柴油车用NH_3选择性催化还原NO_x技术发展现状

文章介绍了NH3选择性催化还原NOx技术(SCR)的基本原理,主要讨论了TiO2和分子筛型催化剂的优缺点,以及这两种催化剂应用于柴油车尾气NOx净化的主要问题和相应的解决措施,为开发车用SCR催化剂提供必要的支持。     

采用SCR技术降低车用柴油机的NOx排放

NOx是车用柴油机排气中的主要有害排放物，机外措施是控制柴油机排放的有效措施，是柴油机排放控制的关键技术。文中重点介绍了降低车用柴油机NOx排放的机外措施之一选择催化还原(SCR)技术。     

对我国中重柴油机排放控制研究策略分析

现有的柴油机废气排放控制技术主要有氧化催化器加废气再循环技术（DOC＋EGR）、选择性催化还原（SCR）、颗粒捕集器（DPF）等技术。现今,国内重型柴油机的运用表明选择性催化（SCR）还原技术最适合国IV重型车用柴油机。2010的商务年会上中国重汽曾宣告在高压共轨基础上采用选择性催化还原对尾气进行后处理。除此之外,国内众柴油机生产企业例如上柴也采用了高压共轨＋选择性催化还原技术。     

SCR催化剂对汞的催化氧化研究进展

文章综述了目前国内外选择性催化还原(SCR)催化剂催化氧化燃煤烟气中汞的研究现状。介绍了钒基、铜基、铁基、锰基、铈基以及贵金属SCR催化剂对汞的催化氧化性能;分别分析了烟气温度、烟气组分(Cl2、HCl、SO2、NH3等)、空速等因素对各催化剂汞氧化性能的影响;最后运用文献对比方法综合概括了燃煤烟气条件对汞氧化的影响,并结合我国燃煤电厂现状,对SCR催化脱汞技术的发展方向提出建议:利用SCR催化剂实现燃煤烟气中汞的氧化,结合现有污染物控制设备实现汞的脱除,是一种经济、高效的燃煤烟气脱汞技术;当前应深入研究SCR催化剂对汞的催化氧化机理,开发能够实现NOx与汞协同控制的,稳定、高效、普适性强的低温SCR催化剂。     

Effect of water vapor on NH3-NO/NO2 SCR performance of fresh and aged MnOx-NbOx-CeO2 catalysts

A MnOx–NbOx–CeO2 catalyst for low temperature selective catalytic reduction(SCR) of NOx with NH3 was prepared by a sol–gel method, and characterized by NH3–NO/NO2 SCR catalytic activity, NO/NH3 oxidation activity, NOx/NH3 TPD, XRD, BET, H2-TPR and in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy(DRIFTS). The results indicate that the Mn Ox–Nb Ox–CeO2 catalyst shows excellent low temperature NH3-SCR activity in the temperature range of 150–300℃. Water vapor inhibits the low temperature activity of the catalyst in standard SCR due to the inhibition of NOx adsorption. As the NO2 content increases in the feed, water vapor does not affect the activity in NO2 SCR. Meanwhile, water vapor significantly enhances the N2 selectivity of the fresh and the aged catalysts due to its inhibition of the decomposition of NH4NO3 into N2O.     

火电厂SCR脱硝催化剂技术研究进展

选择性催化还原(SCR)法是目前火电厂处理烟气中NOx的主要方法。本文对SCR技术及脱硝催化剂进行了综述,重点介绍了SCR脱硝工艺的影响因素、SCR在火电机组实际运行中的问题及解决策略、SCR催化剂的失活及处理方案。     

煅烧温度对γ-Fe_2O_3催化剂结构及其脱硝活性的影响

采用沉淀-微波热解法,以Fe SO4·7H2O为铁源制备环境友好的γ-Fe2O3催化剂,结合XRD(X射线衍射)、N2等温吸附-脱附、SEM(扫描电子显微镜)、EDS(能谱仪)等手段对催化剂样品的晶相、孔结构、表面形貌、表面元素组成等进行表征,并考察其NH3-SCR(选择性催化还原)脱硝性能,研究煅烧温度对γ-Fe2O3催化剂物性及NH3-SCR脱硝性能的影响规律.结果表明:300、350和450℃下煅烧制备的催化剂中生成的杂质α-Fe2O3对SCR反应不利,而400℃煅烧制备的γ-Fe2O3催化剂脱硝性能最优,NOx转化率最高可达95%以上,XRD结果表明其纯度高,并且在60~100 nm孔径区间具有发达的孔隙结构,有利于SCR反应进行;随着煅烧温度升高,γ-Fe2O3催化剂表面晶格氧逐渐增加,颗粒形貌经历了片状颗粒(300、350℃)→球状颗粒(400℃)→针状颗粒(450℃)的变化过程,均匀的球状颗粒形貌及其表面丰富的晶格氧是400℃煅烧制得催化剂具备最优脱硝性能的重要因素.     

车用柴油机环保与节能技术

柴油机环保与节能技术是目前柴油机技术研究的重点，文中从制造技术、排气净化、噪声控制等方面对车用柴油机环保与节能技术进行了介绍。     

不同SAPO分子筛负载MnOx催化剂的低温NH3-SCR性能研究

以磷酸硅铝分子筛SAPO-5、SAPO~(-1)1和SAPO-34为载体,采用乙醇分散法制备了用于低温氨选择性还原(NH_3-SCR)NO_x的分子筛负载MnO_x催化剂.活性测试结果显示,3种分子筛催化剂均展现出优良的NH_3-SCR活性,但三者在低温区间的SCR活性存在较明显差异,其SCR活性顺序如下:MnO_x/SAPO-34MnO_x/SAPO-5MnO_x/SAPO~(-1)1.借助XRD、N2吸附-脱附、XPS、H2-TPR、NH_3-TPD、NH_3FT-IR等技术对催化剂的表面活性物种及表面酸性等进行表征分析,结果表明,MnO_x主要以无定型状态分散于载体上,负载后载体的比表面积和孔体积均有所下降.XPS和H2-TPR分析证实,不同分子筛载体上MnO_x的表面浓度与氧化态明显不同.NH_3-TPD和NH_3FT-IR分析揭示了催化剂表面均存在Bronsted酸位和Lewis酸位,其中,Lewis酸性位对低温SCR反应起着关键作用.研究表明,催化剂的催化性能会因载体不同而存在差异,高Mn4+表面浓度和丰富的Lewis酸性位对催化剂在低温区间实现优良的催化活性尤为重要.     

柴油机颗粒捕集器(DPF)再生技术分析

颗粒物捕集器(DPF)是未来车用柴油机满足排放法规的重要措施,是解决其排气颗粒污染最有效的技术之一。文章介绍了DPF的净化机理,在对DPF各种再生技术原理、研究现状及其存在问题分析的基础上,指出微粒捕集器再生技术的发展趋势。     

以飞灰为载体的金属氧化物催化剂脱硝研究

以飞灰作为催化剂的载体 ,担载Fe、Cu、V、Ni等过渡金属作为活性成分制成脱硝催化剂 .对飞灰作为载体的催化剂进行了各种表征分析 ,考察了催化剂的制备条件对脱硝效率的影响 .利用固定床反应装置进行了催化脱硝实验研究 ,结果发现 ,飞灰作为脱硝催化剂的载体是可行的 ,其中担载Cu作为活性成分时脱硝效率最好 ,在温度为 2 70℃时NO的转化率达90 %以上 .最后 ,对活性炭和页岩灰作载体时的催化脱硝特性进行了对比研究 ,发现飞灰的催化活性仅次于活性炭 ,而页岩灰的活性最差 .     

MnOx/TiO2-ZrO2催化剂的制备及低温催化还原NO的研究

采用共沉淀法制备了TiO2-ZrO2复合氧化物,以其为载体采用等体积浸渍法制备了不同负载量的MnOx/Ti02-Zr02催化剂.低温下以NH3为还原剂考察了催化剂选择性催化还原(SCR)NO的活性.借助N2吸附、XRD、热重-差示扫描量热法(TG-DSC)对催化剂进行微观表征和分析.结果表明,负载量为5%时,生成的MnO2高度分散,NO的转化率较高;负载量为10%和15%时,出现MnO2晶相,NO的转化率有所下降.120-240℃、体积空速为10000 h-1的条件下,3种负载量的催化剂上NO转化率均大于90%.     

Kinetics of selective catalytic reduction of NO by NH3 on Fe-Mo/ZSM-5 catalyst

The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction (SCR) of nitric oxide (NO) with NH3. The kinetics of the SCR reaction in the presence of O2 was studied in this work. The results show that the observed reaction orders were 0.74-0.99, 0.01-0.13, and 0 for NO, O2 and NH3, respectively, at 350-450℃. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst. The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N2 and H2O. Gaseous O2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process. It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH3.     

Kinetics of selective catalytic reduction of NO by NH_3 on Fe-Mo/ZSM-5 catalyst

The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction (SCR) of nitric oxide (NO) with NH_3.The kinetics of the SCR reaction in the presence of O_2 was studied in this work.The results showed that the observed reaction orders were 0.74-0.99,0.01-0.13,and 0 for NO,O_2 and NH_3 at 350-450℃,respectively. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst.The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N_2 and H_2O.Gaseous O_2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process.It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH_3.     

以MnOx/TiO2作为催化剂的低温SCR反应过程中还原剂NH3的作用

研究了在以MnOx/TiO2作为催化剂的低温SCR反应过程中,还原剂NH3所起的作用.当系统中NH3浓度较低时,增加气相中NH3的浓度可以大幅度提高NO的去除率.但当系统中NH3浓度较高时,NO去除率基本不随NH3浓度变化而变化.并且瞬态研究中,NH3对NO去除率的影响较为复杂.为了探明NH3在SCR反应中的作用,用原位傅立叶红外检测了各个反应历程中NH3在催化剂表面形成的基团变化及其活性特征.结果表明,在SCR反应过程中,在催化剂表面形成的配位态的NH3是参与反应的主要物质.并且在催化剂表面,此种NH3会与NO生成的硝酸盐形成竞争吸附,当催化剂活性点首先被硝酸盐占领时,将会影响配位态NH3的生成,从而在一定程度上降低了NO的转化率.     

引入化学反应的600MW火电机组烟气SCR脱硝性能模拟

以600 MW火电机组现有SCR脱硝装置为研究对象,应用CFD软件完成建立模型、划分网格、选择数学模型、设置边界条件、模拟计算等工作,最终得出SCR脱硝系统流速分布及Cv值、压力损失、NH3分布及逃逸浓度等结果。结果表明:SCR脱硝系统流速分布均匀、偏差符合设计要求,NH3与烟气混合均匀,氨逃逸浓度低。     

生活垃圾焚烧发电厂二噁英近零排放技术研究

随着生活垃圾焚烧发电厂的逐渐增多,二噁英首当其冲成为反对呼声的靶子,因此探讨二噁英的防治对策进展显得更为重要.二噁英近零排放控制技术目前主要有两种:选择性催化还原法和热解气化技术.选择性催化还原(SCR)系统一般是用来去除NOx,实际上采用合适的催化剂后,二噁英去除效率能高于90%.热解气化技术被称为第三代焚烧技术,一方面一燃室里垃圾热分解,削弱了二噁英的生成环境;另一方面,二燃室里气体燃烧,温度在1000℃以上,烟气停留时间2 s以上,保证了二噁英的充分分解.     

利用NH3选择性催化还原（SCR）烟气脱硝技术研究进展

介绍了利用NH3选择性催化还原（sCR）烟气脱硝技术的机理、动力学模拟以及着重介绍了用于SCR过程中的各种催化剂的研究进展,最后分析了在SCR脱硝过程中的主要影响因素。并展望了今后脱硝过程中的方向,是进一步探讨各种催化剂的催化机理,从而研究更为合适的催化剂。     

NH3-SCR performance and the resistance to SO2 for Nb doped vanadium based catalyst at low temperatures

Niobium oxide as the promoter was doped in the V/WTi catalyst for the selective catalytic reduction(SCR)of NO.The results showed that the addition of Nb_2O_5could improve the SCR activity at low temperatures and the 6 wt.%additive was an appropriate dosage.The enhanced reaction activity of adsorbed ammonia species and the improved dispersion of vanadium oxide might be the reasons for the elevation of SCR activity at low temperatures.The resistances to SO_2of 3V6Nb/WTi catalyst at different temperatures were investigated.FTIR spectrum and TG-FTIR result indicated that the deposition of ammonium sulfate species was the main deactivation reason at low temperatures,which still exhibited the reactivity with NO above 200°C on the catalyst surface.There was a synergistic effect among NH_3,H_2O and SO_2that NH_3and H_2O both accelerated the catalyst deactivation in the presence of SO_2at 175°C.The thermal treatment at 400°C could regenerate the deactivated catalyst and get SCR activity recovered.The particle and monolith catalysts both kept stable NO_xconversion at 225°C with high concentration of H_2O and SO_2during the long time tests.