汽车尾气净化三效催化剂中N2O和NH3的生成及控制研究进展

N₂O和NH₃的排放主要来自于机动车尾气排放。本文总结了近十几年来轻型汽油车N₂O和NH₃排放的研究进展，阐述了两种气态污染副产物在三效催化剂中的形成机理，通过对影响N₂O和NH₃生成的贵金属种类和含量、载体材料、不同气体组成和浓度、老化条件、不同车辆及测试工况、反应温度等主要影响因素的综述，总结了各要素对N₂O和NH₃形成的影响，得出N₂O和NH₃主要在富燃条件下冷启动阶段生成，NO的解离在N₂O和NH₃的生成中起关键作用；影响N₂O和NH₃生成的各因素之间相互关联，相互影响；催化剂的老化增加N₂O和NH₃的排放；贵金属Rh比Pd和Pt更有利于N₂O和NH₃的分解等结论。发动机、后处理策略系统的升级、更合适测试循环的开发以及催化剂的优化可以进一步降低N₂O和NH₃的排放。     

SCR反应过程中NO/NH3在γ-Al2O3表面吸附特性

采用密度泛函理论（DFT）方法研究了NO和NH₃在完整和有缺陷的γ-Al₂O₃（110）表面吸附与SCR（选择催化还原）反应特性。研究表明,NO在完整的（110）表面的吸附作用较弱,而NH₃分子的吸附作用较强,NH₃分子在Al原子顶位可形成稳定吸附。反应路径研究结果表明完整的（110）表面上SCR反应的决速步为-NH₂NO基团的分解,反应的最大能垒为235.75 kJ·mol^-1。对于产生氧空穴的有缺陷（110）表面,NO和NH₃均可稳定吸附,NH₃在吸附过程中可直接裂解成NH₂和H。另外,SCR反应在有缺陷（110）表面的最大能垒明显较低,说明氧空穴的存在促进了SCR脱硝反应的进行。     

柴油车用NH3-SCR铜基分子筛催化剂孤立态Cu2+研究进展

NH₃选择催化还原技术(NH₃-SCR)作为一种高效去除NO_x的手段,已广泛地应用到柴油车尾气脱硝过程当中。车用NH₃-SCR技术常采用铜基分子筛作为催化剂,尾气中的氮氧化物可在催化剂的作用下,与NH₃反应转化为N₂;但在实际应用过程中,N₂O的生成、催化剂的水热老化与尾气中的SO₂会影响铜基分子筛催化剂的脱硝性能。因此,本文以Cu-SSZ-13分子筛催化剂中孤立态Cu²⁺的研究进展为基础,总结了Cu-SSZ-13中两种孤立态Cu²⁺对NH₃-SCR反应与N₂O生成的影响;综述了两种孤立态Cu²⁺对水热老化与SO₂响应的差异;归纳了诱导Cu-2Z生成的手段。同时,本文以Cu-LTA分子筛催化剂的研究现状为例,简要回顾了Cu-LTA中孤立态Cu²⁺的研究进展,对C...     

选择催化还原(SCR)反应机理研究进展

简述了NH₃和NO在催化剂表面吸附、转化活化和反应历程及H₂O和SO₂对以上反应行为的影响。分析表明,NH₃氧化脱氢进而与NO反应是决定NH₃反应性和最终产物的关键。NO以气态（Eley-Rideal机理）或硝基类物质等吸附态（Langmuir-Hinshelwood机理）形式参与选择催化还原（SCR）反应。提高催化剂酸性和氧化还原循环性能,利于NH₃和NO吸附和转化及相互间反应。高温时,H₂O影响轻微,而SO₂增强催化剂酸性,提高脱硝活性。低温时,H₂O和SO₂抑制NO吸附和转化活化,导致硫铵盐累积和活性位转变为硫酸盐使催化剂失活。因此,提高抗H₂O、抗SO₂性能是低温脱硝催化剂研发的重要方向。而发展在线升温等再生工艺以解决硝酸盐或含硫化合物导致的失活问题,对保障低温脱硝系统长期稳定运行具有重要意义。     

羟基磷灰石负载钯催化剂用于H2和O2直接合成H2O2的动力学

H₂和O₂直接合成H₂O₂过程绿色环保,反应具有原子经济性,是最有潜力的H₂O₂合成新方法之一。采用等量浸渍法,将Pd负载于羟基磷灰石（HAp）载体上,得到了高分散的Pd/HAp纳米催化剂,Pd平均粒径2.5 nm。运用幂指数模型,研究该催化剂在H₂O₂加氢及H₂和O₂直接合成反应中的动力学,计算得到H₂O₂加氢、H₂O₂和H₂O的生成反应的表观活化能及O₂、H₂表观反应级数。结果表明低温及高O₂分压有利于H₂O₂的生成,而高H₂分压则有利于H₂O的生成。     

煤焦异相还原N2O的反应机理

采用两种不同的简化煤焦模型,利用量子化学密度泛函理论研究了煤焦异相还原N₂O的反应机理。通过计算反应物、中间体以及过渡态的结构和能量明确了反应的过程,并通过热力学分析和动力学分析深入分析煤焦异相还原N₂O的反应机理。研究结果表明：单个碳原子无法体现N₂O分子在煤焦表面的吸附和脱附过程,不适于作为煤焦模型研究煤焦异相还原N₂O的反应,六环苯环簇碳基模型可以成功地研究煤焦异相还原N₂O的反应。煤焦异相还原N₂O的反应共经历三个过渡态和两个中间体将N₂O还原成N₂,N₂O分子在煤焦表面的吸附反应的活化能为51.01 kJ·mol^-1,煤焦表面吸附N₂O的过程容易进行。煤焦异相还原N₂O的反应在所研究的温度范围（298.15~1500 K）内为放热反应,可以自发发生,反应平衡常数大于10⁵,可以完全进行,认为是单向反应。煤焦异相还原N₂O的反应在所研究的温度范围（298.15~1500 K）内反应速率较快,反应活化能为43.55 kJ·mol^-1,Arrhenius表达式为1.24×10¹⁰exp（-5238.15/T）。     

CeO2改性再生SCR催化剂的单质汞氧化特性

对国内某1000MW燃煤发电机组失活选择性催化还原（SCR）催化剂进行CeO₂改性再生。对再生前后样品进行N₂吸附-脱附、扫描电子显微镜（SEM）、X射线荧光光谱（XRF）、傅里叶变换红外光谱（FTIR）对比表征分析。在自制固定床反应系统上对CeO₂改性再生催化剂（CeReCat）进行Hg⁰氧化性能测试,同时研究了SO₂、H₂O、NO和NH₃对Hg⁰氧化性能的影响。结果表明,CeO₂改性再生方法可有效清洗失活SCR催化剂表面杂质,恢复催化剂表面活性位点和孔隙结构,可使Ce、V两种活性元素得到有效负载。CeO₂改性后的样品Hg⁰氧化性能显著提升,3.0 CeReCat具有最佳Hg⁰的氧化效率。此外,烟气中加入600μL/L SO₂后,3.0 CeReCat仍具有高达74.4%的Hg⁰氧化效率,抗SO₂性能较好。烟气中的NO可轻微促进Hg⁰的氧化。由于竞争吸附作用,烟气中的H₂O和NH₃会抑制Hg⁰的氧化。CeO₂改性再生催化剂置于SCR系统下层时,由于烟气NH₃浓度较低而具有较高Hg⁰氧化效率,具有良好的应用前景。     

新型双流化床炉内NOx生成特性数值模拟

运用煤燃烧及NO_x生成的详细化学反应机理,通过搭建一维化学反应器网络（1D-CRN）,对一个新型双流化床（DCFB）内燃料型N转化为NO_x的基元化学反应进行了敏感性分析并讨论了反应温度、过量空气系数以及一、二次风配比对燃料型NO_x生成的影响。研究发现,在相同条件下,循环流化床炉膛出口的NO_x排放值为224.48 mg·m^-3,而双流化床炉膛出口的NO_x排放值为97.29 mg·m^-3,双流化床对于燃料型NO_x的减排幅度达到了56.66%。此外,促进NO_x生成的基元反应主要有R398（NH₂+O?HNO+H）、R1-N-1（N-Vol?NH₃+HCN）、R569（NCO+O₂?NO+CO₂）、R17（H+O₂?O+OH）等反应,而抑制NO_x生成的反应包括R411（NH₂+NO?N₂+H₂O）、R412（NH₂+NO?NNH+OH）、R570（NCO+NO?N₂O+CO）、R571（NCO+NO?N₂+CO₂）以及R5（Char+NO?Char+N₂+O₂）和R6（Soot+NO?n Soot+N₂+CO）等反应。这说明反应区域氧气浓度是影响NO_x生成的关键,低氧浓度可抑制燃料N向NO_x转化。另外,NO_x生成值随着反应温度的升高而降低,但随着过量空气系数和一次风所占比例的增大而增加。     

非热等离子体强化TiO2催化尿素分解副产物水解性能的研究

尿素-选择性催化还原技术低温下运行时尿素分解不彻底,易形成缩二脲、三聚氰酸和三聚氰胺等副产物。本研究将TiO₂催化剂与介质阻挡放电等离子体相结合,在程序升温条件下考察了载气中有无O₂时引入等离子体前后TiO₂催化尿素分解副产物水解的性能。结果表明：TiO₂表面缩二脲、三聚氰酸和三聚氰胺分别在43~261℃、217~300℃和199~300℃水解生成NH₃和CO₂,载气中有无O₂对催化水解过程几乎无影响。引入等离子体后缩二脲、三聚氰酸和三聚氰胺水解所需温度显著降低,载气中无O₂时引入等离子体NH₃产率变化不大,副产物仅有少量N₂O和NO,有O₂时NH₃产率显著降低,且生成较多N₂O、NO、NO₂及少量NH₄NO₂和NH₄NO₃。未来需从优化放电条件和催化剂组成等方面解决引入等离子体导致副产物形成等问题。     

二维AuP2材料电催化固氮性能的理论研究

通过电化学反应将氮气（N₂）和水（H₂O）在常温常压的条件下转化为氨气（NH₃）是一种绿色环保的合成氨方法。但由于N₂具有非常高的化学惰性，必须借助电催化剂来加速反应的动力学过程。通过密度泛函理论计算揭示出新型二维无机材料AuP₂对N₂电化学还原制NH₃具有很好的催化活性。在二维AuP₂材料中，Au与P之间由于电负性差异发生显著的电荷转移，使带有正电荷的P可作为活性位点促进氮还原。计算表明整个反应的速控步是N₂生成^*NNH的过程，限制电压为1.2 V，催化活性可以跟部分金属催化剂相媲美。为设计高效氮还原电催化剂提供了新的思路。     

Surface-nitrogen removal in NO and N2O reduction on Pd(1 1 0): Angular distribution studies of desorbing products

This paper is a report of angle-resolved product desorption measurements in the course of catalyzed NO and N₂O reduction on Pd(1 1 0). Surface-nitrogen removal processes show different angular distributions, i.e. normally directed N₂ desorption takes place in process (i) 2N(a) → N₂(g). Highly inclined N₂ desorption towards the [0 0 1] direction is induced in process (ii) N₂O(a) → N₂(g) + O(a). N₂O or NH₃ desorption follows the cosine distribution characterizing the desorption after the thermalization in process (iii) N₂O(a) → N₂O(g) or (iv) N(a) + 3H(a) → NH₃(a) → NH₃(g). Thus, a combination of the angular and velocity distributions provides the analysis of most of surface-nitrogen removal processes in the course of catalyzed NO reduction.

At temperatures below 600 K, processes (ii) and (iii) dominate and process (iv) is enhanced at H₂ pressures higher than NO. Process (i) contributes significantly above 600 K. Only three processes except for NH₃ formation are operative when CO is used. Only process (ii) was observed in a steady-state N₂O + CO (or H₂) reaction.     

Influence of CO2 and H2O on NOx storage and reduction on a Pt–Ba/γ-Al2O3 catalyst

In this paper, the effect of CO₂ and H₂O on NO_x storage and reduction over a Pt–Ba/γ-Al₂O₃ (1 wt.% Pt and 30 wt.% Ba) catalyst is shown. The experimental results reveal that in the presence of CO₂ and H₂O, NO_x is stored on BaCO₃ sites only. Moreover, H₂O inhibits the NO oxidation capability of the catalyst and no NO₂ formation is observed. Only 16% of the total barium is utilized in NO storage. The rich phase shows 95% selectivity towards N₂ as well as complete regeneration of stored NO. In the presence of CO₂, NO is oxidized into NO₂ and more NO_x is stored as in the presence of H₂O, resulting in 30% barium utilization. Bulk barium sites are inactive in NO_x trapping in the presence of CO₂·NH₃ formation is seen in the rich phase and the selectivity towards N₂ is 83%. Ba(NO₃)₂ is always completely regenerated during the subsequent rich phase. In the absence of CO₂ and H₂O, both surface and bulk barium sites are active in NO_x storage. As lean/rich cycling proceeds, the selectivity towards N₂ in the rich phase decreases from 82% to 47% and the N balance for successive lean/rich cycles shows incomplete regeneration of the catalyst. This incomplete regeneration along with a 40% decrease in the Pt dispersion and BET surface area, explains the observed decrease in NO_x storage.     

Kinetics of the NO + H2 reaction over supported noble metal based catalysts: Support effect on their adsorption properties

This paper reports a kinetic investigation of the global reduction of NO by H₂ which has been considered as a probe reaction for characterising the adsorption properties of supported palladium based catalysts. A particular attention has been paid towards the influence of the support on the catalytic properties of Pd, particularly towards the production of undesirable by-products such as nitrous oxide (N₂O) and ammonia (NH₃). It has been found that the kinetics of the overall NO + H₂ reaction on Pd/Al₂O₃ can be correctly depicted according to a Langmuir–Hinshelwood mechanism involving the dissociation of nitrosyl species assisted by chemisorbed hydrogen atoms. On the other hand, Pd/LaCoO₃ exhibits a different kinetic behaviour towards the adsorption of hydrogen depending on the pre-activation thermal treatment. In that case, different mechanisms may occur.     

The role of lanthana loading on the catalytic properties of Pd/Al2O3-La2O3 in the NO reduction with H2

The role of La₂O₃ loading in Pd/Al₂O₃-La₂O₃ prepared by sol–gel on the catalytic properties in the NO reduction with H₂ was studied. The catalysts were characterized by N₂ physisorption, temperature-programmed reduction, differential thermal analysis, temperature-programmed oxidation and temperature-programmed desorption of NO.

The physicochemical properties of Pd catalysts as well as the catalytic activity and selectivity are modified by La₂O₃ inclusion. The selectivity depends on the NO/H₂ molar ratio (GHSV = 72,000 h⁻¹) and the extent of interaction between Pd and La₂O₃. At NO/H₂ = 0.5, the catalysts show high N₂ selectivity (60–75%) at temperatures lower than 250 °C. For NO/H₂ = 1, the N₂ selectivity is almost 100% mainly for high temperatures, and even in the presence of 10% H₂O vapor. The high N₂ selectivity indicates a high capability of the catalysts to dissociate NO upon adsorption. This property is attributed to the creation of new adsorption sites through the formation of a surface PdO_x phase interacting with La₂O₃. The formation of this phase is favored by the spreading of PdO promoted by La₂O₃. DTA shows that the phase transformation takes place at temperatures of 280–350 °C, while TPO indicates that this phase transformation is related to the oxidation process of PdO: in the case of Pd/Al₂O₃ the O₂ uptake is consistent with the oxidation of PdO to PdO₂, and when La₂O₃ is present the O₂ uptake exceeds that amount (1.5 times). La₂O₃ in Pd catalysts promotes also the oxidation of Pd and dissociative adsorption of NO mainly at low temperatures (<250 °C) favoring the formation of N₂.     

FTIR study of aqueous nitrate reduction over Pd/TiO2

The interactions between Pd/TiO₂ catalyst and the reactants and potential reaction intermediates present during aqueous nitrate reduction, including NO₃⁻, NO₂⁻ and NO in the presence of H₂ and H₂O were studied by infrared spectroscopy. Adsorbed forms of NO, nitrite and nitrate could all be detected in the presence of water. In the presence of water/H₂, nitrate was the most stable surface species followed by nitrite and then highly reactive NO, suggesting that the reduction of nitrate to nitrite is the rate-limiting step. High concentrations of adsorbed nitrite appear to be linked to the detection of gaseous N₂O while the formation of ammonia is related to reactions on the Pd surface and the extent of formation is linked to high levels of adsorbed NO in addition to the surface hydrogen availability and the presence of water.     

Alumina- and titania-based monolithic catalysts for low temperature selective catalytic reduction of nitrogen oxides

The selective catalytic reduction of NO+NO₂ (NO_x) at low temperature (180–230°C) with ammonia has been investigated with copper-nickel and vanadium oxides supported on titania and alumina monoliths. The influence of the operating temperature, as well as NH₃/NO_x and NO/NO₂ inlet ratios has been studied. High NO_x conversions were obtained at operating conditions similar to those used in industrial scale units with all the catalysts. Reaction temperature, ammonia and nitrogen dioxide inlet concentration increased the N₂O formation with the copper-nickel catalysts, while no increase was observed with the vanadium catalysts. The vanadium-titania catalyst exhibited the highest DeNO_x activity, with no detectable ammonia slip and a low N₂O formation when NH₃/NO_x inlet ratio was kept below 0.8. TPR results of this catalyst with NO/NH₃/O₂, NO₂/NH₃/O₂ and NO/NO₂/NH₃/O₂ feed mixtures indicated that the presence of NO₂ as the only nitrogen oxide increases the quantity of adsorbed species, which seem to be responsible for N₂O formation. When NO was also present, N₂O formation was not observed.     

Transient analysis of the release and reduction of NOx using a Pt/Ba/Al2O3 catalyst

The release and reduction of NO_x in a NO_x storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O₂ pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al₂O₃ catalyst, the time profiles of several gas products, NO, N₂, NH₃ and H₂O, were obtained as a result of the release and reduction of NO_x caused by H₂ injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO₃)₂/cordierite plate, the release and reduction of NO_x on Pt/Ba/Al₂O₃ catalyst that stored NO_x took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N₂ by H₂ pulse injection. When this H₂ pulse was injected in a large amount, NO was reduced to NH₃ instead of N₂.

A only small amount of H₂O was detected because of the strong affinity for alumina support. We can analyze the NO_x regeneration process to separate two steps of the NO_x release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NO_x release increased as temperature increase.     

Inhibition effect of H2O on V2O5/AC catalyst for catalytic reduction of NO with NH3 at low temperature

The inhibition effect of H₂O on V₂O₅/AC catalyst for NO reduction with NH₃ is studied at temperatures up to 250 °C through TPD, elemental analyses, temperature-programmed surface reaction (TPSR) and FT-IR analyses. The results show that H₂O does not reduce NO and NH₃ adsorption on V₂O₅/AC catalyst surface, but promotes NH₃ adsorption due to increases in Brønsted acid sites. Many kinds of NH₃ forms present on the catalyst surface, but only NH₄⁺ on Brønsted acid sites and a small portion of NH₃ on Lewis acid sites are reactive with NO at 250 °C or below, and most of the NH₃ on Lewis acid sites does not react with NO, regardless the presence of H₂O in the feed gas. H₂O inhibits the SCR reaction between the NH₃ on the Lewis acid sites and NO, and the inhibition effect increases with increasing H₂O content. The inhibition effect is reversible and H₂O does not poison the V₂O₅/AC catalyst.     

Investigation of CO oxidation and NO reduction on three-way monolith catalysts with transient response techniques

The kinetics of CO oxidation and NO reduction reactions over alumina and alumina-ceria supported Pt, Rh and bimetallic Pt/Rh catalysts coated on metallic monoliths were investigated using the step response technique at atmospheric pressure and at temperatures 30–350°C. The feed step change experiments from an inert flow to a flow of a reagent (O₂, CO, NO and H₂) showed that the ceria promoted catalysts had higher adsorption capacities, higher reaction rates and promoting effects by preventing the inhibitory effects of reactants, than the alumina supported noble metal catalysts. The effect of ceria was explained with adsorbate spillover from the noble metal sites to ceria. The step change experiments CO/O₂ and O₂/CO also revealed the enhancing effect of ceria. The step change experiments NO/H₂ and H₂/NO gave nitrogen as a main reduction product and N₂O as a by-product. Preadsorption of NO on the catalyst surface decreased the catalyst activity in the reduction of NO with H₂. The CO oxidation transients were modeled with a mechanism which consistent of CO and O₂ adsorption and a surface reaction step. The NO reduction experiments with H₂ revealed the role of N₂O as a surface intermediate in the formation of N₂. The formation of NN bonding was assumed to take place prior to, partly prior to or totally following to the NO bond breakage. High NO coverage favors N₂O formation. Pt was shown to be more efficient than Rh for NO reduction by H₂.