COAL PROPERTY EFFECTS ON N2O AND NOx FORMATION FROM CIRCULATING FLUIDIZED BED COMBUSTION OF COAL

The effects of coal properties on N₂O and NO_x formation from circulating fluidized bed combustion of coal was examined through burning nine typical coals and a coal shale, widely used in China over a wide range of coal ranks, in a bench-scale circulating fluidized bed. It was found that N₂O and NO_x formation had similar dependence on coal rank. Fixed carbon content and nitrogen content were the most important coal properties to influence N₂O and NO_x emissions from circulating fluidized bed combustion of coal. A coal with high fixed carbon content had high conversion ratio of fuel-N into N₂O and NO_x. The conversion ratio of fuel-N into N₂O or NO_x increased with nitrogen content of coal, whereas it decreased with O/N ratio. No significant correlation between conversion ratio of fuel-N into N₂O or NO_x and C/N ratio was identified. To clarify the coal property effect, investigation of a wide range of coal rank, is important.     

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。     

V2O5-WO3-MoO3/TiO2催化剂在柴油机NH3-SCR系统中的性能

针对柴油机运行工况特点及柴油机尾气成分特点,以工业纯锐钛型二氧化钛、偏钒酸铵、偏钨酸铵、钼酸铵为主要原料制备了颗粒状V₂O₅-WO₃-MoO₃/TiO₂催化剂,以Lister Petter TR1重型直喷式单缸柴油机为依托搭建试验台,研究了在真实柴油机尾气环境下催化剂的脱硝性能。结果表明,柴油机负载增大,催化剂脱硝活性呈现下降趋势。1800 r·min^-1时,脱硝活性最大值87.1%在负载25%、反应温度380℃、空速20000 h^-1、氨氮比1.0处取得。柴油机负载不同,导致催化剂活性温度窗口(脱硝活性>70%)发生较大变化,与负载25%相比,负载50%活性温度窗口减小约60℃。增大柴油机负载可以提高NH₃/N₂O反应起始温度,但是同时会导致高温区间(>400℃)N₂O生成量增大。     

不同规模的煤燃烧装置中燃料-N向N2O和NOx的转化（英文）

With focus on investigating the effect of combustor scale on the conversion of fuel-N to NOx and N20, experiments are carried out in three combustors, including single coal particle combustion test rig, laboratory scale circulating fluidized-bed boiler （CFB） and full scale CFB in this work. For single coal particle combustion, the majority of f-uel-N （65%-82%） is released as NOx, while only a little （less than 8%） fuel-N yields N20. But in labora- tory scale CFB, the conversion of fuel-N to N20 is increases, but the conversion of fuel-N to NOx is quite less than that of single coal particle combustion. This is because much char in CFB can promote the NOx reduction by in- creasing N20 formation. In full scale CFB, both of the conversion of fuel-N to NOx and the conversion of fuel-N to N20 are smaller than laboratory scale CFB.     

重型柴油机主要含氮化合物的排放特性

采用傅里叶变换红外光谱(FTIR)技术,研究了加装选择性催化还原SCR装置的重型柴油机主要含氮化合物排放,重点探索了不同工况下主要含氮化合物NO、NO₂和N₂O的排放特性。结果表明:未加装SCR的原机,随负荷的增加,柴油机NO排放持续上升,NO₂排放先升后降,N₂O排放很少。加装SCR后该柴油机NO与NO₂排放均明显下降,标定转速下NO₂排放降幅较大,主要是其NO₂/NO值稍高导致快速SCR反应较多的原因。由于存在SCR副反应,与原机相比,柴油机N₂O排放比原机平均增加2倍以上,最大转矩转速下N₂O排放升幅更高。N₂O排放随负荷的增加而上升,主要是排温升高导致NH₃氧化生成N₂O反应速率增加的原因。加装SCR后,该机排气中的NO/NO_x值要明显低于原机状态,而外特性的NO₂/NO_x值和N₂O/NO_x值高达12.8%和20.7%,均远高于原机的3.0%和0.5%。     

添加剂对NOxOUT脱硝及N2O、CO生成的影响特性

通过试验研究了NO_x污染的NO_xOUT脱除特点和温室气体N₂O及CO的生成规律,结合动力学分析,探讨了添加剂的作用。结果表明：在不同氨氮比（NSR）下,最佳反应温度为950℃,最高脱硝效率可达76.33%;N₂O随温度的生成曲线类似于效率曲线,在950℃左右达到最大排放量;N₂O的排放随NSR和氧量的增加而升高;温度较高时,N₂O的排放随停留时间的延长先增加后减少;碳酸钠、乙酸钠、谷氨酸钠及乙醇可有效提高低温侧的脱硝效率和拓宽相应的温度窗口,其中谷氨酸钠最为明显;脱硝效率随钠盐添加量的变化与温度有关,钠原子最佳添加量为60 ml·L^-1;上述添加剂均可明显降低中高温段的N₂O、CO排放,低温端则相反;N₂O、CO的排放随温度、添加剂种类及浓度的不同而呈现各自的变化趋势。     

NTP转化C3H6/NO/N2气氛中NO及发射光谱分析

利用介质阻挡放电产生低温等离子体转化C₃H₆/NO/N₂气氛中NO,结合发射光谱诊断法研究了碳氢化合物C₃H₆对NO转化的影响。研究结果表明,随着放电功率的升高,NO转化率先升高后逐渐趋于平缓,NO₂浓度持续降低,N₂O浓度呈先升高后降低趋势,NO主要被还原为N₂;相同放电功率下,随着C₃H₆初始浓度升高,NO_x转化率和N₂O浓度升高、NO₂浓度降低;添加C₃H₆会降低N₂第二正带系和NO-γ带的发射光谱强度,产生CN自由基的激发跃迁谱线,影响NO的化学反应机制,同时生成了棕黄色的聚合物。     

Effect of operating conditions on the reduction of nitrous oxide by propane over a Fe-zeolite monolith

Fluidised bed combustion is an important source of nitrous oxide emissions. The influence of different operating parameters, such as catalyst volume, temperature, gas hourly space velocity, and hydrocarbon addition, on the activity, selectivity, and poisoning tolerance of a Fe-ZSM-5 monolith for the nitrous oxide selective catalytic reduction, has been investigated under realistic conditions, at bench scale.

Both in the absence or in the presence of poisons, such as H₂O, NO, and SO₂, the optimisation of operating conditions gives rise to a broadening of the temperature window for N₂O reduction, making it more compatible with real application conditions, with a simultaneous reduction in hydrocarbon fugitive emission, resulting in an environmental friendly process.

Excessively high reaction temperatures seem to be needed to obtain an acceptable level of N₂O decomposition. On the contrary, high N₂O reduction conversions are obtained, even in the presence of poisons and at relatively low temperatures, which is the preferred situation in the processes of pollutants removal from stationary combustion sources.

The optimum value of C₃H₈/N₂O ratio to be used for reducing N₂O over the catalyst system seems to be about the unity, since higher N₂O and C₃H₈ conversions and lower hydrocarbon unwanted emissions are attained, with a low consume of propane as selective reductant.     

利用Fluent软件对N_2O催化分解反应器数值模拟

为了设计N_2O催化分解反应器,运用Fluent软件对整体式分子筛催化剂进行数值模拟,考察孔密度和操作条件对整体式分子筛催化剂转化率的影响。结果表明,在相同温度下,N_2O的转化率随着催化剂孔密度的减小而降低。在反应器轴向距离120 mm处,气体反应最快;提高入口温度、浓度或降低空速,均有利于在较短的轴向距离内达到较高的N_2O转化率。在固定床反应器中,比较棒状催化剂和整体式催化剂中床层温度、反应转化率及轴向压降的变化规律,为整体式分子筛催化剂工业化设计提供理论基础。     

Combined plasma-catalytic processing of nitrous oxide

The gliding arc discharge, combined with a catalytic bed, has been applied for nitrous oxide processing in oxygen containing gases. It has been found that under conditions of the gliding arc, nitrous oxide in mixtures with oxygen or air not only decomposes to oxygen and nitrogen, but is also oxidised to nitric oxide. The overall conversion of nitrous oxide, as well as the degree of N₂O oxidation to NO were studied as a function of its initial concentration, flow rate, and discharge power. The overall N₂O conversion and degree of oxidation to NO decreased with increasing flow rate and initial N₂O concentration, and increased with increasing discharge power. The degree of N₂O oxidation to NO varied within 20–37%. The overall conversion and degree of N₂O oxidation increased when granular dielectric materials (TiO₂, SiO₂ (quartz glass), and γ-Al₂O₃) were introduced into the reaction zone. The energy efficiency and the overall conversion of N₂O were still further increased due to catalytic effects of a number of metal oxides (CuO, NiO, MnO₂, Fe₂O₃, Co₃O₄, ZrO₂) deposited on γ-Al₂O₃. The activity of the oxide catalysts within the active power range of 300–360 W decreased in the order: CuO>Fe₂O₃>NiO>MnO₂>Co₃O₄>ZrO₂. It has been concluded that the combined plasma-catalytic processing may be an efficient way for the reduction of N₂O emissions.     

Selective catalytic reduction of N2O and NOx in a single reactor in the nitric acid industry

The nitric acid industry is a source of both NO_x and N₂O. The simultaneous selective catalytic reduction of both compounds using propane as a reductant has been investigated. A stacked catalyst bed with first a Co-ZSM-5 catalyst and second a Pd/Fe-ZSM-5 catalyst gives >80% conversion of N₂O and NO_x above 300 °C at atmospheric pressure. At 4 bar absolute pressure (bara) the Co-ZSM-5 DeNO_x catalyst shows higher NO_x and propane conversion. This leaves not enough propane for the Pd/Fe-ZSM-5 DeN₂O catalyst, which causes a ‘dip’ in N₂O conversion. Reducing the space velocity (SV) of the first catalyst bed secures high NO_x and N₂O conversions from 300 °C and up at 4 bara.     

温度和气氛对高K高S糠醛渣灰分的烧结特性研究

糠醛渣的能源化利用是糠醛产业清洁生产和碳减排的有效途径。然而,现有的直接燃烧利用常面临着因糠醛渣高K引起的灰分烧结严重、高S导致的SO_x排放量大和高水含量导致的燃烧效率低等难题。基于此,在管式炉中考察了单一气氛(N₂、CO₂、O₂)和混合气氛(N₂+H₂O、CO₂+H₂O、O₂+H₂O)中糠醛渣灰在不同温度下的烧结特性,并对灰分颜色、收缩率、微观形貌、矿物质成分和K/S释放等特性进行系统分析。灰分热收缩行为显示,随温度升高,灰样收缩率增加;在单一气氛中添加水蒸气能促进灰分烧结。SEM分析发现,在灰分烧结前,其微观结构在低温下已出现熔融和结渣。XRD分析表明,灰分烧结与低熔点矿物生成紧密相关。单一气氛中,高温下N₂促进钾长石生成;CO₂抑制钾长石生成;O₂促进钙铝黄长石和透辉石生成。在混合气氛中,水蒸气的出现促进多种低熔点钾铝硅酸盐生成,如钾长石和白榴石等。XRF分析显示,随温度升高,灰样中K的固留率(G_K)和S的固留率(G_S)降低;在考察的单一气氛中,高温时,N₂中G_K最低;G_S受气氛的影响较小。在考察的复合气氛中,高温时,G_K受气氛影响较小;G_S受气氛影响严重,特别地,O₂+H₂O气氛中G_S最高,S逸散最少。为抑制糠醛渣灰分烧结和K/S元素逸散到气相中,糠醛渣在流化床燃烧过程中应控制运行温度(低于900℃)、降低气氛中N₂的含量。     

氧分级对药渣O2/CO2燃烧NOx生成规律与反应机理的影响

在我国目前能源结构中,化石能源尤其是煤炭资源占比很高,造成了极大的环境压力。抗生素发酵药渣为近年来产量迅速升高的固体废弃物,也是一种生物质燃料资源,但目前对药渣的能源化利用研究较少。以CH4等气体来模拟药渣可燃成分,利用Chemkin模拟软件中的PFR反应器构建了药渣在O₂/CO₂气氛下氧气分级燃烧及非分级燃烧模型,对2种情况下NO_x生成特性进行了模拟研究,探求了氧气分级及非分级燃烧时各种因素的影响,并利用生成速率分析法和敏感性分析法对结果进行了反应机理分析。研究结果表明,在氧气非分级条件下,NO_x转化率随燃烧温度升高先升高后降低,在1500℃左右达到峰值;NO_x转化率随过量氧气系数增加而升高,在过量氧气系数由0.9增至1.1时,增幅显著。在氧气分级条件下,主燃区燃烧温度对NO_x转化率的影响较为复杂;NO_x转化率随燃尽风率增加先降低后升高,随燃尽风位置推后降低。氧气分级条件下,还原气氛促进了NO_x中N向其他组分转化,能够明显降低NO_x生成。当燃烧温度低于1500℃,燃尽风率为0.35左右时,NO_x转化率最低。首次对药渣在O₂/CO₂气氛下的燃烧进行了反应动力学模拟研究,探求了各种因素的影响,为实现药渣能源化利用提供了指导。     

含氮模型化合物用于化学链燃烧的氮氧化物释放特性

以谷氨酸、甘氨酸和苯丙氨酸作为生物质的含氮模型化合物,进行化学链燃烧实验,主要考察了反应温度、氨基酸种类、碱金属钾元素等对化学链燃烧还原反应过程中氮氧化物释放特性的影响。结果显示,挥发分氮的释放迅速,温度的升高有利于NO和NO₂的生成,N₂O的生成会出现波动。模型化合物的氮含量越高,可能越不利于氮向氮氧化物的转化。钾元素对苯丙氨酸的化学链燃烧过程中NO的释放抑制作用较强,而对其他氨基酸化学链燃烧过程中氮氧化物释放的影响则不太显著。     

Catalytic reduction of N2O over steam-activated FeZSM-5 zeolite: Comparison of CH4, CO, and their mixtures as reductants with or without excess O2

The catalytic reduction of N₂O by CH₄, CO, and their mixtures has been comparatively investigated over steam-activated FeZSM-5 zeolite. The influence of the molar feed ratio between N₂O and the reducing agents, the gas-hourly space velocity, and the presence of O₂ on the catalytic performance were studied in the temperature range of 475–850 K. The CH₄ is more efficient than CO for N₂O reduction, achieving the same degree of conversion at significantly lower temperatures. The apparent activation energy for N₂O reduction by CH₄ was very similar to that of direct N₂O decomposition (140 kJ mol⁻¹), being much lower for the N₂O reduction by CO (60 kJ mol⁻¹). This suggests that the reactions have a markedly different mechanism. Addition of CO using equimolar mixtures in the ternary N₂O + CH₄ + CO system did not affect the N₂O conversion with respect to the binary N₂O + CH₄ system, indicating that CO does not interfere in the low-temperature reduction of N₂O by CH₄. In the ternary system, CO contributed to N₂O reduction when methane was the limiting reactant. The conversion and selectivity of the reactions of N₂O with CH₄, CO, and their mixtures were not altered upon adding excess O₂ in the feed.     

Catalytic reduction of NOx by biomass-derived activated carbon supported metals

In this study, to prepare a series of activated carbon-supported metals for the catalytic reduction of NO_x to N₂ in excess O₂, activated carbons derived from lignocellulosic and herbaceous biomasses were selected as the reducing agents, and alkali and transition metals were used as the catalytic active phases. The effects of the type of biomass, carbonization temperature and catalyst composition on NO_x reduction efficiency were analyzed in a fixed-bed flow reactor. The results showed that two temperature regimes are present for the NO_x-carbon reaction:at temperatures below 250℃, the NO_x adsorption process on the carbon surface was predominant, whereas true NO_x reduction by carbon occurred at temperatures above 250℃, producing N₂, CO₂ and CO. The influence of the carbonization temperature on carbon reactivity depended on the effect of the carbonization temperature on the carbon surface area and the reduction of the metal species on carbon. All studied metals catalyzed both NO_x and O₂ reduction by carbon, and potassium could strongly enhance the C-NO_x reaction without substantial carbon consumption by O₂. Moreover, the potassium supported by sawdust-derived activated carbon exhibited higher selectivity and capacity towards NO_x reduction than did its previously reported coal-derived counterparts. These properties were ascribed to the high dispersion of the active potassium species on the carbon surface, as observed through the comparison of X-ray photoelectron spectroscopy and powder X-ray diffraction results for the carbons made from biomass and coal-based precursors.     

Nitrous oxide reduction with ammonia over Co---MgO catalyst and the influence of excess oxygen

N₂O decomposition on Co---MgO was studied under high (6.67 kPa) and low (75 Pa) N₂O pressure and the effect of reductant (C₂H₆, NH₃) was studied. The activity decays because of the strong adsorption of oxygen produced, while the reductant removed the adsorbed oxygen giving a steady catalysis. The reaction between NH₃ and excess amount of O₂ produced N₂O as a main product. Although N₂O gives the same intermediate (O) as O₂ does, the former decomposition seems to proceed faster than the latter on Co---MgO. The reaction mechanism studied here was compared with the SCR (NO---NH₃ in O₂) reaction on V₂O₂-TiO₂. Since NH₃, N₂O and O₂ gives only N₂ and water, Co---MgO can be a possible catalyst used in the boiler exhaust to reduce N₂O concentration by adding ammonia.     

无烟煤化学链燃烧过程燃料氮转化释放特性

基于赤铁矿石载氧体,在小型单流化床反应器上,开展煤挥发分和焦炭的化学链燃烧研究,探讨挥发分氮和焦氮在化学链燃烧过程中的转化特性。研究表明:燃料氮释放的中间产物HCN和NH₃与铁矿石载氧体具有较高的化学反应亲和性,易于被载氧体氧化生成N₂和NO。淮北无烟煤挥发分氮转化过程中,NO是唯一的氮氧化物,反应器出口中间产物NH₃的释放份额略高于HCN。在煤焦化学链燃烧还原过程中,部分燃料氮释放的中间产物HCN和NH₃被铁矿石氧化导致少量NO的生成,还原过程中无N₂O的释放;较高的还原反应温度加速了NO的生成。减少进入载氧体氧化再生过程的焦炭量可减少空气反应器NO和N₂O的生成。     

高含水菌渣流化床燃烧NOx、SO2排放特性

采用流化床反应器，研究了高含水抗生素菌渣直接燃烧的NO_x、SO₂排放特性。结果表明，增加过量空气系数，NO_x排放浓度升高，SO₂排放浓度降低；升高燃烧温度，NO_x及SO₂排放浓度均升高；随着燃料含水率的增加，NO_x及SO₂排放浓度均呈现先降低后升高的趋势。空气分级燃烧能有效降低NO_x排放，二次风率增加，NO_x排放浓度显著降低；当二次风率为3/7时，NO_x排放浓度较传统燃烧降低50%。添加CaCO₃进行炉内脱硫，实验结果显示：随钙硫摩尔比（Ca/S）增加，SO₂排放浓度下降，当Ca/S 3时，SO₂排放浓度降低到25 mg·m^-3以下，脱硫效率超过99%。     

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。