Hydrocarbon Assisted NO Oxidation with Non-thermal Plasma in Simulated Marine Diesel Exhaust Gases

The NO oxidation performance in a non-thermal plasma (NTP) reactor under realistic synthetic exhaust gas compositions is investigated. The gas compositions differ mainly in the NO–NO₂ ratio and represent different modes of operation of a marine diesel engine. It is found that the maximum NO oxidation efficiency is independent on the NO–NO₂ ratio. Up to 55 % of the NO is mainly oxidised to NO₂ in all gas mixtures being analysed. However, the specific energy density needed to reach the highest NO oxidation varies with the gas composition between 15 and 60 J/L. The performance of the NTP-reactor was significantly improved by the addition of propene (C₃H₆) acting as an additional oxidising agent. The energy consumption for NO–NO₂ conversion was found to be between 20 and 45 eV/NO, depending on the ratio of the added propene as well as the initial concentrations of nitrogen oxides.     

富氧条件下Co/ZSM-5催化剂对C_3H_8选择还原NO_x的性能

采用多种物理化学手段研究了在模拟的轻型柴油车尾气中不同Co担载量及Cu掺杂的Co/ZSM-5催化剂的Co组分分散状态、可还原性、NO吸附脱附性质对C3H8选择性催化还原NOx性能的影响。结果表明,浸渍法制备的Co/ZSM-5催化剂上既有外表面上的Co3+和Co2+物种,也有孔内的Co2+离子。富氧条件下Co/ZSM-5催化剂上C3H8选择性催化还原NOx的活性主要与ZSM-5载体孔外表面分散的CoOx物种中的钴离子可还原能力和NO吸附脱附性能密切相关。Co/ZSM-5催化剂上适宜的Co担载量约为4.0wt%,低担载量时随Co担载量增加,表面CoOx物种中钴离子可还原能力增强,C3H8选择性催化还原NOx的低温转化活性增加;高担载量时,随Co担载量增加,单位Co离子的NO吸附量的减少以及催化剂表面活性中心数的减少,导致了Co/ZSM-5催化剂NOx的转化率和催化剂比速率(k)的下降。孔外表面Co3O4晶体的存在使催化剂表面产生较强的NO吸附,并在高温时有利于C3H8的氧化燃烧,使C3H8选择性催化还原NOx的活性降低。     

富氧条件下Co/ZSM-5催化剂对C3H8选择还原NOx的性能

采用多种物理化学手段研究了在模拟的轻型柴油车尾气中不同Co担载量及Cu掺杂的Co/ZSM-5催化剂的Co组分分散状态、可还原性、NO吸附脱附性质对C₃H₈选择性催化还原NO_x性能的影响。结果表明,浸渍法制备的Co/ZSM-5催化剂上既有外表面上的Co³⁺和Co²⁺物种,也有孔内的Co²⁺离子。富氧条件下Co/ZSM-5催化剂上C₃H₈选择性催化还原NO_x的活性主要与ZSM-5载体孔外表面分散的CoO_x物种中的钴离子可还原能力和NO吸附脱附性能密切相关。Co/ZSM-5催化剂上适宜的Co担载量约为4.0wt%,低担载量时随Co担载量增加,表面CoO_x物种中钴离子可还原能力增强,C₃H₈选择性催化还原NO_x的低温转化活性增加;高担载量时,随Co担载量增加,单位Co离子的NO吸附量的减少以及催化剂表面活性中心数的减少,导致了Co/ZSM-5催化剂NO_x的转化率和催化剂比速率（k）的下降。孔外表面Co₃O₄晶体的存在使催化剂表面产生较强的NO吸附,并在高温时有利于C₃H₈的氧化燃烧,使C₃H₈选择性催化还原NO_x的活性降低。     

Ni-Ti-O混合氧化物的制备、表征及其富氧选择性催化还原NO

采用均匀共沉淀法制备了不同Ni/Ti摩尔比的Ni-Ti-O混合氧化物,考察了它们在富氧条件下丙烯选择性催化还原NO反应中的催化性能,并运用X射线衍射,N₂吸附-脱附、吡啶吸附、程序升温脱附和原位红外光谱对催化剂进行了表征.结果表明,Ni/Ti摩尔比为1的催化剂表现出最佳催化活性,430℃时NO_x转化率达68%.该催化剂具有锐钛矿结构,比表面积较高(149m²/g),有利于提高催化活性;其表面Lewis酸性位有利于硝酸盐物种的吸附,而硝酸盐物种是该反应的重要中间体.     

Determination of the standard molar enthalpy of formation of the ternary complex of neodymium with vitamin B3 and 8-hydroxylquinoline by microcalorimetry

A novel solid ternary complex, [Nd(C₆H₄NO₂)₂·C₉H₆NO·2H₂O], was synthesized in a water bath (333.15 K) by three kinds of reagents: neodymium chloride, vitamin B3 (C₆H₅NO₂), and 8-hydroxylquinoline (C₉H₇NO). Its composition and structure were characterized by elemental analysis, IR spectra, UV spectra, molar conductance, and thermogravimetric analysis. During the process of coordination, C₆H₅NO₂ was bidentate-coordinated with Nd³⁺ in the form of an acidic group by removing the proton; hydroxyl oxygen atom and heterocyclic nitrogen atom of C₉H₇NO formed a chelate ring. Particularly, in this article, a thermochemical cycle in the calorimetric solvent (V _HCl:V _DMF:V _EtOH = 3:1:1) was designed on the basis of Hess’s law. At 298.15 K, the dissolution enthalpies of the reactants and products were determined by a advanced solution–reaction isoperibol microcalorimeter, respectively. According to the above results and relevant literature data, the standard molar enthalpy of formation of [Nd(C₆H₄NO₂)₂·C₉H₆NO·2H₂O], was estimated to be $ \Updelta_{f} H_{m}^{\Uptheta} $ [[Nd(C₆H₄NO₂)₂·C₉H₆NO·2H₂O(s)], 298.15 K] = ?(2,129.1 ± 2.5) kJ mol^?1.     

NH3-SCR脱硝催化剂抗硫性能的研究进展

氮氧化物(NO_x)是一种重要的大气污染物, 它造成严重的环境问题, 同时威胁人类健康. 以钢铁烧结烟气为代表的固定源和以柴油机尾气为代表的移动源是氮氧化物的主要来源. 氨气选择性催化还原法(NH₃-SCR)是目前最有效且应用最广泛的NO_x脱除技术. 然而, 无论是固定源还是移动源上NH₃-SCR催化剂, 都不可避免地会被SO₂毒化, 造成催化剂失活, 限制了NH₃-SCR技术的进一步应用. 因此, 研究NH₃-SCR催化剂的SO₂中毒机制以及提高催化剂的抗硫性能至关重要. 我们对固定源脱硝的金属氧化物和移动源上脱硝的Cu基分子筛这两类不同催化剂体系的SO₂中毒机制的研究进展进行了介绍, 并对这两种催化剂上提高抗硫性能改性方法的研究进展进行了评述, 为未来的研究提供了参考.     

Experimental and kinetic modeling study of the effect of NO and SO2 on the oxidation of CO?H2 mixtures

The effect of NO and SO₂ on the oxidation of a CO? H₂ mixture was studied in a jet‐stirred reactor at atmospheric pressure and for various equivalence ratios (0.1, 1, and 2) and initial concentrations of NO and SO₂ (0–5000 ppm). The experiments were performed at fixed residence time and variable temperature ranging from 800 to 1400 K. Additional experiments were conducted in a laminar flow reactor on the effect of SO₂ on CO? H₂ oxidation in the same temperature range for stoichiometric and reducing conditions. It was demonstrated that in fuel‐lean conditions, the addition of NO increases the oxidation of the CO? H₂ mixture below 1000 K and has no significant effect at higher temperatures, whereas the addition of SO₂ has a small inhibiting effect. Under stoichiometric and fuel‐rich conditions, both NO and SO₂ inhibit the oxidation of the CO? H₂ mixture. The results show that a CO? H₂ mixture has a limited NO reduction potential in the investigated temperature range and rule out a significant conversion of HNO to NH through reactions like HNO + CO ?? NH + CO₂ or HNO + H₂ ?? NH + H₂O. The chain terminating effect of SO₂ under stoichiometric and reducing conditions was found to be much more pronounced than previously reported under flow reactor conditions and the present results support a high rate constant for the H + SO₂ + M ?? HOSO + M reaction. The reactor experiments were used to validate a comprehensive kinetic reaction mechanism also used to simulate the reduction of NO by natural gas blends and pure C₁ to C₄ hydrocarbons. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 564–575, 2003     

富氧条件下乙炔选择催化还原NOx

Acetylene as a reducing agent of metal exchanged HY catalysts, for selective catalytic reduction of NO in the reaction system of 0.16% NO, 0 （C2H2-SCR） was investigated over a series 08% C2H2, and 9.95% O2 （volume percent） in He. 75% of NO conversion to N2 with hydrocarbon efficiency about 1.5 was achieved over a Ce-HY catalyst around 300 ℃. The NO removal level was comparable with that of selective catalytic reduction of NOx by C3H6 reported in literatures, although only one third of the reducing agent in carbon moles was used in the C2H2-SCR of NO. The protons in zeolite were crucial to the C2H2-SCR of NO, and the performance of HY in the reaction was significantly promoted by cerium incorporation into the zeolite. NO2 was proposed to be the intermediate of NO reduction to N2, and the oxidation of NO to NO2 was rate-determining step of the C2H2-SCR of NO over Ce-HY. The suggestion was well supported by the results of the NO oxidation with O2, and the C2H2 consumption under the conditions in the presence or absence of NO.     

Point and Multipoint to Plane Barrier Discharge Process for Removal of NOx from Engine Exhaust Gases: Understanding of the Reactional Mechanism by Isotopic Labeling

An experimental study on the removal of NO_x in a simulated vehicle exhaust gas has been carried out using point to plane and multipoint to plane DBD corona reactors. Hydrocarbon (C₃H₆) and NO_x by-products were systematically investigated with a Gas Chromatography coupled to a Mass Spectrometry (GC/MS). NO_x (NO and NO₂) and CO output were also monitored with a gas analyzer in order to complete the mass balance. ¹⁸O tracer technique analyzes is applied to investigate the mechanism of propylene decomposition. From the plasma chemical reaction pathway proposed, it is apparent that the oxygen activation is one of the important steps for initiating the oxidation processes and the R-NO_x formation. We present data for the reaction of the (N₂/O₂/C₃H₆/CO₂NO/H₂O system in the corona discharge reactors mentioned above. This system has been shown to generate a significant amount of aldehyde. CH₃NO₂ and CH₃ONO₂ are the main R-NO_x compounds produced. Reactant composition and discharge energy densities (controlled by a numerical oscilloscope) were the operating parameters under study in wet and dry air mixture. Water vapors played an important role in NO_x removal (especially in NO₂ removal) via the reaction forming HNO₃. Therefore, in wet-gas mixture supplied reactors the highest removal rates of NO_x were as high as 30%, while in dry-gas only 15%. Different dielectric materials such as Al₂O₃/SiO₂ and TiO₂ on Al₂O₃/SiO₂ support have been used.     

Superior Storage Performance for NO in Modified Natural Mordenite

Natural mordenite (NMOR), modified by acid treatment and ion‐exchange, was employed for NO adsorption in the present study. The NO storage capacity of modified NMOR was greatly improved compared with its original correspondents, mainly due to the preservation of crystalline structure and the improvement of surface area of NMOR. Among all the modified NMOR, Ni‐NMOR exhibited the highest adsorption capacity for NO (1.20 mmol·g^?1) in the presence of 10% O₂ at 308 K. The influence of the main ingredients in flue gas on the storage capacity of NMOR for NO had also been investigated. In general, H₂O, CO₂ and SO₂ all displayed negative impact on NO adsorption due to their competitive adsorption on the surface of NMOR with NO, while the presence of O₂ greatly improved the adsorption of NO because of the formation of NO₂ and N₂O₃. Moreover, Ni‐NMOR exhibited high efficiency for NO_x removal through the NO_x adsorption‐plasma discharge process.     

Heat capacities and thermodynamic properties of MgNDC

One-three-dimensional metal-organic frameworks Mg_1.5(C₁₂H₆O₄)_1.5(C₃H₇NO)₂ (MgNDC) has been synthesized solvothermally and characterized by single crystal XRD, powder XRD, FT-IR spectra. The low-temperature molar heat capacities of MgNDC were measured by temperature modulated differential scanning calorimetry (TMDSC) over the temperature range from 205 to 470 K for the first time. No phase transition or thermal anomaly was observed in the experimental temperature range. The thermodynamic parameters of MgNDC such as entropy and enthalpy relative to reference temperature of 298.15 K were derived based on the above molar heat capacities data. Moreover, the thermal stability and decomposition of MgNDC was further investigated through thermogravimetry (TG)?Cmass spectrometer (MS). Three stages of mass loss were observed in the TG curve. TG?CMS curve indicated that the oxidative degradation products of MgNDC are mainly H₂O, CO₂, NO, and NO₂.     

Effect of conversion of NO2 into no on the catalytic reduction of NO2 with C3H6 in excess O2

During the reduction of NO₂ by C₃H₆ in O₂ over alumina-supported Au, Rh and Pt it was found that three parallel reactions take place,i.e., reduction of NO₂ to N₂ and N₂O, partial decomposition of NO₂ to NO and oxidation of C₃H₆ to CO and CO₂. In the absence of C₃H₆, the NO₂→NO+O₂ reaction reaches a fast equilibrium on Rh and Pt but not on Au and γ-Al₂O₃. Addition of C₃H₆ to the NO₂+O₂ mixture leads to the formation of NO above equilibrium conversion levels.     

SO2 Resisting Pd-doped Pr1-xCexMnO3 Perovskites for Efficient Denitration at Low Temperature

H₂-SCR is served as the promising technology for the controlling of NO_x emission, and the Pd-based derivative catalyst exhibited high NO_x reduction performance. Effectively regulating the electronic configuration of the active component is favorable to the rational optimization of noble Pd. In this work, a series of Pr_1-xCe_xMn_1-yPd_yO₃@Ni were successfully synthesized and exhibited superior NO conversion efficiency at low temperatures. 92.7 % conversion efficiency was achieved at 200 °C over Pr_0.9Ce_0.1Mn_0.9Pd_0.1O₃@Ni in the presence of 4 % O₂ with a GHSV of 32000 h⁻¹. Meanwhile, the outstanding performance was obtained in the resistance to SO₂ (200 ppm) and H₂O (8 %). Deduced from the results of XRD, Raman, XPS, and H₂-TPR, the modification of d orbit states in palladium was confirmed originating from the incorporation in the B site of Pr_0.9Ce_0.1Mn_0.9Pd_0.1O₃. The existence of higher valence (Pd³⁺ and Pd⁴⁺) than the bivalence in Pr_0.9Ce_0.1Mn_0.9Pd_0.1O₃ catalyst was evidenced by XPS analysis. Our research provides a new sight into the H₂-SCR through the higher utilization of Pd.     

Sb modified Fe–Mn/TiO<Subscript>2</Subscript> catalyst for the reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> with NH<Subscript>3</Subscript> at low temperatures

Manganese-based catalysts have attracted much attention due to their excellent performance for NO reduction with NH₃ (NH₃-SCR) at low temperatures. In the current study, the novel metal Sb was modified into Mn/TiO₂ and Fe–Mn/TiO₂, and the NO _x conversion was compared with those of Mn/TiO₂ and Fe–Mn/TiO₂ catalysts to investigate the effect of the Sb. The NO _x reduction activities of the catalysts were evaluated in the temperature range of 100–250 °C at a space velocity of 60,000 h^?1. The physicochemical properties of all the catalysts were characterized by Brunauer–Emmett–Teller surface area, temperature-programmed desorption of ammonia, temperature-programmed reduction, X-ray photoelectron spectroscopy, X-ray diffraction, and high-resolution transmission electron microscopy. Interestingly, the Sb-promoted Mn-based catalysts showed significantly higher NO _x conversion than the other catalysts with or without 6 vol% of H₂O. The high performance of the Sb-modified catalysts could be related to the increase of acid sites and redox properties.     

臭氧氧化结合湿法喷淋对玻璃窑炉烟气同时脱硫脱硝实验研究

采用臭氧氧化结合湿法喷淋对模拟玻璃窑炉烟气开展了同时脱硫脱硝实验研究.采用不同溶液(NaOH、Na₂S)进行了喷淋实验.结果表明,保证溶液pH值在10以上,NaOH浓度对NO_x脱除效率无影响,SO₂的存在促进了NO_x吸收.当O₃/NO物质的量比为1.6、溶液NaOH浓度为0.5%时,NO_x脱除效率可达70%,SO₂脱除效率在99%以上.往喷淋液中添加Na₂S,NO_x脱除效率随Na₂S浓度增加而提高,SO₂的存在对NO_x脱除效率无影响.当O₃/NO物质的量比为1.2、溶液中NaOH浓度为0.5%、添加剂Na₂S浓度为0.6%时,NO_x脱除效率可达70%,SO₂脱除效率在95%以上.60 min长时间运行实验证明,模拟烟气中的NO_x经碱液和添加剂吸收后主要以NO^-₂的形式存在于喷淋液中,且NO_x脱除效率不随溶液pH值的变化而变化.     

Organolithium complex as a gas sensing material for oxides from ab initio calculations and molecular dynamics simulations

Gas sensing study of C₂H₄Li complex toward oxides viz. CO, CO₂, NO, NO₂, SO, and SO₂ gas molecules has been carried out using ab initio method. Different possible configurations of gas molecule adsorption on C₂H₄Li complex are considered. The structural parameters of most stable configuration of gas molecule adsorbed complexes are thoroughly analysed. Electronic properties are studied using total density of states (DOS) plot. Charge transferred between the gas molecule and the substrate is studied using NBO charge analysis. Gas sensing of all the six gas molecules is possible at ambient conditions. Atom centred density matrix propagation (ADMP) molecular dynamics simulations confirmed that all the gas molecules remain adsorbed on C₂H₄Li complex at room temperature during the simulation. This study suggests that the C₂H₄Li complex acts as a novel gas sensing material for CO, CO₂, NO, NO₂, SO, and SO₂ gas molecules at ambient conditions, below room temperature as well as at high pressure.     

Shock-tube studies of the reactions of NO2 with NO2, SO2, and CO

The thermal decomposition of NO₂ and its atom-transfer reactions with SO₂ and CO have been studied behind incident shock waves using photometric detection methods. From the decomposition study it is possible to obtain information on the rate of the reaction 2NO₂ → antisymmetric-NO₃ + NO. The results on the reaction, NO₂ + SO₂ → NO + SO₃ extend the earlier work of Armitage and Cullis to about 2000°K. The reaction with CO [NO₂ +] [CO NO + CO₂] at shock temperatures is somewhat faster than predicted from available low-temperature data and provides a modification of the rate-constant expression that is applicable over a wide temperature range.     

铁基催化剂用于氨选择性催化还原氮氧化物研究进展

氨选择性催化还原NO_x技术可以有效控制氮氧化物的排放。V_2O_5-WO_3(MoO_3)/TiO_2脱硝催化剂虽然已经工业化应用,但其工作温度偏高,不能满足低温宽工作温度窗口等工况的需要。因此,开发具有宽工作温度窗口的低温脱硝催化剂成为研究热点。其中,铁基催化剂因其具有良好的氧化还原性,以及储量丰富、价格低廉、无毒无害等特点,使其在低温氨选择性催化还原(NH_3-SCR)反应中得到了广泛研究。基于Fe_2O_3在NH_3-SCR催化体系中所起的作用不同,从Fe_2O_3作为载体、助剂、活性组分以及新型结构的铁基催化剂等方面系统地介绍了近年来铁基催化剂在NH_3-SCR反应中的最新研究进展。此外,还总结了铁基催化剂的NH_3-SCR反应机理以及抗水抗硫性,并对该领域未来可能的发展方向进行了展望。     

Synthesis of CeO2 by thermal decomposition of oxalate and kinetics of thermal decomposition of precursor

CeO₂ was synthesized by calcining Ce₂(C₂O₄)₃·8H₂O above 673 K in air. The precursor and its calcined products were characterized using thermogravimetry and differential scanning calorimetry, Fourier transform infrared spectra, X-ray powder diffraction, scanning electron microscopy, and UV–Vis absorption spectroscopy. The result showed that cubic CeO₂ was obtained when the precursor was calcined above 673 K in air for 2 h. The UV–Vis absorption spectroscopy studies showed that superfine CeO₂ behaved as an excellent UV-shielding material. The thermal decomposition of the precursor in air experienced two steps, which are: first, the dehydration of eight crystal water molecules, then the decomposition of Ce₂(C₂O₄)₃ into cubic CeO₂. The values of the activation energies associated with the thermal decomposition of Ce₂(C₂O₄)₃·8H₂O were determined based on the Starink equation.     

Kinetic modeling of the CO/H2O/O2/NO/SO2 system: Implications for high‐pressure fall‐off in the SO2 + O(+M) = SO3(+M) reaction

Flow reactor experiments were performed to study moist CO oxidation in the presence of trace quantities of NO (0–400 ppm) and SO₂ (0–1300 ppm) at pressures and temperatures ranging from 0.5–10.0 atm and 950–1040 K, respectively. Reaction profile measurements of CO, CO₂, O₂, NO, NO₂, SO₂, and temperature were used to further develop and validate a detailed chemical kinetic reaction mechanism in a manner consistent with previous studies of the CO/H₂/O₂/NO_X and CO/H₂O/N₂O systems. In particular, the experimental data indicate that the spin‐forbidden dissociation‐recombination reaction between SO₂ and O‐atoms is in the fall‐off regime at pressures above 1 atm. The inclusion of a pressure‐dependent rate constant for this reaction, using a high‐pressure limit determined from modeling the consumption of SO₂ in a N₂O/SO₂/N₂ mixture at 10.0 atm and 1000 K, brings model predictions into much better agreement with experimentally measured CO profiles over the entire pressure range. Kinetic coupling of NO_X and SO_X chemistry via the radical pool significantly reduces the ability of SO₂ to inhibit oxidative processes. Measurements of SO₂ indicate fractional conversions of SO₂ to SO₃ on the order of a few percent, in good agreement with previous measurements at atmospheric pressure. Modeling results suggest that, at low pressures, SO₃ formation occurs primarily through SO₂ + O(+M) = SO₃(+M), but at higher pressures where the fractional conversion of NO to NO₂ increases, SO₃ formation via SO₂ + NO₂ = SO₃ + NO becomes important. For the conditions explored in this study, the primary consumption pathways for SO₃ appear to be SO₃ + HO₂ = HOSO₂ + O₂ and SO₃ + H = SO₂ + OH. Further study of these reactions would increase the confidence with which model predictions of SO₃ can be viewed. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 317–339, 2000