乙醇胺对介质阻挡耦合电晕放电同时脱除NO、SO2的影响

采用自行设计的介质阻挡耦合电晕放电等离子体反应装置进行了模拟烟气同时脱硫脱硝的研究,分别考察乙醇胺（HOCH₂CH₂NH₂,MEA）在不同模拟烟气体系中对NO、SO₂脱除的影响,深入探讨了MEA在放电过程中与NO的作用机理。结果表明：在N₂/O₂/SO₂/NO体系中,0.56% MEA的加入可以显著消除O₂对NO脱除的抑制作用;在N₂/CO₂/SO₂/NO体系中,MEA会吸收进入体系中的部分CO₂,以减弱CO₂对NO脱除的抑制;在N₂/O₂/CO₂/H₂O/NO/SO₂体系中,0.56% MEA的加入既可以有效减弱H₂O的影响,也可以使NO的脱除率达到71.28%,继续将MEA的体积分数增大至1.20%时,可将该体系下NO脱除率提高到81.25%;同时,MEA可以在短时间内高效吸收体系内的SO₂,且几乎不受其他气体成分的影响,SO₂脱除率保持在95%左右。     

水蒸气对oxy-coal燃烧中NO生成的影响

为了研究H₂O对燃料N向NO转化各个阶段的影响,采用可沿程取样的沉降炉反应器,研究了一种烟煤在1273 K温度下,O₂/N₂、O₂/CO₂以及O₂/CO₂/H₂O气氛下燃烧的燃尽与NO生成的情况.并通过在停留时间为0.2、0.3、0.5、1.1 s与O₂浓度为5%、21%及30%情况下的实验来研究H₂O对NO生成的影响.实验结果表明,相对于O₂/CO₂气氛,H₂O的添加抑制了NO的生成,且该影响主要集中在燃烧初期挥发分N的氧化过程.随着O₂浓度的增加,H₂O添加对oxy-coal燃烧方式下NO生成影响加大.     

O2/H2O燃烧方式下石灰石的间接硫化反应特性

利用水平管式炉和热重实验台架,对O₂/H₂O、O₂/N₂和O₂/CO₂ 3种不同燃烧方式下石灰石的间接硫化反应特性进行了研究。重点探究了燃烧方式、水蒸气浓度对石灰石间接硫化反应的影响规律与机理。同时,对硫化产物进行了X射线荧光光谱（XRF）、X射线衍射（XRD）、孔结构特性和扫描电镜（SEM）分析。结果表明,O₂/H₂O燃烧方式相比于相同氧浓度下的O₂/N₂和O₂/CO₂燃烧方式,石灰石间接硫化反应的钙转化率在化学反应控制阶段基本相同,在扩散控制阶段O₂/H₂O燃烧方式下的钙转化率有显著的提高。主要原因是水蒸气促进了硫化反应后期产物层内的固态离子扩散。此外,O₂/H₂O燃烧方式下,不同的水蒸气浓度对石灰石的钙转化率基本没有影响。     

不同烟气组分对粉状活性焦吸附汞的影响机理

在模拟燃煤热烟气为热源和介质条件下，以准东褐煤为原料，通过一维沉降炉进行炭化活化（一步法）制备粉状活性焦，考察了活性焦对Hg⁰的吸附能力，探索了SO₂、H₂O、O₂、CO₂、H₂O+O₂、SO₂+O₂及H₂O+SO₂+O₂气氛对活性焦吸附Hg⁰的影响机理。结果表明：一步法获得的活性焦对Hg⁰具有较高的吸附性能。N₂气氛作对比，H₂O、H₂O+O₂、CO₂和SO₂气氛下抑制活性焦对Hg⁰的吸附；O₂、SO₂+O₂和H₂O+SO₂+O₂促进活性焦对Hg⁰的吸附。通过Hg 4f的XPS分析证明了不同气氛组成对活性焦吸附Hg⁰的抑制和促进机理。H₂O覆盖在活性焦活性位上和堵塞孔隙而抑制活性焦对Hg⁰的吸附；SO₂与Hg⁰在活性焦上发生竞争吸附而抑制对Hg⁰的吸附；CO₂ 吸附在活性焦微孔上而抑制对Hg⁰的吸附；O₂气氛下主要形成了HgO, SO₂+O₂气氛下Hg⁰被氧化成HgSO₃，进一步氧化成HgSO₄； H₂O+SO₂+O₂气氛下，Hg⁰被氧化成HgO和HgSO₄。     

等速升温流态化下CaO/生物质焦的SO2/NO联合脱除特性

燃煤锅炉污染物超低排放标准对电厂脱硫和脱硝系统提出了更高的要求。CaO作为脱硫剂可以实现循环流化床锅炉烟气中SO₂的高效脱除,焦炭作为还原剂直接还原NO,同时CaO的存在对焦炭还原NO起催化作用,可以实现燃煤烟气中SO₂/NO的联合脱除。为了探究连续温度变化对CaO/生物质焦联合脱硫脱硝性能的影响,在钙循环捕集CO₂技术背景下,研究了等速升温流态化下CaO/生物质焦的SO₂/NO联合脱除特性。探究了烟气中O₂和CO₂对CaO/椰壳焦脱除SO₂/NO的影响。结果表明,O₂通过对椰壳焦表面碳原子的活化作用降低了异相还原NO温度,在300~950℃等速升温过程中CaO/椰壳焦的NO脱除效率逐渐增加,780℃以上能实现100%脱硝。O₂也提高了CaO/椰壳焦的脱硫效率。CO₂与CaO的碳酸化反应以及与椰壳焦的气化反应对同时脱除SO₂/NO有明显抑制作用。O₂和CO₂共同作用下,在500~800℃内CaO/椰壳焦的脱硝效率随温度升高而增加,脱硫效率先降低后升高。NO促进了CaO/椰壳焦脱除SO₂,而SO₂对脱硝有抑制作用。800℃时CaO/椰壳焦同时脱除SO₂和NO的效率分别为97.7%和93.9%。     

低温等离子体用于柴油机尾气脱硝的实验

柴油机作为卡车、重型机械以及船舶的主动力装置仍被广泛采用,其尾气中氮氧化物的脱除技术也是目前的研究热点。本文搭建了模拟柴油机尾气的配气系统,采用介质阻挡放电产生低温等离子体（non-thermal plasma,NTP）的方法对模拟柴油机尾气进行了脱硝的实验研究。实验结果表明：针对本系统,电源效率和能量密度随着输入电压的增大而升高,当输入电压高于60V时,电源效率在90%以上;在O₂/N₂条件下,随着O₂浓度以及能量密度的增加,NO生成量逐渐增加,NO₂生成量先增加后降低最终趋于稳定;在NO/N₂条件下,低温等离子体对NO的脱除率接近100%;在NO/O₂/N₂条件下,随着NO浓度的增加,临界O₂浓度升高,O₂体积分数为1%时脱硝效率在90%以上,O₂体积分数高于14%时低温等离子体的脱硝率为负值,且随着能量密度的增加,生成的NO _x 浓度也更高,O₂浓度对低温等离子体的脱硝性能起决定性作用;在低能量密度时,加入NH₃会提高脱硝性能,高能量密度时NH₃会略微降低NTP的脱硝性能,当加入H₂O模拟真实柴油机尾气成分且喷氨时,获得的脱硝率最高为40.6%。     

O2浓度对污泥燃烧还原性气体产生及还原NO的双重影响

在模拟水泥预分解炉装置上研究污泥燃烧过程中还原性气体的产生及其对NO的还原,并系统研究了O₂浓度（体积分数为0～5%）对还原性气体产生及NO还原的双重影响。TG-FTIR特征分析表明,污泥燃烧产生的还原性气体主要为HCN、NH₃、CO和CH₄。进一步实验研究发现O₂浓度对HCN和NH₃的产生有明显影响,HCN和NH₃在O₂体积分数为3%时产生速率最大。同时,O₂浓度对污泥燃烧还原NO有较大影响。在污泥燃烧温度为900℃,烟气中CO₂体积分数为25%、NO浓度为600mg/m³、SO₂浓度为200mg/m³、O₂体积分数为3%时,NO还原率可达到最大（55.8%）。通过还原性物质（NH₃、CO、CH₄和污泥焦）对NO的还原实验研究进一步发现,NH₃和CO是污泥燃烧过程中NO还原的关键物质,且NH₃对NO的还原随着O₂浓度的增加而增加,而CO对NO的还原受O₂浓度的限制。综合分析表明,O₂浓度对污泥燃烧NO还原的影响主要是由NH₃的产生速率差异、NH₃和CO对NO的还原起主导作用且受O₂浓度影响较大等多种因素综合导致。采用污泥作为还原剂进行NO还原是一种高效的方法,在水泥生产中可通过控制O₂浓度获得较高的NO还原率。     

煤粉炉SNCR对SO3生成影响的数值模拟

基于详细化学反应机理,利用CHEMKIN-PRO软件中的平推流反应器研究了选择性非催化还原（SNCR）脱硝过程对SO₃生成作用,以及烟气中SO₂、NO、O₂和H₂O的体积浓度对SO₃生成量的影响。结果表明,氨的注入改变了SO₃生成机理和主要路径,明显促进烟气中SO₂向SO₃氧化。在NH₃的体积浓度为300 μl·L^-1、SO₂的体积浓度为2000 μl·L^-1、停留时间1.9 s内温度从1373 K降低至573 K时,生成的SO₃体积浓度大于10 μl·L^-1。随着SO₂体积分数的降低,生成的SO₃体积浓度减小,但转化率有所增加;此外生成的SO₃体积浓度随O₂体积浓度、NO体积浓度和停留时间的增加而增加,随着H₂O体积浓度的增加而减小。燃用高硫煤时,SNCR对SO₃的生成作用必须给予重视。     

二乙烯三胺五亚甲基膦酸/Fenton体系氧化脱除NO

针对当前Fenton氧化法脱除燃煤烟气中NO的过程中H₂O₂大量无效分解生成氧气的缺点,本文采用二乙烯三胺五亚甲基膦酸(DTPMPA)/Fenton系统进行氧化脱除NO的实验研究。结果表明：该系统在NO脱除效率为95.1%的情况下,H₂O₂无效分解占比降低至15.5%。DTPMPA浓度的增加抑制了H₂O₂无效分解,其浓度较低时促进NO脱除而浓度较高时抑制NO脱除;H₂O₂及Fe²⁺浓度的增加均对NO脱除及H₂O₂无效分解有一定的促进作用,但二者浓度过高时亦均对脱除NO有一定抑制作用;降低反应温度对NO脱除影响较小,但会削弱H₂O₂无效分解;SO₂对NO的脱除及H₂O₂无效分解影响甚小。电子自旋共振技术和淬灭剂添加实验结果表明：DTPMPA的...     

介质阻挡放电中气体成分对NOx脱除的影响

利用介质阻挡放电(DBD)产生低温等离子体进行烟气的脱硝实验,研究了在乙烯存在的条件下,温度和其他烟气成分对NO_x脱除率的影响。结果表明:随着温度的升高,NO脱除速率增快;模拟烟气中加入CO₂,在能量密度较低时,CO₂作为电负性分子会降低自由基的生成,导致NO的脱除率降低,随着能量密度的升高,CO₂对NO脱除的影响减小;模拟烟气中加入水后可以产生更多的OH、HO₂等自由基,促进NO的氧化;SO₂的加入会与自由基O反应,使初始反应中O与C₂H₄的反应速率减弱,从而影响了NO的氧化速率,但O₃、HO₂等强氧化自由基会优先与NO反应,因此SO₂的加入不会影响NO最终的脱除率。     

Role of active oxygen transients in selective catalytic reduction of N2O with CH4 over Fe-zeolite catalysts

Sharp NO and O₂ desorption peaks, which were caused by the decomposition of nitro and nitrate species over Fe species, were observed in the range of 520–673 K in temperature-programmed desorption (TPD) from Fe-MFI after H₂ treatment at 773 K or high-temperature (HT) treatment at 1073 K followed by N₂O treatment. The amounts of O₂ and NO desorption were dependent on the pretreatment pressure of N₂O in the H₂ and N₂O treatment. The adsorbed species could be regenerated by the H₂ and N₂O treatment after TPD, and might be considered to be active oxygen species in selective catalytic reduction (SCR) of N₂O with CH₄. However, the reaction rate of CH₄ activation by the adsorbed species formed after the H₂ and N₂O or the HT and N₂O treatment was not so high as that of the CH₄ + N₂O reaction over the catalyst after O₂ treatment. The simultaneous presence of CH₄ and N₂O is essential for the high activity of the reaction, which suggests that nascent oxygen species formed by N₂O dissociation can activate CH₄ in the SCR of N₂O with CH₄.     

NO decomposition and reduction by CH4 over Sr/La2O3

Both NO decomposition and NO reduction by CH₄ over 4%Sr/La₂O₃ in the absence and presence of O₂ were examined between 773 and 973 K, and N₂O decomposition was also studied. The presence of CH₄ greatly increased the conversion of NO to N₂ and this activity was further enhanced by co-fed O₂. For example, at 773 K and 15 Torr NO the specific activities of NO decomposition, reduction by CH₄ in the absence of O₂, and reduction with 1% O₂ in the feed were 8.3·10⁻⁴, 4.6·10⁻³, and 1.3·10⁻² μmol N₂/s m², respectively. This oxygen-enhanced activity for NO reduction is attributed to the formation of methyl (and/or methylene) species on the oxide surface. NO decomposition on this catalyst occurred with an activation energy of 28 kcal/mol and the reaction order at 923 K with respect to NO was 1.1. The rate of N₂ formation by decomposition was inhibited by O₂ in the feed even though the reaction order in NO remained the same. The rate of NO reduction by CH₄ continuously increased with temperature to 973 K with no bend-over in either the absence or the presence of O₂ with equal activation energies of 26 kcal/mol. The addition of O₂ increased the reaction order in CH₄ at 923 K from 0.19 to 0.87, while it decreased the reaction order in NO from 0.73 to 0.55. The reaction order in O₂ was 0.26 up to 0.5% O₂ during which time the CH₄ concentration was not decreased significantly. N₂O decomposition occurs rapidly on this catalyst with a specific activity of 1.6·10⁻⁴ μmol N₂/s m² at 623 K and 1220 ppm N₂O and an activation energy of 24 kcal/mol. The addition of CH₄ inhibits this decomposition reaction. Finally, the use of either CO or H₂ as the reductant (no O₂) produced specific activities at 773 K that were almost 5 times greater than that with CH₄ and gave activation energies of 21–26 kcal/mol, thus demonstrating the potential of using CO/H₂ to reduce NO to N₂ over these REO catalysts.     

Catalytic reduction of NOx with H2/CO/CH4 over PdMOR catalysts

Conversion of NO_x with reducing agents H₂, CO and CH₄, with and without O₂, H₂O, and CO₂ were studied with catalysts based on MOR zeolite loaded with palladium and cerium. The catalysts reached high NO_x to N₂ conversion with H₂ and CO (>90% conversion and N₂ selectivity) range under lean conditions. The formation of N₂O is absent in the presence of both H₂ and CO together with oxygen in the feed, which will be the case in lean engine exhaust. PdMOR shows synergic co-operation between H₂ and CO at 450–500 K. The positive effect of cerium is significant in the case of H₂ and CH₄ reducing agent but is less obvious with H₂/CO mixture and under lean conditions. Cerium lowers the reducibility of Pd species in the zeolite micropores. The catalysts showed excellent stability at temperatures up to 673 K in a feed with 2500 ppm CH₄, 500 ppm NO, 5% O₂, 10% H₂O (0–1% H₂), N₂ balance but deactivation is noticed at higher temperatures. Combining results of the present study with those of previous studies it shows that the PdMOR-based catalysts are good catalysts for NO_x reduction with H₂, CO, hydrocarbons, alcohols and aldehydes under lean conditions at temperatures up to 673 K.     

The effect of oxygen concentration on the reduction of NO with propylene over CuO/γ-Al2O3

The effect of oxygen concentration on the pulse and steady-state selective catalytic reduction (SCR) of NO with C₃H₆ over CuO/γ-Al₂O₃ has been studied by infrared spectroscopy (IR) coupled with mass spectroscopy studies. IR studies revealed that the pulse SCR occurred via (i) the oxidation of Cu⁰/Cu⁺ to Cu²⁺ by NO and O₂, (ii) the co-adsorption of NO/NO₂/O₂ to produce Cu²⁺(NO₃⁻)₂, and (iii) the reaction of Cu²⁺(NO₃⁻)₂ with C₃H₆ to produce N₂, CO₂, and H₂O. Increasing the O₂/NO ratio from 25.0 to 83.4 promotes the formation of NO₂ from gas phase oxidation of NO, resulting in a reactant mixture of NO/NO₂/O₂. This reactant mixture allows the formation of Cu²⁺(NO₃⁻)₂ and its reaction with the C₃H₆ to occur at a higher rate with a higher selectivity toward N₂ than the low O₂/NO flow. Both the high and low O₂/NO steady-state SCR reactions follow the same pathway, proceeding via adsorbed C₃H₇---NO₂, C₃H₇---ONO, CH₃COO⁻, Cu⁰---CN, and Cu⁺---NCO intermediates toward N₂, CO₂, and H₂O products. High O₂ concentration in the high O₂/NO SCR accelerates both the formation and destruction of adsorbates, resulting in their intensities similar to the low O₂/NO SCR at 523–698 K. High O₂ concentration in the reactant mixture resulted in a higher rate of destruction of the intermediates than low O₂ concentration at temperatures above 723 K.     

Study of Ag/La0.6Ce0.4CoO3 catalysts for direct decomposition and reduction of nitrogen oxides with propene in the presence of oxygen

Perovskite-type oxide La_0.6Ce_0.4CoO₃ and its doped Ag catalysts were prepared and their catalytic performances were evaluated for the direct decomposition of NO and the selective reduction of NO with propene in the presence of oxygen. A noticeable enhancement in activity was achieved by doping Ag and the optimum Ag loading was 1%. The effects of H₂O, SO₂, CO₂ and O₂ on the performances of Ag/La_0.6Ce_0.4CoO₃ catalysts for NO decomposition were also investigated. The resistance against H₂O and SO₂ appears satisfactory. The inhibition by CO₂ is strong, although it is reversible. Oxygen did not inhibit the NO decomposition reaction but significantly promoted it. Compared with other perovskite-type oxides reported previously, higher conversions were obtained over the present catalysts for the NO reduction by propene. We speculate that the decomposition of NO is the predominant process even in the presence of propene. The catalysts were characterized by N₂-adsorption, XRD, XPS and NO-TPD and some explanations were put forward.     

低温燃烧下NH3的氧化特性

NH₃的气相氧化是低温燃烧过程中NO_x（NO和NO₂）与N₂O的重要来源,为了深入认识其反应规律,在管式流动反应器系统中进行了实验研究。重点考察了挥发分中的可燃气（CO、CH₄或H₂）和NO对NH₃氧化及氮氧化物排放的影响规律,并根据化学反应机理对实验结果进行了分析。研究结果表明,低温氧化性气氛下微量的可燃气就能够显著促进NH₃的氧化,并使NO_x和N₂O的生成量大幅度升高。当可燃气体浓度相同时,H₂对NH₃氧化的影响最大,CO的影响最小,CH₄对NH₃氧化的影响略大于CO。随着可燃气体浓度的升高,其对NH₃氧化与氮氧化物生成的影响先逐渐增加,然后趋于稳定。反应初始气体中存在NO时,也会加速NH₃的氧化。     

Modifications to the surface chemistry of low-rank coal-based carbon catalysts to improve flue gas nitric oxide removal

The effectiveness of carbons as low-temperature selective catalytic reduction (SCR) catalysts will depend upon their physical and chemical properties. Surface functional groups containing oxygen are closely related to the catalytic activity of carbons. These groups are expected to change the interaction between the carbon surface and the reactants through a variation in adsorption and reaction characteristics. This paper presents a more detailed study of the effects of either gas-phase sulfuric acid or oxygen oxidation treatments on the catalytic NO reduction by low-rank coal-based carbon catalysts. Raw and treated carbons were characterized by N₂ and CO₂ surface areas, TPD and ash content. NO removal capacity of carbons was determined by passing a flow containing NO, H₂O, O₂, NH₃ and N₂ through a fixed bed of carbon at 150°C and 4 s of residence time, the effluent concentration being monitored continuously during the reaction. The effects of varying the type and conditions of the treatment on the physicochemical features of carbons were studied. The gas-phase sulfuric acid treatment (corresponding to a first step SO₂ removal) markedly enhanced carbon activities for NO removal. On the contrary, oxygen oxidation enhanced NO removal capacity of chars to a lower extent. Therefore, the carbons studied could be used in a combined SO₂/NO removal process, because the use and regeneration of the carbon in the first step is beneficial for the performance in the second one.