铁基SCR脱硝催化剂改性研究
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摘要
氮氧化物是一种主要的大气污染物。随着国民经济的发展,我国氮氧化物排放总量逐年增加,污染日益严重,近十年来,我国部分地区的酸雨污染正由过去的硫酸型向硫酸和硝酸复合型转变。作为我国氮氧化物的主要排放源,对燃煤火电厂氮氧化物排放减量化迫在眉睫。选择性催化还原法(Selective Catalytic Reduction, SCR)由于其技术相对成熟且脱除NOx效率高,己成为燃煤发电厂主流的脱硝技术。目前,钒钨钛催化剂因具有较好的脱硝效率和抗二氧化硫毒化性能,己被广泛应用于脱除燃煤火电厂等固定源所排放的氮氧化物,但其存在脱硝温度高,脱硝成本高,钒易流失,造成二次污染等缺点；因此急需开发适合我国国情的高效、低污染、脱硝成本低的SCR脱硝技术。与钒钨钛催化剂相比,铁基催化剂具有无毒、脱硝成本低廉等优点,为一种极具开发潜力的SCR脱硝催化剂；但其低温脱硝活性偏低,限制了其大规模工业应用。针对铁基催化剂SCR脱硝活性温度偏高等缺点,本文从掺杂助剂及改进催化剂制备方法两方面来优化其中低温SCR脱硝性能；使其脱硝温度窗口向低温拓宽；并揭示助剂掺杂及催化剂制备方法的优化对铁基催化剂SCR脱硝的促进机理。
本文利用共沉淀法制备了高脱硝活性的铁基催化剂,探讨了掺杂铈等助剂及对催化剂前驱体进行微波水热处理对铁基催化剂SCR脱硝活性的影响规律；系统考察了铁基催化剂SCR脱硝特性,构建其脱硝反应模型；揭示了掺杂铈等助剂及微波水热处理对铁基催化剂中低温SCR脱硝性能的优化机理。
(1)沉淀剂种类对共沉淀法制备的铁铈复合氧化物催化剂SCR脱硝性能具有重要影响,与碱金属沉淀剂相比,氨基沉淀剂制备的铁铈复合氧化物催化剂表现出良好的SCR脱硝性能。通过对不同沉淀剂制备的铁铈复合氧化物催化剂及前驱体进行IR和XRD测试分析可知：NaOH和Na2CO3等碱金属沉淀剂会促使铁铈复合氧化物催化剂前驱体中形成α-FeOOH和α-Fe2O3,而氨基沉淀剂会抑制前驱体中α-FeOOH和α-Fe2O3的形成,促使铁、铈组分在铁铈复合氧化物催化剂中形成固溶体；N2吸附结果也表明：相比于碱金属沉淀剂,氨基沉淀剂制备的铁铈复合氧化物催化剂具有大的比表面积和比孔容,能为SCR脱硝反应提供大量活性位点,从而促使其具有良好中低温SCR脱硝活性。
(2)以NH4OH为沉淀剂,利用共沉淀法掺杂铈氧化物能够提高铁氧化物的中低温SCR脱硝性能；铈掺杂量通过影响铁铈复合氧化物催化剂中铁、铈元素的相互作用而对其SCR脱硝活性产生影响。实验研究表明：当Ce/(Ce+Fe)摩尔比x由0.025增至0.10,铁铈复合氧化物催化剂低温SCR脱硝性能逐渐增大,而其高温SCR脱硝性能先增大后减少,当Ce/(Ce+Fe)摩尔比x为0.05时,铁铈复合氧化物催化剂具有最宽的脱硝温度窗口。
(3)借助XRD、N2吸附和TPD等催化剂表征手段,揭示了铈掺杂对铁氧化物中低温SCR脱硝的促进机理。研究发现：利用共沉淀法掺杂的铈氧化物与铁氧化物存在较好相互作用,形成固溶体；使铁铈复合氧化物催化剂表面形成高活性的吸附氧和晶格氧,提高了铁氧化物的低温催化氧化NO为N02性能；当增大烟气中N02/NOx,至0.3时,可分别提高Fe203和Fe0.95Ce0.050z催化剂150℃时的NOx转化率55.9和19.9个百分点；且掺杂铈氧化物会优化铁氧化物的微观孔隙结构,促使其平均孔径减少,使其比表面积和比孔容增大；掺杂0.05摩尔比的铈氧化物会促使铁氧化物比表面积和比孔容由44.53m2/g和0.205cm3/g增至107.25m2/g和0.285cm3/g,分别增大了1.4倍和1.44倍,同时,掺杂铈氧化物会促使铁氧化物表面形成更多Lewis酸位,提升了铁氧化物的低温吸附NH3和NO性能,从而促进了铁氧化物中低温SCR脱硝性能。
(4)利用积分实验系统,详细考察了煅烧温度、空速比、活性温度、O2浓度和NH3浓度等操作参数对铁铈复合氧化物催化剂SCR脱硝特性的影响规律。研究结果表明：合适的煅烧温度对铁铈复合氧化物催化剂SCR脱硝性能非常关键；当煅烧温度高于其前驱体完全分解温度时,会导致α-Fe2O3从铁铈复合氧化物中析出,使其比表面积和比孔容减少,抑制了铈掺杂对铁氧化物SCR脱硝的促进作用；合适的煅烧温度为400℃。氧在铁铈复合氧化物催化剂SCR脱硝反应中起着重要的作用；掺杂铈氧化物会促使铁氧化物表面形成高活性的吸附氧和品格氧,促使其在无气态O2条件下表现出较高的SCR脱硝性能；且气态O2易使铁铈复合氧化物催化剂表面快速形成吸附氧和晶格氧,参与到SCR反应中,从而提高铁铈复合氧化物催化剂的脱硝活性；当烟气中02浓度低于1%时,增加02浓度会促使铁铈复合氧化物催化剂的脱硝效率迅速上升,但当烟气中O2浓度高于3%后,O2浓度对其NOx脱除率的影响不明显；随着烟气中[NH3]/[NO]由0增至1.0,催化剂脱硝效率先迅速增大,后增速减缓,进一步增大烟气中[NH3]/[NO]并不会提高其脱硝效率。
(5)借助微分实验系统探讨了Fe0.95Ce0.05Oz催化剂SCR脱硝反应动力学,构建了其催化脱硝动力学模型。在本文的研究工况下,Fe0.95Ce0.05Oz催化剂的NO、NH3和O2的反应级数依次为1.0,0和0.5。175～275℃范围内其催化反应活化能为42.6kJ/mol。
(6)对铁铈复合氧化物催化剂进行过渡金属掺杂,探讨掺杂第三种过渡金属离子对Fe0.95Ce0.05Oz催化剂SCR脱硝性能的影响规律。研究结果表明：与W、Mo和Zr相比,掺杂Ti能够明显提高Fe0.95Ce0.05Oz催化剂的低温SCR脱硝性能,促使其脱硝温度窗口向低温偏移,其中,合适的钛掺杂摩尔比(Ti/(Ti+Fe+Ce))为0.15。
(7)掺杂的钛与铁、铈元素存在较好的相互作用,细化铁铈复合氧化物催化剂的孔径,使其比表面积和比孔容增大；降低铁铈复合氧化物催化剂表面铁、铈活性组分浓度,提高了铁、铈组分的分散度；掺杂钛会改变铁铈复合氧化物表面结构,增强其表面弱酸Lewis酸位,提高NH3还原剂在铁铈复合氧化物催化剂表面的低温吸附；掺杂钛也会促使铁铈复合氧化物表面吸附氧浓度增大,增强其表面低温催化氧化NO为NO2性能,从而优化了铁铈复合氧化物催化剂的低温SCR脱硝性能。
(8)将微波水热处理引入到铁铈钛复合氧化物催化剂的制备中,可进一步提高其低温SCR脱硝性能,使其脱硝温度窗口向低温偏移；且微波水热处理的低温优化效果与铁铈钛复合氧化物催化剂中Fe/Ti摩尔比密切相关,Fe/Ti摩尔比越小,微波水热处理对催化剂脱硝性能的优化效果越强；交替微波加热方式和微波辐射时间会影响微波水热处理对铁铈钛复合氧化物催化剂SCR脱硝性能的低温优化。在相同微波辐射时间条件下,当交替微波加热方式由P30逐渐变为P80,微波水热处理对铁铈钛复合氧化物催化剂低温SCR脱硝的促进作用降低；在P30交替微波加热方式下；微波辐射15min使铁铈钛复合氧化物催化剂低温SCR脱硝活性最强。
(9)微波水热处理会加速铁铈钛复合氧化物催化剂前驱体的晶化速率；调整其微观孔隙结构,使其平均孔径和比孔容增大；并加强了铁铈钛复合氧化物催化剂中铁、钛组分的相互作用,形成铁钛复合氧化物。微波水热处理会促使铁铈钛复合氧化物催化剂表面Ce3+/Ce4+比值增加,促使其表面Ce3+离子相对含量增加,增强了Ce4+和Ce3+之间的氧化还原转换,提高铁铈钛复合氧化物催化剂表面的晶格氧缺陷值,促使其表面晶格氧浓度增加,增强了其氧化还原性能；并使铁铈复合氧化物催化剂表面Lewis酸性增强,提高NH3在其表面的低温吸附,从而优化了铁基催化剂低温SCR脱硝性能。
Nitric oxides(NOx) are a major pollution which is severe harmful to environment. In our country, the total amount of NOx increases year by year with the development of the national economy, and the pollution caused by NOx emission became severe gradually. In recent ten years, the type of acid rain changed from the sulfuric acid type to the composite of sulfuric acid and nitric acid by degrees in some regions of China. As a major source of NOx emission, it is urgent to reduce NOx in exhaust flue gas from coal-fired power plant. Due to being a relatively mature with high NOx removal efficiency, selective catalytic reduction (SCR) is a well-known mainstream technology for NO*abatement emitted from coal-fired power plant. For the moment, V2O5/TiO2catalyst promoted by MoO3or WO3is the most effectively and widely commercial SCR catalyst used to reduce the nitric oxides emitted from the station source as the coal-fired power plant owing to the high activity and the durability to sulfur compounds. However, V2O5-WO3(MoO3)/TiO2catalyst would bring about some disadvantages in practical use, such as high denitrification temperature, high cost, and toxicity of vanadium pent-oxide to environment and human health. Therefore, it is in dire need of developing a novel SCR technology with high activity, low cost, and absence of toxicity which is suitable for the national conditions of China. Compared with the traditional V2O5-WO3(MoO3)/TiO2catalyst, iron-based catalyst has some advantages with low cost and absence of toxicity, and is a potential catalyst for SCR of NOx Nevertheless, iron-based catalyst shows lower activity at relatively low-temperature, which restricts its large-scare industrial application. On account of higher reaction temperature for iron-based catalyst, the purpose of this paper was to optimize its low-temperature SCR activity through doping other metal oxide and improving the preparation method of catalyst, and to make its SCR reaction temperature window shifted to the low-temperature. Finally, the promotional mechanisms for doping other metal oxide and improving the preparation method of catalyst have also been studied and given in paper.
In this paper, we firstly obtained iron-based catalyst prepared through co-precipitation method showing high SCR activity. The effects of doping the additives as cerium oxide and the hydrothermal treatment of catalyst precursor by using microwave radiation on SCR activity over iron-based catalysts were investigated. The denitrification characteritics of iron-based catalyst were also under systematic investigation, and its denitration reaction model was founded. Finally, we gave the promotion mechanisms for doping the additives as cerium oxide and the hydrothermal treatment of catalyst precursor by using microwave radiation on SCR activity over iron-based catalysts.
(1) The types of precipitants showed an important effect on SCR activity over iron-based catalysts prepared through co-precipitation method. Compared with the alkali metal precipitants, the catalysts prepared by using amino precipitants showed high SCR activity. From the IR and XRD results for iron-cerium mixed oxides catalysts and their precursors prepared with different precipitants, it can be seen that: the alkali metal precipitants such as NaOH and Na2CO3could promot the formation of α-FeOOH and α-Fe2O3in the precursors of iron-cerium mixed oxides catalysts. However, amino precipitants would depress the formation of α-FeOOH and α-Fe2O3in the precursors of iron-cerium mixed oxides catalysts, and made iron oxide and cerium oxide to form the solid solution in iron-cerium mixed oxides catalysts. The results of N2adsorption for different catalysts also indicated that the iron-cerium mixed oxides catalysts prepared with amino precipitants had large BET surface areas and pore volumes compared to the catalysts prepared with alkali metal precipitants. The larger BET surface areas and pore volumes could provide huge amount of reactive sites for SCR reaction, and thereby promoted the catalysts showed high medium-low temperature SCR activity.
(2) The doping of cerium oxide could enhance the medium-low temperature SCR activity of iron oxide catalyst prepared through co-precipitation with NH4OH as the precipitant. The cerium doping amount showed an effect on SCR activity over iron-cerium mixed oxide catalysts through influencing the interaction of cerium oxide and iron oxide in catalysts. The results of research indicated that when the
molar ratio of Ce/(Ce+Fe) was increased from0.025to0.1, the low-temperature SCR activity over iron-cerium mixed oxide catalysts increased gradually, meanwhile, its high-temprature SCR activity firstly increased and then decreased. The iron-cerium mixed oxide catalysts at the molar ratio of Ce/(Ce+Fe) being0.05showed the most wide temperature window for SCR reaction.
(3) By means of the catalyst characterizations such as XRD, N2adsorption, TPD and so on, the promotion mechanism by doping cerium oixde on SCR activity over iron oxide catalyst was revealed. The results indicated that the doping cerium oxide could interact well with iron oxide in catalysts prepared though co-precipitation method, and led to the formation of the solid solution between them. The interaction between iron oxide and cerium oxide promoted a large mount of adsorbed oxygen and lattice oxygen with high activity in catalysts, and improved the low-temperature activity of oxidizing NO to NO2over iron oxide catalyst. Meanwhile, when the molar ratio of NO2/NOx was increased to0.3in the simulated flue gas, the conversions of NOx over Fe2O3and Fe0.95Ce0.05O2catalysts at150℃were enhanced by55.9%and19.9%, respectively. The doping of cerium oxide could optimize the microscopic pore structure of iron oxide, made its pore size become smaller, and enhanced the BET surface area and pore volume of iron oxide. The BET surface area and the pove volume of Fe2O3were enlarged from44.53m2/g and0.205cm3/g to107.25m2/g and0.285cm3/g after doping cerium oxide with the molar ratio of Ce/(Ce+Fe) being0.05, and were enhanced1.4and1.44times, respectively. At the same time, The doping of cerium oxide could promote the formation of Lewis acid over iron oxide, which improved the low-temperature adsorption of NH3and NO over iron oxide catalyst, thereby enhanced its medium-low temperature SCR activity.
(4) The effects of operation parameters such as calcination temperature, Gas hourly space velocity(GHSV), O2concentration and NH3concentration were examined detailly in the intergral experiment system. And the research results demonstrated that the suitable calcination temperature was vital to the SCR activity over iron-cerium mixed oxide catalyst. When the calcination temperature is higher than the complete decompotition temperature for the precursors of iron-cerium mixed oxide catalyst, higher temperature would lead α-Fe2O3separated out from iron-cerium mixed oxide catalyst, and made the BET surface area and the pore volume of catalyst decrease, thereby depressed the promotion of doping cerium oxide on SCR activity over iron oxide. The suitable calcinations temperature was400℃. Oxygen played an important role on SCR activity over iron-cerium mixed oxide catalysts. The doping of cerium oxide could promote the formation of adsorbed oxygen and lattice oxygen with high activity, which made the iron-cerium mixed oxide catalyst show high SCR activity in the absence of gaseous O2within the simulated gas. Meanwhile, gaseous O2could oxidize the surface of iron-cerium mixed oxide catalyst and promoted the formation of absorbed and lattice oxygen on it, thereby enchanced the SCR activity over iron-cerium mixed oxide catalyst. When the concentration of gaseous O2in the simulated gas was lower than1%, the improvement of gaseous O2could lead the SCR activity of iron-cerium mixed oxide catalyst increase sharply. However, the concentration of gaseous O2showed no influence almost on SCR activity of catalyst when the concentration of gaseous O2was higher than3.0%. The SCR activity of catalyst firstly increased sharply and then slowly with the molar ratio of NH3/NO in the simulated gas increasing from0to1, and the SCR activity of catalyst could be not enhanced again by further improving the molar ratio of NH3/NO.
(5) The kinetics of SCR over Fe0.95Ce0.05O2catalyst had been studied in a differential system, and its catalytic kinetics model for SCR reaction was founded. Under the reaction conditions in this paper, the rate of NO conversion on Fe0.95Ce0.05O2is first-order with respect to NO, zero-order with respect to NH3and nearly0.5-order with respect to O2. The apparent activation energy of the NH3-SCR reaction was42.6kJ/mol at175～275℃.
(6) By doping other transition metal oxide into iron-cerium mixed oxide catalyst, and we investigated the effect of doping another transition metal oxide on SCR activity over iron-cerium mixed oxide catalyst. The research results indicated that, compared with W、Mo and Zr, the doping of Ti could obviously enhance the low-temperature SCR activity over iron-cerium mixed oxide catalyst, and made its reactive temperature window of SCR shift to the low-temperature region. Thereinto, the suitable molar ratio of Ti/(Ti+Fe+Ce) is0.15.
(7) There existed better interaction between the doping titanium with other elements as iron and cerium, which could refine the pore diameter of iron-cerium mixed oxide catalyst, and enlarged the BET surface area and pore volume of catalyst. The doping of titanium led the concentration of iron and cerium elements on the surface of catalyst decrease, and enhanced the dispersion of iron and cerium groups on the surface of catalyst. The doping of titanium might change the surface structure of iron-cerium mixed oxide, enhanced the weak Lewis acid, and improved the low-temperature adsorption of NH3over catalyst. At the same time, the adsorted oxygen concentration over iron-cerium mixed oxide catalyst could also be improved after doping titanium which enhanced the low-temperature catalytic oxidation of NO to NO2over catalyst, and thereby promoted the low-temperature SCR activity over iron-cerium mixed oxide catalyst.
(8) The SCR activity of iron-cerium-titanium mixed oxide catalyst could be enhanced further by introducing microwave hydrothermal treatment into the preparation of catalyst which could make the reactive SCR temperature window shift to the low-temperature region. Meanwhile, the promotional effect of microwave hydrothermal treatment on low-temperature SCR activity is closely related to the molar ratio of Fe and Ti in the mixed oxide catalyst. When the molar ratio of Fe and Ti is smaller, the promotion of microwave hydrothermal treatment is higher. The alternate microwave heating method and the microwave iddiation time played an important role on the promotion of low-temperature SCR activity over iron-cerium-titanium mixed oxide catalyst by using microwave to treat the precursors of catalyst. Under the same microwave iddiation time, when the alternate microwave heating method changed from P30to P80, the promotional effect of microwave hydrothermal treatment on low-temperature SCR activity over iron-cerium-titanium mixed oxide catalyst decreased gruadually. Under the condition of P30, the promotion of microwave hydrothermal treatment was the highest when the microwave iddiation time is15min.
(9) Microwave hydrothermal treatment could accelerate the crystallite rate of the precursors for iron-cerium-titanium mixed oxide catalysts, adjusted the microscopic pore structure of catalyst, and enlarged the pore diameter and the pore volume of iron-cerium-titanium mixed oxide catalyst. Microwave hydrothermal treatment could strengthen the interaction between iron oxide and titanium oxide in mixed oxide, and promoted the formation of iron-titantium composite oxide. At the same time, the molar ratio of Ce3+/Ce4+on the surface of mixed oxide catalyst could be enhanced after microwave hydrothermal treatment, and improved the relative concentration of Ce3+on the surface of catalyst which enhanced the reduction and oxidation conversion between Ce3+and Ce+, and improved the defect value of lattice oxygen on the surface of iron-cerium-titanium mixed oxide catalyst. Therefore, the concentration of lattice oxygen over catalyst could be improved after microwave hydrothermal treatment, and enhanced the oxidation and reduction properties of catalyst. At the same time, microwave hydrothermal treatment enhanced the Lewis acid of the mixed oxide catalyst, and improved the low-temperature adsorption of NH3over catalyst, thereby enhanced the low-temperature SCR activity over iron-based catalyst.
本文利用共沉淀法制备了高脱硝活性的铁基催化剂,探讨了掺杂铈等助剂及对催化剂前驱体进行微波水热处理对铁基催化剂SCR脱硝活性的影响规律；系统考察了铁基催化剂SCR脱硝特性,构建其脱硝反应模型；揭示了掺杂铈等助剂及微波水热处理对铁基催化剂中低温SCR脱硝性能的优化机理。
(1)沉淀剂种类对共沉淀法制备的铁铈复合氧化物催化剂SCR脱硝性能具有重要影响,与碱金属沉淀剂相比,氨基沉淀剂制备的铁铈复合氧化物催化剂表现出良好的SCR脱硝性能。通过对不同沉淀剂制备的铁铈复合氧化物催化剂及前驱体进行IR和XRD测试分析可知：NaOH和Na2CO3等碱金属沉淀剂会促使铁铈复合氧化物催化剂前驱体中形成α-FeOOH和α-Fe2O3,而氨基沉淀剂会抑制前驱体中α-FeOOH和α-Fe2O3的形成,促使铁、铈组分在铁铈复合氧化物催化剂中形成固溶体；N2吸附结果也表明：相比于碱金属沉淀剂,氨基沉淀剂制备的铁铈复合氧化物催化剂具有大的比表面积和比孔容,能为SCR脱硝反应提供大量活性位点,从而促使其具有良好中低温SCR脱硝活性。
(2)以NH4OH为沉淀剂,利用共沉淀法掺杂铈氧化物能够提高铁氧化物的中低温SCR脱硝性能；铈掺杂量通过影响铁铈复合氧化物催化剂中铁、铈元素的相互作用而对其SCR脱硝活性产生影响。实验研究表明：当Ce/(Ce+Fe)摩尔比x由0.025增至0.10,铁铈复合氧化物催化剂低温SCR脱硝性能逐渐增大,而其高温SCR脱硝性能先增大后减少,当Ce/(Ce+Fe)摩尔比x为0.05时,铁铈复合氧化物催化剂具有最宽的脱硝温度窗口。
(3)借助XRD、N2吸附和TPD等催化剂表征手段,揭示了铈掺杂对铁氧化物中低温SCR脱硝的促进机理。研究发现：利用共沉淀法掺杂的铈氧化物与铁氧化物存在较好相互作用,形成固溶体；使铁铈复合氧化物催化剂表面形成高活性的吸附氧和晶格氧,提高了铁氧化物的低温催化氧化NO为N02性能；当增大烟气中N02/NOx,至0.3时,可分别提高Fe203和Fe0.95Ce0.050z催化剂150℃时的NOx转化率55.9和19.9个百分点；且掺杂铈氧化物会优化铁氧化物的微观孔隙结构,促使其平均孔径减少,使其比表面积和比孔容增大；掺杂0.05摩尔比的铈氧化物会促使铁氧化物比表面积和比孔容由44.53m2/g和0.205cm3/g增至107.25m2/g和0.285cm3/g,分别增大了1.4倍和1.44倍,同时,掺杂铈氧化物会促使铁氧化物表面形成更多Lewis酸位,提升了铁氧化物的低温吸附NH3和NO性能,从而促进了铁氧化物中低温SCR脱硝性能。
(4)利用积分实验系统,详细考察了煅烧温度、空速比、活性温度、O2浓度和NH3浓度等操作参数对铁铈复合氧化物催化剂SCR脱硝特性的影响规律。研究结果表明：合适的煅烧温度对铁铈复合氧化物催化剂SCR脱硝性能非常关键；当煅烧温度高于其前驱体完全分解温度时,会导致α-Fe2O3从铁铈复合氧化物中析出,使其比表面积和比孔容减少,抑制了铈掺杂对铁氧化物SCR脱硝的促进作用；合适的煅烧温度为400℃。氧在铁铈复合氧化物催化剂SCR脱硝反应中起着重要的作用；掺杂铈氧化物会促使铁氧化物表面形成高活性的吸附氧和品格氧,促使其在无气态O2条件下表现出较高的SCR脱硝性能；且气态O2易使铁铈复合氧化物催化剂表面快速形成吸附氧和晶格氧,参与到SCR反应中,从而提高铁铈复合氧化物催化剂的脱硝活性；当烟气中02浓度低于1%时,增加02浓度会促使铁铈复合氧化物催化剂的脱硝效率迅速上升,但当烟气中O2浓度高于3%后,O2浓度对其NOx脱除率的影响不明显；随着烟气中[NH3]/[NO]由0增至1.0,催化剂脱硝效率先迅速增大,后增速减缓,进一步增大烟气中[NH3]/[NO]并不会提高其脱硝效率。
(5)借助微分实验系统探讨了Fe0.95Ce0.05Oz催化剂SCR脱硝反应动力学,构建了其催化脱硝动力学模型。在本文的研究工况下,Fe0.95Ce0.05Oz催化剂的NO、NH3和O2的反应级数依次为1.0,0和0.5。175～275℃范围内其催化反应活化能为42.6kJ/mol。
(6)对铁铈复合氧化物催化剂进行过渡金属掺杂,探讨掺杂第三种过渡金属离子对Fe0.95Ce0.05Oz催化剂SCR脱硝性能的影响规律。研究结果表明：与W、Mo和Zr相比,掺杂Ti能够明显提高Fe0.95Ce0.05Oz催化剂的低温SCR脱硝性能,促使其脱硝温度窗口向低温偏移,其中,合适的钛掺杂摩尔比(Ti/(Ti+Fe+Ce))为0.15。
(7)掺杂的钛与铁、铈元素存在较好的相互作用,细化铁铈复合氧化物催化剂的孔径,使其比表面积和比孔容增大；降低铁铈复合氧化物催化剂表面铁、铈活性组分浓度,提高了铁、铈组分的分散度；掺杂钛会改变铁铈复合氧化物表面结构,增强其表面弱酸Lewis酸位,提高NH3还原剂在铁铈复合氧化物催化剂表面的低温吸附；掺杂钛也会促使铁铈复合氧化物表面吸附氧浓度增大,增强其表面低温催化氧化NO为NO2性能,从而优化了铁铈复合氧化物催化剂的低温SCR脱硝性能。
(8)将微波水热处理引入到铁铈钛复合氧化物催化剂的制备中,可进一步提高其低温SCR脱硝性能,使其脱硝温度窗口向低温偏移；且微波水热处理的低温优化效果与铁铈钛复合氧化物催化剂中Fe/Ti摩尔比密切相关,Fe/Ti摩尔比越小,微波水热处理对催化剂脱硝性能的优化效果越强；交替微波加热方式和微波辐射时间会影响微波水热处理对铁铈钛复合氧化物催化剂SCR脱硝性能的低温优化。在相同微波辐射时间条件下,当交替微波加热方式由P30逐渐变为P80,微波水热处理对铁铈钛复合氧化物催化剂低温SCR脱硝的促进作用降低；在P30交替微波加热方式下；微波辐射15min使铁铈钛复合氧化物催化剂低温SCR脱硝活性最强。
(9)微波水热处理会加速铁铈钛复合氧化物催化剂前驱体的晶化速率；调整其微观孔隙结构,使其平均孔径和比孔容增大；并加强了铁铈钛复合氧化物催化剂中铁、钛组分的相互作用,形成铁钛复合氧化物。微波水热处理会促使铁铈钛复合氧化物催化剂表面Ce3+/Ce4+比值增加,促使其表面Ce3+离子相对含量增加,增强了Ce4+和Ce3+之间的氧化还原转换,提高铁铈钛复合氧化物催化剂表面的晶格氧缺陷值,促使其表面晶格氧浓度增加,增强了其氧化还原性能；并使铁铈复合氧化物催化剂表面Lewis酸性增强,提高NH3在其表面的低温吸附,从而优化了铁基催化剂低温SCR脱硝性能。
Nitric oxides(NOx) are a major pollution which is severe harmful to environment. In our country, the total amount of NOx increases year by year with the development of the national economy, and the pollution caused by NOx emission became severe gradually. In recent ten years, the type of acid rain changed from the sulfuric acid type to the composite of sulfuric acid and nitric acid by degrees in some regions of China. As a major source of NOx emission, it is urgent to reduce NOx in exhaust flue gas from coal-fired power plant. Due to being a relatively mature with high NOx removal efficiency, selective catalytic reduction (SCR) is a well-known mainstream technology for NO*abatement emitted from coal-fired power plant. For the moment, V2O5/TiO2catalyst promoted by MoO3or WO3is the most effectively and widely commercial SCR catalyst used to reduce the nitric oxides emitted from the station source as the coal-fired power plant owing to the high activity and the durability to sulfur compounds. However, V2O5-WO3(MoO3)/TiO2catalyst would bring about some disadvantages in practical use, such as high denitrification temperature, high cost, and toxicity of vanadium pent-oxide to environment and human health. Therefore, it is in dire need of developing a novel SCR technology with high activity, low cost, and absence of toxicity which is suitable for the national conditions of China. Compared with the traditional V2O5-WO3(MoO3)/TiO2catalyst, iron-based catalyst has some advantages with low cost and absence of toxicity, and is a potential catalyst for SCR of NOx Nevertheless, iron-based catalyst shows lower activity at relatively low-temperature, which restricts its large-scare industrial application. On account of higher reaction temperature for iron-based catalyst, the purpose of this paper was to optimize its low-temperature SCR activity through doping other metal oxide and improving the preparation method of catalyst, and to make its SCR reaction temperature window shifted to the low-temperature. Finally, the promotional mechanisms for doping other metal oxide and improving the preparation method of catalyst have also been studied and given in paper.
In this paper, we firstly obtained iron-based catalyst prepared through co-precipitation method showing high SCR activity. The effects of doping the additives as cerium oxide and the hydrothermal treatment of catalyst precursor by using microwave radiation on SCR activity over iron-based catalysts were investigated. The denitrification characteritics of iron-based catalyst were also under systematic investigation, and its denitration reaction model was founded. Finally, we gave the promotion mechanisms for doping the additives as cerium oxide and the hydrothermal treatment of catalyst precursor by using microwave radiation on SCR activity over iron-based catalysts.
(1) The types of precipitants showed an important effect on SCR activity over iron-based catalysts prepared through co-precipitation method. Compared with the alkali metal precipitants, the catalysts prepared by using amino precipitants showed high SCR activity. From the IR and XRD results for iron-cerium mixed oxides catalysts and their precursors prepared with different precipitants, it can be seen that: the alkali metal precipitants such as NaOH and Na2CO3could promot the formation of α-FeOOH and α-Fe2O3in the precursors of iron-cerium mixed oxides catalysts. However, amino precipitants would depress the formation of α-FeOOH and α-Fe2O3in the precursors of iron-cerium mixed oxides catalysts, and made iron oxide and cerium oxide to form the solid solution in iron-cerium mixed oxides catalysts. The results of N2adsorption for different catalysts also indicated that the iron-cerium mixed oxides catalysts prepared with amino precipitants had large BET surface areas and pore volumes compared to the catalysts prepared with alkali metal precipitants. The larger BET surface areas and pore volumes could provide huge amount of reactive sites for SCR reaction, and thereby promoted the catalysts showed high medium-low temperature SCR activity.
(2) The doping of cerium oxide could enhance the medium-low temperature SCR activity of iron oxide catalyst prepared through co-precipitation with NH4OH as the precipitant. The cerium doping amount showed an effect on SCR activity over iron-cerium mixed oxide catalysts through influencing the interaction of cerium oxide and iron oxide in catalysts. The results of research indicated that when the
molar ratio of Ce/(Ce+Fe) was increased from0.025to0.1, the low-temperature SCR activity over iron-cerium mixed oxide catalysts increased gradually, meanwhile, its high-temprature SCR activity firstly increased and then decreased. The iron-cerium mixed oxide catalysts at the molar ratio of Ce/(Ce+Fe) being0.05showed the most wide temperature window for SCR reaction.
(3) By means of the catalyst characterizations such as XRD, N2adsorption, TPD and so on, the promotion mechanism by doping cerium oixde on SCR activity over iron oxide catalyst was revealed. The results indicated that the doping cerium oxide could interact well with iron oxide in catalysts prepared though co-precipitation method, and led to the formation of the solid solution between them. The interaction between iron oxide and cerium oxide promoted a large mount of adsorbed oxygen and lattice oxygen with high activity in catalysts, and improved the low-temperature activity of oxidizing NO to NO2over iron oxide catalyst. Meanwhile, when the molar ratio of NO2/NOx was increased to0.3in the simulated flue gas, the conversions of NOx over Fe2O3and Fe0.95Ce0.05O2catalysts at150℃were enhanced by55.9%and19.9%, respectively. The doping of cerium oxide could optimize the microscopic pore structure of iron oxide, made its pore size become smaller, and enhanced the BET surface area and pore volume of iron oxide. The BET surface area and the pove volume of Fe2O3were enlarged from44.53m2/g and0.205cm3/g to107.25m2/g and0.285cm3/g after doping cerium oxide with the molar ratio of Ce/(Ce+Fe) being0.05, and were enhanced1.4and1.44times, respectively. At the same time, The doping of cerium oxide could promote the formation of Lewis acid over iron oxide, which improved the low-temperature adsorption of NH3and NO over iron oxide catalyst, thereby enhanced its medium-low temperature SCR activity.
(4) The effects of operation parameters such as calcination temperature, Gas hourly space velocity(GHSV), O2concentration and NH3concentration were examined detailly in the intergral experiment system. And the research results demonstrated that the suitable calcination temperature was vital to the SCR activity over iron-cerium mixed oxide catalyst. When the calcination temperature is higher than the complete decompotition temperature for the precursors of iron-cerium mixed oxide catalyst, higher temperature would lead α-Fe2O3separated out from iron-cerium mixed oxide catalyst, and made the BET surface area and the pore volume of catalyst decrease, thereby depressed the promotion of doping cerium oxide on SCR activity over iron oxide. The suitable calcinations temperature was400℃. Oxygen played an important role on SCR activity over iron-cerium mixed oxide catalysts. The doping of cerium oxide could promote the formation of adsorbed oxygen and lattice oxygen with high activity, which made the iron-cerium mixed oxide catalyst show high SCR activity in the absence of gaseous O2within the simulated gas. Meanwhile, gaseous O2could oxidize the surface of iron-cerium mixed oxide catalyst and promoted the formation of absorbed and lattice oxygen on it, thereby enchanced the SCR activity over iron-cerium mixed oxide catalyst. When the concentration of gaseous O2in the simulated gas was lower than1%, the improvement of gaseous O2could lead the SCR activity of iron-cerium mixed oxide catalyst increase sharply. However, the concentration of gaseous O2showed no influence almost on SCR activity of catalyst when the concentration of gaseous O2was higher than3.0%. The SCR activity of catalyst firstly increased sharply and then slowly with the molar ratio of NH3/NO in the simulated gas increasing from0to1, and the SCR activity of catalyst could be not enhanced again by further improving the molar ratio of NH3/NO.
(5) The kinetics of SCR over Fe0.95Ce0.05O2catalyst had been studied in a differential system, and its catalytic kinetics model for SCR reaction was founded. Under the reaction conditions in this paper, the rate of NO conversion on Fe0.95Ce0.05O2is first-order with respect to NO, zero-order with respect to NH3and nearly0.5-order with respect to O2. The apparent activation energy of the NH3-SCR reaction was42.6kJ/mol at175～275℃.
(6) By doping other transition metal oxide into iron-cerium mixed oxide catalyst, and we investigated the effect of doping another transition metal oxide on SCR activity over iron-cerium mixed oxide catalyst. The research results indicated that, compared with W、Mo and Zr, the doping of Ti could obviously enhance the low-temperature SCR activity over iron-cerium mixed oxide catalyst, and made its reactive temperature window of SCR shift to the low-temperature region. Thereinto, the suitable molar ratio of Ti/(Ti+Fe+Ce) is0.15.
(7) There existed better interaction between the doping titanium with other elements as iron and cerium, which could refine the pore diameter of iron-cerium mixed oxide catalyst, and enlarged the BET surface area and pore volume of catalyst. The doping of titanium led the concentration of iron and cerium elements on the surface of catalyst decrease, and enhanced the dispersion of iron and cerium groups on the surface of catalyst. The doping of titanium might change the surface structure of iron-cerium mixed oxide, enhanced the weak Lewis acid, and improved the low-temperature adsorption of NH3over catalyst. At the same time, the adsorted oxygen concentration over iron-cerium mixed oxide catalyst could also be improved after doping titanium which enhanced the low-temperature catalytic oxidation of NO to NO2over catalyst, and thereby promoted the low-temperature SCR activity over iron-cerium mixed oxide catalyst.
(8) The SCR activity of iron-cerium-titanium mixed oxide catalyst could be enhanced further by introducing microwave hydrothermal treatment into the preparation of catalyst which could make the reactive SCR temperature window shift to the low-temperature region. Meanwhile, the promotional effect of microwave hydrothermal treatment on low-temperature SCR activity is closely related to the molar ratio of Fe and Ti in the mixed oxide catalyst. When the molar ratio of Fe and Ti is smaller, the promotion of microwave hydrothermal treatment is higher. The alternate microwave heating method and the microwave iddiation time played an important role on the promotion of low-temperature SCR activity over iron-cerium-titanium mixed oxide catalyst by using microwave to treat the precursors of catalyst. Under the same microwave iddiation time, when the alternate microwave heating method changed from P30to P80, the promotional effect of microwave hydrothermal treatment on low-temperature SCR activity over iron-cerium-titanium mixed oxide catalyst decreased gruadually. Under the condition of P30, the promotion of microwave hydrothermal treatment was the highest when the microwave iddiation time is15min.
(9) Microwave hydrothermal treatment could accelerate the crystallite rate of the precursors for iron-cerium-titanium mixed oxide catalysts, adjusted the microscopic pore structure of catalyst, and enlarged the pore diameter and the pore volume of iron-cerium-titanium mixed oxide catalyst. Microwave hydrothermal treatment could strengthen the interaction between iron oxide and titanium oxide in mixed oxide, and promoted the formation of iron-titantium composite oxide. At the same time, the molar ratio of Ce3+/Ce4+on the surface of mixed oxide catalyst could be enhanced after microwave hydrothermal treatment, and improved the relative concentration of Ce3+on the surface of catalyst which enhanced the reduction and oxidation conversion between Ce3+and Ce+, and improved the defect value of lattice oxygen on the surface of iron-cerium-titanium mixed oxide catalyst. Therefore, the concentration of lattice oxygen over catalyst could be improved after microwave hydrothermal treatment, and enhanced the oxidation and reduction properties of catalyst. At the same time, microwave hydrothermal treatment enhanced the Lewis acid of the mixed oxide catalyst, and improved the low-temperature adsorption of NH3over catalyst, thereby enhanced the low-temperature SCR activity over iron-based catalyst.
引文
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