Optimization of an electrochemical cell with an adsorption layer for NOx removal

The structure of a multilayer electrochemical cell with an adsorption layer was optimized by removing an yttria-stabilized zirconia cover layer. It was found that the NO_x removal properties of the electrochemical cell were dramatically enhanced through the optimization, especially under conditions of low voltage, intermediate temperature, and high O₂ concentration. The pronounced increase in activity and selectivity for NO_x decomposition after removing the ytrria-stabilized zirconia cover layer was attributed to the extensive release of selective reaction sites for NO_x species and a strong promotion for NO_x reduction from the interaction of the directly connected adsorption layer with both the Pt and catalytic layers. The optimized electrochemical cell may provide a promising solution for NO_x emission control.     

Total Diesel Emission Control Technology Using Ozone Injection and Plasma Desorption

An innovative total diesel emission control system for diesel particulate and NOx simultaneous reduction is proposed. In this system, the plasma reactor is located outside the emission exhaust pipe and activated gas induced from ozone activated by the plasma is injected into the exhaust pipe. On the other hand, the NOx reduction is achieved using oxygen-poor nonthermal plasma desorption. The concentration of oxygen can be changed either by controlling the incineration state of the engine or by injecting oxygen-poor gas. Experiments are carried out for the emission of small diesel engine generator and high performance is demonstrated. The effective or apparent required plasma energy can be decreased further using this system because of the periodic or intermittent application of the plasma. In the present study, the excellent reduction energy efficiencies of 6.6 g/kWh for PM and 16 g (NO₂)/kWh for NOx are achieved.     

Pilot-Scale Aftertreatment Using Nonthermal Plasma Reduction of Adsorbed NOx in Marine Diesel-Engine Exhaust Gas

Regulations governing marine diesel engine NO_x emissions have recently become more stringent. As it is difficult to fulfill these requirements by combustion improvements alone, effective aftertreatment technologies are needed to achieve efficient NO_x reductions. In this study, we develop an effective NO_x-reduction aftertreatment system for a marine diesel engine that employs combined nonthermal plasma (NTP) and adsorption. Compared with selective catalytic reduction, the proposed technology offers the advantages of not requiring a urea solution or harmful heavy-metal catalysts and low operating temperatures of less than 150 °C. The NO_x reduction comprises repeated adsorption and desorption flow processes using NTP combined with NO_x adsorbents made of MnO_x–CuO. High concentrations of NO_x are treated by NTP after NO_x adsorption and desorption, and this aftertreatment system demonstrates excellent energy efficiencies of 161 g(NO₂)/kWh, which fulfills the most recent International Maritime Organization emission NO_x standards in the Tier II–III regulations for 2016 and requires only 4.3 % of the engine output power.     

Review of Ag/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Reductant System in the Selective Catalytic Reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Ag/Al₂O₃ is a promising catalyst for the selective catalytic reduction (SCR) by hydrocarbons (HC) of NO _x in both laboratory and diesel engine bench tests. New developments of the HC-SCR of NO _x over a Ag/Al₂O₃ catalyst are reviewed, including the efficiencies and sulfur tolerances of different Ag/Al₂O₃-reductant systems for the SCR of NO _x ; the low-temperature activity improvement of H₂-assisted HC-SCR of NO _x over Ag/Al₂O₃; and the application of a Ag/Al₂O₃-ethanol SCR system with a heavy-duty diesel engine. The discussions are focused on the reaction mechanisms of different Ag/Al₂O₃-reductant systems and H₂-assisted HC-SCR of NO _x over Ag/Al₂O₃. A SO₂-resistant surface structure in situ synthesized on Ag/Al₂O₃ by using ethanol as a reductant is proposed based on the study of the sulfate formation. These results provide new insight into the design of a high-efficiency NO _x reduction system. The diesel engine bench test results showed that a Ag/Al₂O₃-ethanol system is promising for catalytic cleaning of NO _x in diesel exhaust.     

Development of PGM-free catalysts for automotive applications

The activity of Ag-based catalysts in soot oxidation using NO₂ and oxygen as oxidants has been characterized in laboratory tests (TGA) and under real conditions on an engine dynamometer. Under low-temperature NO₂-assisted and high-temperature O₂-assisted soot oxidation conditions, the activity of Ag-based catalysts was found to be comparable or higher than that of commercial Pt-catalysts. In addition, Ag-based compositions also revealed noticeable NO _x storage, some passive NO _x reduction ability, and activity in NO oxidation. Ag-catalysts characterized in the present paper may be promising for the retrofit applications and high-temperature periodical regenerations with air for diesel passenger cars.     

Reduction of nitrogen oxides in diesel exhaust: Prospects for use of synthesis gas

Already commercialized and some of the most promising technologies of nitrogen oxide reduction in automotive diesel exhaust are compared. The Boreskov Institute of Catalysis (Siberian Branch, Russian Academy of Sciences) is developing an advanced method for the selective catalytic reduction of NO _x with synthesis gas produced on board by the catalytic conversion of diesel fuel. The activity of the Ag/Al₂O₃ catalytic system in NO _x reduction by H₂ + CO admixtures is studied for both a model composition of the exhaust gas and under real diesel operation conditions.     

Low Temperature Plasma Assisted Catalytic Reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> in Simulated Marine Diesel Exhaust

Plasma Assisted Catalytic Reduction (PACR) of NO _x has been investigated at laboratory scale for gas stream compositions representative of marine diesel exhausts. PACR NO _x reduction in excess of 90% was measured at 350°C, a plasma specific energy of 60 J/l and two NO _x concentrations (1,200 and 1,800 ppm). PACR NO _x reduction of over 50% was measured for simulated marine engine conditions at 250°C, 60 J/l and 1,200 ppm NO _x . The performance under these conditions could be increased, achieving a peak of ∼74% NO _x reduction, although at a relatively high plasma power. Water, present in diesel exhaust, was shown to inhibit the poisoning effects of fuel sulphur using SO₂ as a representative exhaust component. The PACR system performance demonstrated tolerance to simulated fuel sulphur levels of up to 1% for the duration of the tests. PACR performance was also shown to be sensitive to the amount of hydrocarbon reductant used.     

Shielded Sliding Discharge-Assisted Hydrocarbon Selective Catalytic Reduction of NOx over Ag/Al2O3 Catalysts Using Diesel as a Reductant

The nonthermal plasma generated in a shielded sliding discharge reactor was used to reform diesel for the hydrocarbon-selective catalytic reduction (HC-SCR) of NO_x on Ag/Al₂O₃ catalysts. Compared with raw diesel, the reformed diesel enhanced the NO_x reduction efficiency, mitigated hydrocarbon poisoning of the catalyst and reduced the fuel penalty for the HC-SCR reaction. The NO_x conversion values obtained with a commercial Ag/Al₂O₃ catalyst exceeded that of a 2.0 wt% Ag/Al₂O₃ catalyst prepared by wet impregnation. A significant amount of NH₃ was produced as a by-product during the HC-SCR reaction, which suggests that further NO_x conversion enhancement can be achieved by placing a second NH₃-SCR catalyst in series with the Ag/Al₂O₃ catalyst.     

氧化铈在氨选择性催化还原氮氧化物中的应用

NH₃选择性催化还原NO_x（NH₃-SCR）是一种广泛应用于以燃煤电厂为代表的固定源和以柴油发动机为代表的移动源NO_x排放控制的技术. 近年来,氧化铈由于具有优异的氧化-还原、储氧和表面酸性等特性而在NH₃-SCR催化剂研究中受到广泛关注. 本文系统综述了氧化铈用作NH₃-SCR催化剂载体、助剂和主催化组分的相关研究,并对该领域未来可能的研究方向进行展望.     

Recent lean NOx catalyst technologies for automobile exhaust control

The current status of our development work on lean NO_x catalysts for application to future gasoline and diesel engines is described. As a result of further improvements in fuel economy, the temperature of exhaust gas will be lower and there will be smaller quantities of hydrocarbons (HCs) in the exhaust of future engines. Therefore, it is necessary to improve the activity of lean NO_x catalysts at lower temperatures and achieve higher selectivity of the NO_x–HC reaction. Utilizing precious metal catalysts is one effective way of improving catalyst activity at lower temperatures, and HC adsorption and reforming are two key technologies for improving the catalyst selectivity for the NO_x–HC reaction.     

Recent lean NOx catalyst technologies for automobile exhaust control

The current status of our development work on lean NO_x catalysts for application to future gasoline and diesel engines is described. As a result of further improvements in fuel economy, the temperature of exhaust gas will be lower and there will be smaller quantities of hydrocarbons (HCs) in the exhaust of future engines. Therefore, it is necessary to improve the activity of lean NO_x catalysts at lower temperatures and achieve higher selectivity of the NO_x–HC reaction. Utilizing precious metal catalysts is one effective way of improving catalyst activity at lower temperatures, and HC adsorption and reforming are two key technologies for improving the catalyst selectivity for the NO_x–HC reaction.     

Production of Reactive Oxygen Species and Application for NOx Control

Current gas ionization discharge techniques used in the removal of NOx from waste gases require large plasma sources, have high energy consumption, and may feature low NOx removal rates. We develop a system to generate reactive oxygen species through a strong ionization discharge, which is injected into a flow of simulated waste gas. The relative proportions and temperatures of input gases were controlled and the rate of consumption by reactive species was monitored. HNO₃ oxidization products of NOx were also collected and measured. The molar ratio of reactive oxygen species to NO was optimized to improve the rate of NOx removal. A input gas temperature of 58–60 °C was also found to be optimal. The O₂ volume fraction has almost no influence on NOx removal, while H₂O volume fractions above 6 %, gave rise to NOx removal rates of 97.2 %. The present study addresses disadvantages of current gas ionization discharge and requires no catalyst, reducing agent or oxidant.     

Sulfur impact on diesel emission control- A review

The effect of sulfur on diesel emission control is reviewed in this paper. Diesel exhaust differs from that of petrol engine exhaust in two major characteristics. Firstly, diesel exhaust contains a far higher amount of particulate matter, and secondly, the exhaust is far leaner, that is, far more oxidizing than a typical exhaust from petrol engines. Under these conditions, the conventional three-way catalysts are not effective in reducing NO_x . Emission from diesel engines is a complex phenomenon. The composition, the properties and the amount of these emissions depend on strictly technical parameters such as engine design and engine operation characteristics and on fuel and lube oil composition. Diesel fuel contains a small amount of sulfur which has an adverse effect even on the raw particulate emissions. The investigations on the effect of sulfur on hydrocarbons, CO and NO_x abatement in diesel exhaust gas is reviewed together with the newest technologies to avoid catalyst deactivation by unwanted SO₂ reactions.     

NH3选择性还原NOx技术在重型柴油车尾气净化中的应用

基于实验室对柴油车用V₂O₅-WO₃/TiO₂催化剂配方以及涂覆成型技术的大量研究,设计了一条产量为6000只/月的NH₃选择性催化还原NO_x （NH₃-SCR）催化剂中试生产线,并对生产的催化剂产品进行了发动机台架测试. 结果表明,实验室制备的V₂O₅-WO₃/TiO₂粉体催化剂和生产线产品,在空速为50000 h^-1和200-450 ℃条件下NO_x转化率均可达80%以上;采用大尺寸堇青石载体涂覆后制备的V₂O₅-WO₃/TiO₂整体催化剂经实验室小样测试,在空速为10000-30000 h^-1和250-450 ℃条件下NO_x转化率也为80%以上. 发动机台架测试结果表明,该催化剂产品可使重型柴油机NO_x排放达到国IV标准中欧洲稳态循环（ESC）和欧洲瞬态循环（ETC）排放限值的要求. 该生产线经适当调整后也可用于生产非钒基NH₃-SCR整体催化剂,以满足未来钒基NH₃-SCR催化剂更新换代的需求.     

BaCo1-xFexO3-δ缺陷钙钛矿NOx储存还原催化剂的制备、结构与性能

制备了B位Fe取代的BaCo1-xFexO3-δ系列缺陷钙钛矿型NOx储存还原(NSR)催化剂,考察了其储存NOx与抗硫性能;应用N2吸附-脱附,X射线衍射,红外光谱,程序升温还原和程序升温脱附等技术对催化剂进行了表征.结果表明,Fe的取代提高了BaCoO3的抗硫能力,当x=0.4时,样品具有相对最大的NOx储存量,且...     

Development of a TG-FTIR system for investigations with condensable and corrosive gases

A thermogravimetric analyzer and a Fourier-transform infrared (FTIR) spectrometer were combined and redesigned for investigations with corrosive and condensable reactive gases. The standard gas inlet and outlet of the thermogravimetric analyzer were changed in order to heat the gas tubes, which are lead through the flanges, and avoid condensation in these parts of the system. Furthermore, all tubes upstream and downstream of the thermogravimetric analyzer were trace heated up to 180 °C. The gas measuring cell of the FTIR spectrometer was designed such that an optimum compromise between the small flow rates through the thermogravimetric analyzer and a short residence time of the gases in the gas measuring cell could be achieved. The gas supply allows the dosage of different gas compositions containing nitrogen, oxygen, water, NH₃, and NO₂, for example. The system was validated by analyzing the composition of a diesel particulate matter (PM) sample with a temperature-programmed desorption followed by oxidation (TPD/O) experiment, which showed good agreement with the established analysis methods. The reactivity of the PM sample was investigated by temperature-programmed oxidation (TPO) experiments with different reactive gas mixtures of oxygen, water, and NO₂ in nitrogen. By adding NO₂, the soot oxidation started at lower temperatures and the addition of water lead to a shift of the maxima of the carbon oxidation rates to lower temperatures. The ratio of formed CO₂ and CO was shifted to higher values by the addition of NO₂ and water whereby the influence of water was much more pronounced.     

Reactivity of NO with NH3 in the Presence of O2 over Ce-ZSM5 with and without Moisture

Cerium based ZSM5 catalysts are used to study NO reduction with NH₃ in the presence of oxygen with and without moisture. The Ce-ZSM5 was prepared by wet impregnation method and characterized by X-ray diffraction technique, BET surface and SEM. Ce-ZSM5 showed better NO_x reduction than H-ZSM5 which is a poor catalyst for NO_x reduction with NH₃. The metal incorporation in H-ZSM5 has increased the catalytic activity. The catalytic activity showed significant difference in NO_x conversion with and without moisture. The disperse Ce species are the active centers for the reduction of NO with NH₃ in the presence of oxygen. This revised version was published online in June 2006 with corrections to the Cover Date.     

Investigation of the promotion effect of Mo doped CuO catalysts for the low-temperature performance of NH3-SCR reaction

A novel Mo-doped CuO catalyst is developed and used for low-temperature NH₃-SCR reaction. Compared with the undoped CuO sample, the Mo doped CuO catalyst shows an increased SCR performance with above 80% NO_x conversion at 175 °C. The XRD and Raman results have confirmed the incorporation of Mo metal ions into CuO lattice to form Mo-O-Cu species which may be related to the enhanced SCR activity. The XPS and UV–vis results reveal the creation of electron interaction between Cu and Mo in this Mo-O-Cu system which provides an increased amount of Lewis and Brønsted acid sites, thereby promoting the adsorption capacity of NH₃ and NO_x as verified by NH₃-TPD and NO_x-TPD characterization. Besides, it also promotes the formation of oxygen vacancies, leading to the increasing of chemisorbed oxygen species, which improves the NO oxidation to NO₂ activity. Furthermore, in situ DRIFTS technology was also used to study the reaction mechanism of this Mo doped CuO catalyst. The formed NO₂ could react with NH_x (x = 3, 2) species to enhance the low-temperature NH₃-SCR activity via the “fast-SCR” reaction pathway. The nitrate and nitrite ad-species may react with NH₃ and NH₄⁺ ad-species through the L-H pathway.     

Mn1-x(Li,Ti)xCo2O4尖晶石型复合氧化物的制备、表征与催化性能

用柠檬酸配位燃烧法合成了Mn_1-x(Li,Ti)_xCo₂O₄系列尖晶石型复合氧化物催化剂，使用FTIR和XRD方法对催化剂结构进行表征，通过程序升温氧化反应(TPO)技术对这些催化剂在模拟柴油机尾气条件下进行同时消除NO_x和柴油碳黑反应的活性评价。结果表明，掺杂Li或Ti后的Mn_1-x(Li,Ti)_xCo₂O₄系列催化剂仍然保持了完整的尖晶石型复合氧化物结构，这些催化剂对同时消除柴油机尾气中的碳黑颗粒和NO_x具有良好的催化性能，其中Li或Ti的掺杂量为x=0.05较佳，结合碳黑燃烧与NO_x还原总的催化效果，Mn_0.95Li_0.05Co₂O₄具有最好的催化活性。     

低于300℃时两种氧化铈材料对稀燃阶段NOx存储性能的影响

研究了低于300 ℃时两种氧化铈对稀燃阶段NO_x存储性能的影响,催化剂由2%（w）Pt/Al₂O₃（PA）与CeO₂-X（X=S,I）机械混合制备. X射线衍射（XRD）,BET表面积和扫描电子显微镜（SEM）用于表征材料的物理结构. X射线光电子能谱（XPS）和H₂程序升温还原（H₂-TPR）用于表面Ce³⁺和活性氧定量. 原位漫反射傅里叶变换红外光谱（in-situ DRIFTS）用于分析表面NO_x吸附物种. 相比于CeO₂-I,CeO₂-S 具有优良的物理化学性能,包括高比表面积、丰富的空隙结构、较高的抗老化能力及表面Ce³⁺浓度. 因而,Pt/Al₂O₃+CeO₂-S 表现出优异的NO_x存储能力. 此外,PA+CeO₂-X（X=S,I）上存在Pt 与CeO₂之间的相互作用,可提高表面氧物种的活性进而促进NO氧化及NO_x存储. PA+CeO₂-S上的这种相互作用要强于PA+CeO₂-I. 研究表明,表面Ce³⁺浓度和活性氧含量对NO_x存储起到重要作用. 然而经过水热处理后,Pt 与老化的氧化铈（ACS,ACI）之间的相互作用降低,并且两种氧化铈NO_x存储性能显著下降. 另外,与PA+ACS（ACI）相比,PA+PACS（PACI）样品NO_x存储能力得到改善,这归因于表面氧物种活性增加能促进硝酸盐的形成.