration reaction is a clean and efficient eco-route, can effectively avoid the NH3-SCR route already industrialization of many shortcomings, has significant economic and social effects. 目前, 关于贵金属与分子筛的H2-SCR催化剂用于氮氧化物氢气选择催化还原的研究和实际应用鲜有公开,但是在贵金属与分子筛的催化剂中引入了稀土金属元素未见报道。 Currently, the noble metal on the molecular sieve catalyst for the H2-SCR of nitrogen oxides and hydrogen Selection of the actual fresh catalytic reduction are disclosed, but the introduction of rare earth metal elements in the noble metal catalyst and molecular sieves has not been reported.

发明内容 SUMMARY

[0004] 本发明目的在于提供一种新型用于氮氧化物氢气选择催化还原的催化剂及其应用。 [0004] The object of the present invention to provide a novel catalyst and its application for selective catalytic reduction of nitrogen oxides in hydrogen gas. 本发明是以贵金属活性组分pt,稀土元素助剂(La、Ce或Sm等)以及分子筛载体(MFI, 8已八,(:说^£1?,1;101?等)组成的催化剂。以氢气作为还原剂,在富氧条件下将氮氧化物转化为无害的氮气,是一种高性能净化氮氧化物催化剂,可达到较高的氮氧化物转化率,并且工艺流程简单、绿色节能,适于大规模工业化推广应用。 The present invention is based on the noble metal active component Pt, a rare earth element aids (La, Ce or Sm, etc.) and the molecular sieve support (MFI, 8 has eight (: said ^ £ 1, 1; 101, etc.) of the catalyst composition??. hydrogen as a reducing agent, the excess oxygen in the nitrogen oxides into harmless nitrogen gas is a high nitrogen oxide purifying catalyst, nitrogen oxide can achieve a higher conversion rate, and the process is simple, green energy saving, suitable for large-scale industrial application.

[0005] 本发明提供的用于氮氧化物氢气选择催化还原的催化剂是由贵金属Pt、稀土元素助剂以及分子筛为载体组成,其中的质量百分比组成为: [0005] The present invention provides a nitrogen oxide catalytic reduction catalyst hydrogen is selected from the noble metals Pt, rare earth elements as additives and a carrier composed of zeolite, wherein the mass percentage composition:

[0006] Pt 0.1-5.0% [0006] Pt 0.1-5.0%

[0007] 稀土元素0.2-20.0% [0007] 0.2-20.0% of rare earth elements

[0008] 分子筛75-99.7%。 [0008] The molecular sieve 75-99.7%.

[0009] (各组分的质量百分比之和为100%)。 [0009] (mass percentages of the components is 100%).

[0010] 其中,稀土元素:La、Ce、Sm中的一种或几种;所述的分子筛为具有下述结构的硅酸铝分子筛:1^1、8£八、0^、? [0010] wherein, rare earth elements: La, Ce, Sm of one or more; the molecular sieve is a silicate molecular sieve having the following structure: 1 ^ 1,8 £ eight, 0 ^ ,? £1?或抓)1?,以及它们的磷酸硅铝分子筛等。 £ 1? Or catch) 1 ?, and their silicoaluminophosphate molecular sieve.

[0011] 可选地,所述的稀土元素为〇• 2-5 • 0% ;所述的分子筛为SAP0-34 (Si/Al = 0 • 1)或ZSM-5(Si/Al = 30)。 [0011] Alternatively, the rare earth element is square • 2-5 • 0%; the molecular sieve is SAP0-34 (Si / Al = 0 • 1) or ZSM-5 (Si / Al = 30) .

[0012]本发明提供的用于氮氧化物氢气选择还原催化剂的制备方法包括以下步骤: [0012] The present invention provides a production method for the selective catalytic reduction of nitrogen oxides in hydrogen gas comprises the steps of:

[0013] (1)按计量以具有1^1,8£4,〇^^£1?,]^01?等拓扑结构的硅酸铝分子筛或它们的磷酸硅铝分子筛作为载体,通过湿法浸渍引入稀土元素,在空气中450-550°C焙烧6-8h备用。 Aluminosilicate zeolite topology [0013] (1) having metered 1 ^ 1,8 £ 4, square ^^ £ 1?,] ^ 01?, Or the like as a carrier of silicoaluminophosphate molecular sieve by a wet introduction of the rare earth element impregnation, 450-550 ° C in air for alternate firing 6-8h. [0014] (2)将上述处理好的样品浸溃在氯铂酸溶液中,低温蒸干,在空气中450-650X:焙烧6-8h,形成催化剂粉末。 [0014] (2) The above prepared sample impregnated in the chloroplatinic acid solution, evaporated to dryness low, 450-650X in air: 6-8h calcination, form the catalyst powder.

[0015] (3)催化剂粉末通过直接挤压成型或涂敷于具有固定形状的基质(如堇青石陶瓷或金属波纹板),获得整体式催化剂。 [0015] (3) a powder catalyst or by direct extrusion coating to a substrate (e.g., cordierite or corrugated sheet metal) having a fixed shape, to obtain a monolith catalyst.

[0016]本发明提供的用于氮氧化物氢气选择还原催化剂的应用方法包括以下步骤:将上述催化剂放入固定床反应器中,应用于氢气选择催化还原氮氧化物反应中,反应温度为100-400°C,反应入口氮氧化物浓度为100-2000ppm,氢气/氮氧化物质量比为2-6;反应的体积空速(GHSV)为1000-60000h_1。 [0016] a nitrogen oxide selected hydrogen present invention provides a method of application of the reduction catalyst comprises the steps of: the catalyst into a fixed bed reactor, hydrogen gas is applied to the selective catalytic reduction of nitrogen oxides in the reaction, the reaction temperature is 100 -400 ° C, reactor inlet concentration of nitrogen oxides is 100-2000ppm, hydrogen / nitrogen oxide mass ratio of 2-6; LHSV reaction (a GHSV) of 1000-60000h_1.

[0017]本发明提供的用于氮氧化物氢气选择还原催化剂可应用于固定源氮氧化物排放后处理,如火电厂烟气脱硝,水泥厂烟气脱硝以及硝酸厂尾气净化过程。 [0017] a nitrogen oxide selective reduction catalyst can be applied to hydrogen stationary sources of nitrogen oxide exhaust after-treatment, flue gas denitrification coal fired power plants, cement plants and the nitric acid plant flue gas denitration process of the present invention, the exhaust gas purifying provided.

[0018]本发明提供的用于氮氧化物氢气选择还原催化剂与现有技术相比,本发明具有的优点和效果如下: [0018] a nitrogen oxide of the present invention provides a hydrogen selective reduction catalyst as compared with the prior art, the present invention has the following advantages and effects:

[0019] 1)催化剂表现出优异的氮氧化物净化效果,氮氧化物净化效率可达75-85%。 [0019] 1) the catalyst exhibits an excellent effect of the nitrogen oxide purification, the purification efficiency of nitrogen oxides of up to 75-85%. 2)催化剂组分绿色无毒,原料广泛而普遍;3)氢选择催化还原氮氧化物反应温度低,大大节约能源。 2) the catalyst component green non-toxic, broad and general feedstock; 3) hydrogen selective catalytic reduction of nitrogen oxides in the reaction temperature is low, significant savings in energy.

附图说明 BRIEF DESCRIPTION

[0020]图1为本发明使用的Pt-Ce/SAPO-34催化剂应用于模拟火电厂烟气脱硝流程及效果示意图。 Pt-Ce [0020] FIG. 1 of the present invention / SAPO-34 catalyst for Simulated Flue Gas of Thermal Power Plant schematic denitration processes and effects.

[0021]图2为本发明pt-Ce/SAP0-34催化剂应用于氢气选择催化还原氮氧化物效果图。 / SAP0-34 hydrogen catalyst for selective catalytic reduction of nitrogen oxides renderings pt-Ce [0021] FIG. 2 of the present invention. [0022]图3为本发明pt-La/ZSM-5催化剂应用于氢气选择催化还原氮氧化物效果图。 [0022] FIG. 3 pt-La / ZSM-5 catalyst for selective catalytic reduction of nitrogen oxides hydrogen renderings of the present invention.

具体实施方式 Detailed ways

[0023] 下述实施例中所涉及的具体实验方法和设备如无特殊说明,均为常规方法或按照制造厂商说明书建议的条件实施。 [0023] Specific experimental methods and apparatus related to the following Examples without special embodiment described, are implemented in accordance with a conventional method or conditions recommended by the manufacturer's instructions. 所涉及的试剂均为市售。 Agents involved are commercially available.

[0024] 实施例i [0024] Example embodiments i

[0025] 1) Pt-Ce/SAPO-34催化剂制备 [0025] 1) Pt-Ce prepared / SAPO-34 catalyst

[0026] 将Ce (N03) 3完全溶于水得到1M的溶液,将己除模板剂的SAP0-34 (Si/Al = 0.1)加入上述溶液中,控制Ce/SAPO-34质量分数为0.02,常温搅拌后于8(TC烘干剩余水分,然后在500°C焙烧6h,得到2%Ce/SAP0-34。以氯铂酸溶液为前驱体,通过等体积渍法在2%Ce/ SAPO-34 中引入0 •5 % Pt,然后在550 °C 焙烧6h,得到0.5 % Pt-2 % Ce/SAPO-34。 [0026] The Ce (N03) 3 was completely dissolved in water to give a 1M solution, in addition to the already templating agent SAP0-34 (Si / Al = 0.1) was added to the above solution, the control Ce / SAPO-34 mass fraction of 0.02, was stirred at room temperature after 8 (TC remaining moisture drying, 500 ° C and then calcined 6h, to give 2% Ce / SAP0-34. chloroplatinic acid solution as precursor by an equal volume blot in 2% Ce / SAPO- introducing 34 0 • 5% Pt, and then calcined at 550 ° C 6h, to give 0.5% Pt-2% Ce / SAPO-34.

[0027] 2)将0 • 5 % Pt-2 % Ce/SAPO-34催化剂通过湿法涂覆于堇青石蜂窝陶瓷基质表面, 0.5 % Pt-2 % Ce/SAPO-34催化剂涂覆量为20 %。 [0027] 2) 0 • 5% Pt-2% Ce / SAPO-34 catalyst is prepared by wet coating cordierite ceramic honeycomb substrate surface, 0.5% Pt-2% Ce / SAPO-34 catalyst coated in an amount of 20 %.

[0028] 3)将0.5 % Pt-2 % Ce/SAf>0-34/堇青石整体式催化剂5g放入长为50cm、内径2cm的不锈钢固定床反应器中,催化剂放在反应器的中部恒温区,反应入口处:氮氧化物= 15〇Oppm;氢气=5〇OOppm;氧气=5 % ;水蒸气=8 % ;二氧化硫=25ppm;反应温度=120-150 °C,反应空速为500001T1。 [0028] 3) 0.5% Pt-2% Ce / SAf> 0-34 / cordierite monolith catalyst placed 5g length 50cm, inner diameter of 2cm stainless steel fixed bed reactor, the catalyst is placed in the middle of the reactor temperature area, the inlet of the reaction: = 15〇Oppm nitrogen oxides; hydrogen = 5〇OOppm; = 5% oxygen; = 8% water vapor; = 25ppm sulfur; reaction temperature = 120-150 ° C, space velocity of 500001T1.

[0029] 4)产物用氮氧化物分析仪与小型质谱仪进行在线分析。 [0029] 4) The product was analyzed by online analyzers and nitrogen oxides miniature mass spectrometer. 所用氮氧化物分析伩型号为瑞士Eco Physics CLD62,质谱仪型号为德国普发Omnistar,催化反应检测结果见图2。 The nitrogen oxides Xin analysis model Switzerland Eco Physics CLD62, German model spectrometer Pfeiffer Omnistar, the detection results shown in Figure 2 the catalytic reaction. [0030]催化结果表明:Pt-Ce/SAP0-34具有优异的H2-SCR性能,入口氮氧化物浓度为1500ppm左右,经过催化净化过程,出口处氮氧化物浓度低至400ppm左右,氮氧化物转化率可达75%。 [0030] The results show that the catalyst: Pt-Ce / SAP0-34 H2-SCR having an excellent performance, the inlet concentration of approximately 1500 ppm of nitrogen oxides, through a catalytic purification process, low concentration of nitrogen oxides at the outlet of about 400 ppm of nitrogen oxides conversion rate of up to 75%.

[0031] 实施例2 [0031] Example 2

[0032] l)Pt-La/ZSM-5 催化剂制备 [0032] l) Pt-La preparation / ZSM-5 Catalyst

[0033] 将La (N〇3) 3完全溶于水得到1M的溶液,将已除模板剂的ZSM-5 (Si/Al = 30)加入上述溶液中,控制La/ZSM-5质量分数为0• 05,常温搅拌后于80°C烘干剩余水分,然后在550°C 焙烧6h,得到5 % La/ZSM-5。 [0033] The La (N〇3) 3 completely soluble in water to give a 1M solution, was ZSM-5 (Si / Al = 30) in addition to the templating agent added to the solution, controlling La / ZSM-5 mass fraction of 0 • 05, stirred at room temperature 80 ° C after drying the residual moisture, and then calcined at 550 ° C 6h, to give 5% La / ZSM-5. 以氯铀酸溶液为前驱体,通过等体积渍法在5 % La/ZSM-5中引入0 • 3 % Pt,然后在550 °C 焙烧h,得到0 • 3 % Pt-5 % La/ZSM-5。 Chlorine uranium acid solution as precursor by an equal volume blot introducing 0 • 3% Pt in 5% La / ZSM-5, and then at 550 ° C calcined H, to give 0 • 3% Pt-5% La / ZSM -5.

[0034] 2)将0• 3%Pt_5%La/ZSM_5催化剂通过直接挤压成型法,得到自支撑整体式催化剂。 [0034] 2) 0 • 3% Pt_5% La / ZSM_5 catalyst by direct extrusion molding, to obtain a self-supporting monolithic catalyst.

[0035] 3)将0 • 3%Pt-5%La/ZSM-5整体式催化剂5g放入长为50cm、内径2cm的不锈钢固定床反应器中,催化剂放在反应器的中部恒温区,反应入口处:氮氧化物= 600pptn;氢气= 2500ppm;氧气=5 % ;水蒸气=10 % ;二氧化硫=20ppm;反应温度=120-150°C,反应空速为20000^1 〇 [0035] 3) 0 • 3% Pt-5% La / ZSM-5 monolithic catalyst into 5g length 50cm, inner diameter of 2cm stainless steel fixed bed reactor, the catalyst temperature in the middle zone of the reactor, the reaction entrance: nitrogen oxides = 600pptn; = 2500 ppm of hydrogen; = 5% oxygen; = 10% water vapor; = 20ppm sulfur; reaction temperature = 120-150 ° C, space velocity of 20,000 square ^ 1

[0036] 4)产物用氮氧化物分析仪与小型质谱仪进行在线分析。 [0036] 4) The product was analyzed by online analyzers and nitrogen oxides miniature mass spectrometer. 所用氮氧化物分析仪型号为Eco The nitrogen oxide analyzer Model Eco

[0037] Physics CLD62,质谱仪型号为德国普发Omnistar,催化反应检测结果见图3。 [0037] Physics CLD62, German model spectrometer Pfeiffer Omnistar, detecting catalytic reaction results shown in Figure 3.

[0038] 催化结果表明:Pt-La/ZSM-5具有优异的H2-SCR性能,入口氮氧化物浓度为600ppm 左右,经过催化净化过程,出口处氮氧化物浓度低至80ppm左右,氮氧化物转化率可达… 85%。 [0038] The results show that the catalyst: Pt-La / ZSM-5 in the H2-SCR having an excellent performance, the inlet concentration of nitrogen oxides is about 600ppm, through a catalytic purification process, low nitrogen oxides concentration at the outlet is about 80ppm, nitrogen oxides ... conversion rate of up to 85%.

Claims (2)

1.一种用于氮氧化物氢气选择还原催化剂的应用方法,其特征在于:该催化剂为0.3% Pt-5 % La/ZSM-5或0 • 5 % Pt-2 % Ce/SAPO-34,步骤为: A hydrogen gas for selecting the application of nitrogen oxides reduction catalyst, wherein: the catalyst is 0.3% Pt-5% La / ZSM-5 or 0 • 5% Pt-2% Ce / SAPO-34, steps:
0.3 % Pt-5 % La/ZSM-5催化剂的制备: 将La (N〇3)3完全溶于水得到1M的溶液,将已除模板剂的ZSM-5,Si/Al = 30,加入上述溶液中,控制La/ZSM-5质量分数为0 • 05,常温搅拌后于8〇°C烘干剩余水分,然后在550r焙烧6h,得到5%La/ZSM-5;以氯铂酸溶液为前驱体,通过等体积渍法在5%La/ZSM—5中引入0.3%Pt,然后在550°C 焙烧6h,得到0.3 % Pt-5 % La/ZSM-5; 将0.3 % Pt-5 % La/ZSM-5催化剂通过直接挤压成型法,得到自支撑整体式催化剂; 将0.3 %Pt-5 % La/ZSM-5整体式催化剂5g放入长为50cm、内径2cm的不锈钢固定床反应器中,催化剂放在反应器的中部丨旦温区,反应入口处:氮氧化物= 600ppm;氨气= 2500ppm; 氧气=5 % ;水蒸气=10 % ;二氧化硫=20ppm;反应温度=120-15(TC,反应空速为20000111; 或催化剂Pt-Ce/SAP0-34的制备: 将Ce (N03) 3完全溶于水得到1M的溶液,将已除模板剂的SAP0-34,Si/Al = 0.1,加入上述溶液中,控制Ce/SA Preparation of 0.3% Pt-5% La / ZSM-5 Catalyst: The La (N〇3) 3 completely soluble in water to give a 1M solution, in addition to the above-mentioned templating agent is ZSM-5, Si / Al = 30, was added solution, controlling La / ZSM-5 content of 0 • 05, stirred at room temperature 8〇 ° C after drying the residual moisture, and then calcined at 550r 6h, to give 5% La / ZSM-5; to a solution of chloroplatinic acid precursor, volume blot incorporated by like 5% La / ZSM-5 in a 0.3% Pt, and then at 550 ° C calcined 6h, to give 0.3% Pt-5% La / ZSM-5; the 0.3% Pt-5% La / ZSM-5 catalyst is prepared by direct extrusion molding, to obtain a self-supporting monolithic catalyst; and 0.3% Pt-5% La / ZSM-5 monolithic catalyst into 5g length 50cm, 2cm internal diameter stainless steel fixed bed reactor the catalyst in the reactor Shu denier central zone, the inlet of the reaction: = 600ppm of nitrogen oxides; = 2500 ppm of ammonia; = 5% oxygen; = 10% water vapor; = 20ppm sulfur; reaction temperature = 120-15 (the TC, space velocity is 20000111; or preparation of the catalyst Pt-Ce / SAP0-34: a mixture of Ce (N03) 3 was completely dissolved in water to give a 1M solution, has been eliminated SAP0-34 templating agent, Si / Al = 0.1, was added to the above solution, the control Ce / SA PO-34质量分数为0 • 02,常温搅拌后于80°C烘干剩余水分,然后在500°C 焙烧6h,得到2 % Ce/SAP0-34;以氯铂酸溶液为前驱体,通过等体积渍法在2 %Ce/SAPO-34中引入0.5 % Pt,然后在550°C 焙烧6h,得到0.5 % Pt-2 % Ce/SAPO-34; 将0.5 % Pt-2 % Ce/SAPO-34催化剂通过湿法涂覆于堇青石蜂窝陶瓷基质表面,0.5 % Pt-2%Ce/SAP0-34催化剂涂覆量为20% ; 将0.5%?1:-2%06/5八?0-34/堇青石整体式催化剂5§放入长为50(;111、内径2〇11的不锈钢固定床反应器中,催化剂放在反应器的中部恒温区,反应入口处:氮氧化物=1500ppni;氢气=5000ppm;氧气=5 % ;水蒸气=8 % ;二氧化硫=25ppm;反应温度=120-150 °C,反应空速为50000h-1。 PO-34 mass fraction of 0 • 02, stirred at room temperature 80 ° C after drying the residual moisture, and then 500 ° C and calcined 6h, to give 2% Ce / SAP0-34; chloroplatinic acid solution as precursor by other volume blot introduction of 0.5% Pt on 2% Ce / SAPO-34, and then at 550 ° C calcined 6h, to give 0.5% Pt-2% Ce / SAPO-34; the 0.5% Pt-2% Ce / SAPO-34 catalyst is prepared by wet coating cordierite ceramic honeycomb substrate surface, 0.5% Pt-2% Ce / SAP0-34 catalyst coating amount is 20%; 0.5% 1: 2% 06/5 eight 0-34?? / cordierite monolith catalyst placed 5§ length 50 (; 111, internal diameter stainless steel fixed bed reactor 2〇11, the catalyst placed in the middle temperature zone of the reactor, the inlet of the reaction: nitrogen oxides = 1500ppni; hydrogen = 5000 ppm of; = 5% oxygen; = 8% water vapor; = 25ppm sulfur; reaction temperature = 120-150 ° C, space velocity of 50000h-1.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08131838A (en) * 1994-11-10 1996-05-28 Honda Motor Co Ltd Catalyst for purification of exhaust gas
JP2003190782A (en) * 2001-12-27 2003-07-08 Mitsubishi Electric Corp Adsorption removing agent for nitrogen oxide and the removing method
CN101730575A (en) * 2007-04-26 2010-06-09 约翰逊马西有限公司 transition metal/zeolite scr catalysts
CN103619478A (en) * 2011-02-28 2014-03-05 庄信万丰股份有限公司 High-temperature scr catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08131838A (en) * 1994-11-10 1996-05-28 Honda Motor Co Ltd Catalyst for purification of exhaust gas
JP2003190782A (en) * 2001-12-27 2003-07-08 Mitsubishi Electric Corp Adsorption removing agent for nitrogen oxide and the removing method
CN101730575A (en) * 2007-04-26 2010-06-09 约翰逊马西有限公司 transition metal/zeolite scr catalysts
CN103619478A (en) * 2011-02-28 2014-03-05 庄信万丰股份有限公司 High-temperature scr catalyst

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