甲胺作还原剂的选择性非催化还原脱硝特性的实验研究

为改善工业窑炉以及锅炉低负荷运行工况下的脱硝特性,本文对甲胺作还原剂的选择性非催化还原（SNCR）脱硝特性进行了实验研究,探讨了各控制因素对脱硝特性的影响以及分析了反应机理。实验结果表明：脱硝效率随反应温度呈双峰特性,拐点温度为750℃,最佳温度窗口为450～600℃;脱硝效率随氨氮比（NSR）增大而升高,反应产生的副产物NO₂和N₂O浓度随之增大;氧含量对SNCR脱硝特性具有双重特性,高浓度和低浓度氧气均对脱硝反应不利;物料浓度随NO初始浓度增加而增大,脱硝效率和副产物也提高; SO₂浓度越高,脱硝效率下降越多;水汽含量增大,脱硝效率也随之增大。本文的实验结论有助于SNCR脱硝工艺应用于工业窑炉以及优化锅炉低负荷运行时的脱硝特性。     

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。     

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。     

气流床煤粉工业锅炉非催化还原脱硝试验

选择性非催化还原(SNCR)脱硝技术是燃煤工业锅炉领域重要的脱硝技术之一，目前电站锅炉SNC■脱硝效率普遍偏低，且工业锅炉SNCR应用研究较少。针对一台20 t/h气流床煤粉工业锅炉测量了炉膛温度以及不同喷枪位置和气液压力下炉膛出口的NO_x排放浓度，研究了气流床煤粉工业锅炉中SNCR的脱硝性能。结果表明，采用尿素进行脱硝反应的最佳温度窗口为790～850℃,最佳温度窗口位于炉膛中心截面附近，喷枪设置在炉膛侧壁中心优于炉膛顶部，喷枪插入深度和角度对脱硝效率的影响较小，喷枪位于最优位置时，脱硝效率可达87.2%,出口NO_x质量浓度为38 mg/m³,满足超低排放。喷枪流量随液压升高和气压降低而增大，气压大于液压时，喷枪雾化较好，整个扇面液滴分布较均匀，2.38≤氨氮物质的量比≤3.00时，液压越低，脱硝效率越高，0.30 MPa≤液压≤0.35 MPa, 0.29 MPa≤气压≤0.40 MPa时，SNCR脱硝效率较高，且氨逃逸较少。喷枪液滴雾化情况对脱硝效率的影响高于扇面角度。     

循环流化床锅炉SNCR反应机理与脱硝特性数值模拟

为验证SNCR反应简化机理的准确性,将SNCR反应的复杂机理与两步简化机理进行化学动力学对比计算分析,结果表明,在920~1 040℃,2种机理对反应器出口NO和NH3体积分数的计算结果比较接近。利用Fluent软件结合两步简化机理进行数值模拟,结果表明,随着温度的升高,脱硝效率先增加后降低,在925℃左右达到最大值,而氨逃逸量持续降低;增加还原剂用量,最佳反应温度保持在925℃左右,脱硝效率和氨逃逸量都会提高,但脱硝效率的涨幅会逐渐降低,而氨逃逸的涨幅逐渐升高;提高烟气氧含量能使反应的温度窗口向低温方向移动,使氨逃逸量和脱硝效率同时降低。     

循环流化床燃煤机组SNCR脱硝过程气液传质和反应特性

采用CFD模拟方法预测了300 MW循环流化床机组SNCR脱硝过程中的还原剂液滴蒸发、烟气混合和反应特性。结果表明烟气在旋风分离器内贴壁旋转流动并形成外旋流为准自由涡和内旋流为刚性涡的双涡结构，使液滴与烟气接触约0.01 s后开始恒温蒸发，并强化了烟气与气态还原剂的混合效果。氨水为还原剂时，NH₃主要分布于旋风分离器锥体上方；尿素为还原剂时，蒸发后快速分解的HNCO消耗速率高于NH₃，其中NH₃浓度分布与氨水为还原剂相似，相同烟气温度和氨氮摩尔比时氨水和尿素溶液对应脱硝效率分别约为79.5%和76.5%。温度对脱硝效率的影响表现为先上升后下降趋势，当温度由1023 K提高至1173 K时NH₃与NO反应速率提高，脱硝效率由19.7%提高至81.0%；而当温度由1173 K进一步提高至1323 K时，NH₃由于自身氧化速率显著提高而导致脱硝效率降低至17.4%。脱硝效率随氨氮摩尔比(NSR)增大而升高，但还原剂利用率的降低致使氨逃逸率增大，综合考虑本台CFB锅炉SNCR脱硝效率和...     

甲胺作还原剂的选择性非催化还原脱硝特性的实验研究

为改善工业窑炉以及锅炉低负荷运行工况下的脱硝特性,本文对甲胺作还原剂的选择性非催化还原(SNCR)脱硝特性进行了实验研究,探讨了各控制因素对脱硝特性的影响以及分析了反应机理。实验结果表明:脱硝效率随反应温度呈双峰特性,拐点温度为750℃,最佳温度窗口为450~600℃;脱硝效率随氨氮比(NSR)增大而升高,反应产生的副产物NO_2和N_2O浓度随之增大;氧含量对SNCR脱硝特性具有双重特性,高浓度和低浓度氧气均对脱硝反应不利;物料浓度随NO初始浓度增加而增大,脱硝效率和副产物也提高;SO_2浓度越高,脱硝效率下降越多;水汽含量增大,脱硝效率也随之增大。本文的实验结论有助于SNCR脱硝工艺应用于工业窑炉以及优化锅炉低负荷运行时的脱硝特性。     

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%。     

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。     

烧成系统中CO对SNCR系统运行效率 的影响及应对措施

分析了当烧成系统煤燃烧不完全对SNCR系统运行效率的影响,结果表明:煤燃烧不完全使得窑尾烟气中CO浓度上升,会明显降低SNCR系统的脱硝效率,必须通过大幅提高SNCR系统的氨氮比从而满足环保排放要求(320mg/m~3,标况下),这样不仅大幅提高了系统运行成本,而且造成烟囱氨逃逸增加。通过调节雾化压力、调整喷枪布置、脱硝反应区温度等措施来降低系统运行氨水耗量。结果表明:雾化压力、喷枪布置对系统氨水耗量几乎没有影响,降低反应区温度可显著减小系统氨氮比,同时保持排放满足环保要求,说明反应区CO的存在会拉低SNCR系统的最佳温度窗口。     

化学计量比、雾化压力对电站锅炉SNCR脱硝的影响

引言 电厂锅炉作为化学能向蒸汽热能转换的一种设备,是火电生产过程中一个重要的环节.但是,锅炉燃烧化石燃料进行能量转化的同时也向环境排放了各种污染物质.     

Ammonia and nitrous oxide emissions from grass and alfalfa mulches

Ammonia (NH₃) and nitrous oxide (N_-2O) emissions were measured in the field for three months from three different herbage mulches and from bare soil, used as a control. The mulches were grass with a low N-content (1.15% N in DM), grass with a high N-content (2.12% N in DM) and alfalfa with a high N-content (4.33% N in DM). NH₃ volatilization was measured using a micrometeorological technique. N_-2O emissions were measured using closed chambers. NH₃ and N_-2O emissions were found to be much higher from the N-rich mulches than from the low-N grass and bare soil, which did not differ significantly. Volatilization losses of NH₃ and N_-2O occurred mainly during the first month after applying the herbage and were highest from wet material shortly after a rain. The extent of NH₃-N losses was difficult to estimate, due to the low frequency of measurements and some problems with the denuder technique, used on the first occasions of measurements. Nevertheless, the results indicate that NH₃-N losses from herbage mulch rich in N can be substantial. Estimated losses of NH₃-N ranged from the equivalent of 17% of the applied N for alfalfa to 39% for high-N grass. These losses not only represent a reduction in the fertilizer value of the mulch, but also contribute appreciably to atmospheric pollution. The estimated loss of N_-2O-N during the measurement period amounted to 1% of the applied N in the N-rich materials, which is equivalent to at least 13 kg N_-2O-N ha^-1 lost from alfalfa and 6 kg ha^-1 lost from high-N grass. These emission values greatly exceed the 0.2 kg N_-2O-N ha^-1 released from bare soil, and thus contribute to greenhouse gas emissions.     

Experimental study of the influence of sodium salts as additive to NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>OUT process

An experimental study of the SNCR process with urea as reducing agent and sodium salts as additive has been carried out, and detailed analysis of the reaction mechanism has been given here. In the temperature range of 800–975 °C, NO concentration decreases at first and then increases while the concentration of N₂O increases at first and then decreases with the increasing of temperature, and the turning point is 900 °C. With increasing of normalized stoichiometric ratio of reduction nitrogen to NO _x (NSR), NO removal efficiency increases, while the concentration of N₂O also increases, which decreases overall NO _x removal efficiency. With sodium salts as additive, the concentration of N₂O decreases with increasing of sodium salts addition at all temperatures, while the concentration of NO decreases at first and then increases at low-temperature side of the temperature window and increases at high-temperature side with additional increasing, whose changing extent is smaller than N₂O. Since sodium salts as additive can remove N₂O effectively and have no large influence on the removal of NO, the effect of sodium salts as additive is the combined effect of the production of active radicals and the removal of HNCO produced by the decomposition of urea through neutralization reactions, which is more important. To achieve the same effect under each condition, the needed addition of NaOH and CH₃COONa is less than that of Na₂CO₃ counting as Na atom. For the decomposition of CH₃COONa can produce CH₃COO, its addition can promote the reduction of NO more obviously at the lower temperature than Na₂CO₃ or NaOH. Overall NO _x removal efficiency at 900 ‡C with NSR=1.5 had been improved from about 30% to 70.45% through the addition of sodium salts. Sodium salts as additive caused the flue gas to become alkaline gas, but it was not serious for sodium salts existing as NaNCO.     

Effects of NH3·H2O pretreatment on the fabrication of uniform titania nanocoating in an aqueous solution

An investigation is reported of the TiO₂ nanocoating on the ZnS-based phosphor via a sol-gel method in an aqueous solution using titanium diethanolamine complex as the precursor. The pretreatment of ZnS phosphors with NH₃·H₂O is important to the coating process. When NH₃·H₂O was added into the ZnS phosphor suspension, OH⁻ promoted the hydrolysis of Zn²⁺ on the surface of ZnS phosphors, which resulted in the formation of Zn-OH. Zn-OH reacted with the hydrolysis product of titanium diethanolamine complex, thus the titania coatings were obtained. The coating morphology was strongly dependant on the pH of the pretreated ZnS phosphor suspension and the weight ratio of ZnS to TiO₂.     

Effect of the Presence of Ceria in the NSR Catalyst on the Hydrothermal Resistance and Global DeNOx Performance of Coupled LNT–SCR Systems

The global performance of coupled LNT–SCR systems, addressed to high NOx-to-N₂ conversion, minimal ammonia slip and null N₂O production, as well as the hydrothermal resistance of single NSR and SCR monolith catalysts and their coupling is discussed. Pt–Ba/Al₂O₃ and Pt–Ce–Ba/Al₂O₃ were washcoated on cordierite monoliths as NSR catalysts, and Cu/CHA was washcoated on similar monoliths as SCR catalysts. Both monoliths were coupled in two subsequent reactors to conform the LNT–SCR system. Previously to washcoating, the fresh powder catalysts and after severe hydrothermal aging were fully characterized by N₂ adsorption–desorption isotherms at 77 K, X-ray diffraction, NH₃ temperature-programmed desorption, and H₂ chemisorption to relate textural and chemical characteristics with the DeNO_x performance. The Cu/CHA catalyst shows an excellent hydrothermal resistance for the NH₃–SCR reaction. Incorporation of ceria to the model Pt–BaO/Al₂O₃is beneficial for the NO-to-NOx oxidation and NO₂ storage, improving NO conversion at low temperature and reducing the NH₃ slip. However, addition of ceria is detrimental for the hydrothermal resistance of the NSR catalyst. However, this detrimental effect is minimized when the NSR catalyst is coupled with the Cu/CHA monolith downstream of the NSR catalyst, achieving the coupled LNT–SCR device high NO conversion and minimal NH₃ slip with superior N₂ selectivity for an extended temperature windows, including as low as 220 °C, and maintaining performance even after severe hydrothermal aging.     

Porous Si3N4 ceramics prepared via slip casting of Si and reaction bonded silicon nitride

Slip casting process combined with reaction bonded silicon nitride (RBSN) was used to prepare porous Si₃N₄ ceramic with near-net and complex shape. A butyl stearate (BS) coated process was introduced to restrain the hydrolysis of Si, and ammonium polyacrylate (NH₄PAA) was used to enhance the dispersion of coated Si. The measured oxygen content showed that the hydrolysis of Si was strongly prohibited by BS coating, and relatively low viscosity was obtained with the addition of 0.25-1.5 wt% NH₄PAA to the 60 wt% solid load slurry. 40-60 wt% solid load slurries were used for slip casting in the experiment. After vacuum degassing, slip casting, debindering and nitridation, a density of 1.57-1.92 g/cm³ (porosity 50.9-40%) and a flexural strength of 47-108 MPa were obtained. The samples without vacuum degassing showed a large number of nanowires grown in the large pores.     

A kinetic study of NOx reduction over Pt/SiO2 model catalysts with hydrogen as the reducing agent

Flow reactor experiments and kinetic modeling have been performed in order to study the mechanism and kinetics of NO_x reduction over Pt/SiO₂ catalysts with hydrogen as the reducing agent. The experimental results from NO oxidation and reduction cycles showed that N₂O and NH₃ are formed when NO_x is reduced with H₂. The NH₃ formation depends on the H₂ concentration and the selectivity to NH₃ and N₂O is temperature dependent. A previous model has been used to simulate NO oxidation and a mechanism for NO_x reduction is proposed, which describes the formation/consumption of N₂, H₂O, NO, NO₂, N₂O, NH₃, O₂ and H₂. A good agreement was found between the performed experiments and the model.     

An assessment of N loss from agricultural fields to the environment in China

Using the 1997 IPCC Guidelines for National Greenhouse Gas Inventory Methodology, and statistical data from the China Agricultural Yearbook, we estimated that the direct N₂O emission from agricultural fields in China in 1990 was 0.282 Tg N. Based on micro-meteorological field measurement of NH₃ volatilization from agricultural fields in different regions and under different cropping systems, the total NH₃ volatilization from agricultural fields in China in 1990 was calculated to be 1.80 Tg N, which accounted for 11% of the applied synthetic fertilizer N. Ammonia volatilization from agricultural soil was related to the cropping system and the form of N fertilizer. Ammonia volatilization from paddy fields was higher than that from uplands, and NH₄HCO₃ had a higher potential of NH₃ volatilization than urea. N loss through leaching from uplands in north China accounted for 0.5–4.2% of the applied synthetic fertilizer N. In south China, the leaching of applied N and soil N from paddy fields ranged from 6.75 to 27.0 kg N ha^-1 yr^-1, while N runoff was between 2.45 and 19.0 kg N ha^-1 yr^-1.     

负载型钒钛脱硝催化剂酸化处理与性能

以商业TiO₂为载体,采用浸渍法制备了V₂O₅-WO₃-TiO₂/SO₄^2-催化剂,考察了硫酸酸化载体TiO₂的顺序及硫酸酸化量对氨气选择性催化还原NO活性的影响,采用XRD、BET、FT-IR、TG-DTA、TPD等手段对催化剂进行了表征。BET表征结果表明,随着酸化处理的用酸量增大,催化剂表面积降低;但FT-IR、TG结果表明,增大酸化处理用硫酸量提高了硫酸根与钨之间的电子交互作用。程序升温的活性测试结果表明,硫酸酸化处理对催化剂活性具有促进作用,结合NH₃-TPD表征证实了具有酸化处理程序制备的催化剂可以增强表面酸性位,从而使催化剂具有高活性。