氢氧催化气相耦合反应过程研究

以微尺寸反应器为基础,对氢空催化燃烧反应过程进行分析,探究气相反应和表面催化反应的耦合效果,通过建立微尺寸反应模型对反应过程进行模拟,考察氢空流量、氢体积分数及催化层位置等参数对反应过程和反应效率的影响,并通过仿真分析对爆炸极限内反应可靠性进行验证,研究表明氢气的体积分数、氢空混合气流速、催化层位置均对催化效率及反应速率产生影响,通过探究上述因素的影响规律可为氢氧催化反应应用提供技术参考。     

1kW SOFC-CHP系统用催化燃烧耦合蒸汽重整反应器的实验研究

针对1 kW 固体氧化物燃料电池热电联供(SOFC-CHP)系统开发了集成催化燃烧、换热及蒸汽重整的反应器,搭建了性能评价系统,系统研究了燃烧侧气体组分及工艺参数对该反应器性能的影响规律。实验结果表明:在反应器燃烧侧气体入口温度为300℃、空燃比为10:1、电堆燃料利用率为65%、水碳比为3 的条件下,重整侧转化率达到73.6%,重整尾气中H₂ 含量为67.5%。电堆燃料利用率对重整反应转化效率影响较大,其值大于80%时,采用尾气燃烧的余热回收方式无法有效为蒸汽重整提供所需热量。在150~350℃范围内,降低燃烧侧气体入口温度对重整反应效率影响较小,建议采用尾气先换热再进行催化燃烧的流程设计,保证重整效率的前提下可有效提升系统热效率。空燃比的降低可小幅度提升重整效率,在保证电堆反应温度稳定的前提下,适当降低空燃比可减少空气压缩机的功耗,从而提升整个系统的效率。研究成果对SOFC-CHP 系统的优化和整体效率提升具有指导意义。     

耐火材料燃气窑炉的氮氧化物减排技术研究

为降低工业燃气窑炉的NO_x排放浓度,寻找适合耐火材料燃气窑炉的氮氧化物减排的解决方案,开展了对实验室1 m~3高温梭式窑(1 800℃)和生产企业的耐火材料燃气高温隧道窑的低氮氧燃烧技术与烟气干法催化吸附的试验研究,以及对烟气组成的实测与分析。结果表明:采用低NO_x预混型高速燃烧器可从源头减少NO_x生成,燃烧产物喷出速度在100 m·s~(-1)以上,能显著降低高温燃气窑炉NO_x排放浓度,实现过程减排(减排量40%),减除投资和运行费用较高的烟气脱硝负担;对于使用温度1 400℃以下的燃气窑炉使用此技术NO_x排放浓度100 mg·m~(-3);对于使用温度1 400℃以上的燃气窑炉通过源头控制、过程减排,使烟气中NO_x显著降低,末端治理再采用无机复合固体吸附剂干法催化吸附技术,可以在相对比较低的投入条件下取得理想的减排效果,NO_x排放浓度50 mg·m~(-3),实现了NO_x超低排放的要求。     

基于氢气低温催化燃烧的燃料电池低温启动研究进展

相比于传统动力系统,基于燃料电池的动力系统具有很多优点,但在实际运用中仍有许多亟需解决的问题,其中包括燃料电池系统的低温启动问题。本文对比了各种燃料电池低温启动方案的工作机理及其优缺点,归纳并分析了氢气催化燃烧所用催化剂和催化燃烧反应过程以及燃料电池低温启动过程等方面的相关研究成果,研究了影响催化燃烧的主要因素,得出以下结论：基于氢气低温催化燃烧的燃料电池低温启动策略具有较高的可行性;在不同反应模型的情况下,氢气都可以在微尺度管道内实现稳定的燃烧;表面催化反应对空间气相反应有抑制作用;空间气相与表面催化的耦合反应能得到最高的温度;氢气/空气预混合气体入口流速、导热壁及导热壁材料、管径和当量比均对催化燃烧有着重要的影响。     

燃气比及气体流量对低温干馏炉燃烧场的影响

在煤低温干馏过程中燃烧过程的诊断及控制对于提高干馏效率,减少污染物排放有着至关重要的意义。以工业上所使用的10万t/a SJ低温干馏方炉为研究对象,采用Fluent软件对SJ低温干馏炉内燃烧场进行仿真模拟。通过改变燃气比以及气体流量研究其对干馏炉燃烧场的影响,结果表明,随着燃气比的增加,干馏炉内的最高温度和最高压力均呈现出先增加至峰值而后减小至稳态的趋势;随着气体流量的增加,干馏炉内的最高温度逐渐减小,而干馏炉内的最高压力逐渐增大。最优的工艺条件根据温度分布应该具有高占比的最佳温度区间以及低占比的高温区域这一规律确定,最终选择燃气比为1.8,气体流量为14 000 m~3/h,可以更好地提高干馏效率。     

天然气催化燃烧理论和应用

在一个置于大气压下,稳态的滞止点流动反应器内的多晶铂箔上,对贫甲烷/氧气/氮气混合气体的燃烧进行了实验研究,同时用数值模拟方法重现了实验结果.从实验和模拟的角度提出了燃料转化率和一氧化碳选择性与铂表面温度(一直到超过了单相点燃温度区)的关系,铂表面的异相反应抑制了气相氧化反应的程度,并且提高了单相点燃的表面温度.实验观察到的抑制作用比预料的要强烈,实验表明在催化燃烧的高温区,抑制作用在这一较大区域里一直起主导作用.在此理论的指导下,开发研制催化燃烧V型冷凝锅炉,其排出的烟气平均温度仅为21℃.热效率也会随之提高,平均为100%左右.天然气高温催化燃烧排放物NO_x、CO已低于4×10~(-6),达到近零污染排放,同时燃烧效率达近100%.且因催化燃烧与普通不能完全燃烧相比具有节能的优势.     

新型低氮燃烧器在加热炉脱硝改造中的应用

抑制燃气燃烧装置产生的NO_x对保护大气环境是至关重要的一个方面。通过采用低NO_x的燃烧技术,改变燃烧条件抑制氮氧化物生成,从而降低NO_x的排放。影响燃烧过程中NO_x生成的主要因素是燃烧温度、烟气在高温区的停留时间、烟气中各种组分的浓度以及混合程度,对其进行了探讨。由于燃烧方法和燃烧条件对NO_x的生成有较大影响,因此可以通过改进燃烧技术来降低NO_x。选择新型低NO_x的燃烧器需考虑单台热负荷、燃料性质、空气供给量、温度、炉膛的高度,以及炉管与燃烧器的距离等影响因素,低氮燃烧器在加热炉脱硝改造中的应用取得了较好的效果。     

催化助热燃烧—一项重要的燃烧新技术

催化助热燃烧利用催化剂点燃和保持气相反应,保证燃料完全燃烧,提高了热效率,稳定地调节火焰温度,减少NO_x排放量,对提高能源利用率和保护环境有好处。采用蜂窝状陶瓷负载贵金属,(复)氧化物活性组分,或以多种材质的活性独石,可满足许多燃烧场合的要求。今后在催化剂体系选取时,应把高温热稳定性放在首位。     

提高热效,降低污染的催化燃烧法

传统的火焰燃烧法热利用率不高，且伴随着产生相当数量的ＮＯＸ。催化助燃烧技术利用催化剂点燃和保持气相反应，确保燃料完全燃烧，提高热效率；又因稳定地调节火焰温度，减少ＮＯＸ的排放量，减少了空气污染，具有相当实用价值。研究活性组分和优质载体是实现催化燃烧的关键因素。     

稀燃汽车尾气中氮氧化物的催化消除技术

稀薄燃烧(简称稀燃)技术能够使燃料在发动机内充分燃烧,既提高了燃油的经济性,同时又减少了温室气体CO2的排放,因而是一项节能减排的重要技术.但在稀燃条件下氧气大量过剩,加剧了三效催化剂对还原剂的催化氧化,降低了还原剂对NOx催化还原的效率.目前,国际上对稀燃气氛下NOx的消除主要采用NO直接分解、选择性催化还原(SCR...     

Synthetic gas bench study of a 4-way catalytic converter: Catalytic oxidation, NOx storage/reduction and impact of soot loading and regeneration

The so-called 4-way catalytic converter (4WCC) has the ability to simultaneously convert CO, HC, NOx and particulate matter on a single support. It allows diesel vehicles to obey to increasingly stringent emission regulations while at the same time decreasing the space needed by the exhaust aftertreatment system. It is combined with fine engine control strategies so as to ensure conversion of all pollutants. It is hence associated with a large number of catalytic reactions which interact with each other and compete for active sites. The behavior of a commercial 4WCC was characterized on a synthetic gas bench. Gas composition, temperatures and gas hourly space velocity were chosen close to real engine operating conditions. Samples were loaded with soot on an engine bench test. Oxidation reactions were dominant in a lean environment: CO oxidation by NO₂ at low temperature followed by H₂, CO, NO and HC oxidation by O₂. NOx were stored on barium storage sites. In rich conditions H₂, CO and HC were used to reduce NOx. NH₃ production from H₂ was also observed. It could be used to further reduce NOx in lean conditions if stored on a downstream SCR system like in the Honda system [1]. A further conversion of HC was obtained at high temperature due to steam reforming. Interactions and inhibitions were also found. NOx storage appeared to be inhibited by CO oxidation with NO₂ at low temperatures and also by HC, maybe through competition for storage sites with CO₂ produced during HC oxidation. Catalytic reactions were affected by the soot deposit. Continuous oxidation of soot by NO₂ also induced a slower NOx storage rate.     

煤粉锅炉高效低NOx局部富氧燃烧技术模拟研究

针对某公司150 t/h煤粉锅炉燃烧效率低、NOx排放浓度高、炉膛结焦等问题,提出了用富氧风作为炉顶燃尽风和贴壁风的分级燃烧新思路,采用计算机数值模拟技术和k-e- -g气相湍流燃烧模型及煤双挥发反应热解模型,对锅炉炉内速度场、温度场及燃烧过程中的NOx生成浓度进行数值模拟. 技术改造后锅炉的燃烧效率保持在96%以上,锅炉综合热效率在91.40%以上,NOx排放量为625~763 mg/m3,未发现炉膛水冷壁和高温过热器上有结渣现象.     

Monoliths in catalytic oxidation

Catalytic combustion is useful to avoid emission of nitrogen oxides, to combust fuel gas of different calorific levels, and to combust low contents of badly smelling or hazardous gaseous compounds. After dealing with some characteristics of catalytic combustion it is argued that catalytic combustion to a final temperature lower than about 800°C calls for a rapid transport of thermal energy out of the reactor. A fluidized bed in which combustion has been successfully performed is dealt with as well as a reactor filled with metal bodies sintered to each other and to the wall of the reactor. To achieve a sufficiently high catalytically active surface area a thin layer of silicone rubber is applied to the surface of the metal bodies and subsequently pyrolyzed to a highly porous layer of silica. To raise the thermostability alumina can be added to the silica layer.

To establish a final temperature above 900°C the homogeneous gas-phase combustion can be ignited by a solid catalyst or the reaction can be performed completely catalytically. Since the combustion reaction proceeds very rapidly at elevated temperatures, a large gas flow can be utilized, which calls for a reactor exhibiting a low-pressure drop. For catalytic combustion monoliths and gauzes are appropriate. The chemical composition of ceramic and metallic monoliths is dealt with as well as the cell densities and wall thicknesses of commercial monoliths. The application of active components to the surface of the walls of monoliths is subsequently discussed. Since monoliths do not allow radial mixing, a homogeneous gas mixture has to be fed to the monolith to prevent very high temperature levels moving randomly over the channels of the monolith and deactivating the catalyst.

With monoliths in gas turbines often catalytic ignition is used. To limit the temperature a fraction of the fuel feed is injected into the homogeneous combustion chamber. A number of alternatives of transporting the fresh fuel to the homogeneous combustion zone is mentioned. The cause of the catalyst temperature being higher than that of the gas flow is dealt with as well as the low volatility at elevated temperatures required for the catalytic components. Selection of the catalytically active materials is discussed and the procedure to bring the gas flow at the light-off temperature of the catalyst.

Monolithic combustors used in radiant heaters display often an oscillatory behavior. After dealing with the cause of the oscillations, prevention by means of a flame arrestor is mentioned.     

新型低氮燃气分级燃烧器燃烧特性和NOx排放的CFD研究

应用CFD软件Fluent数值模拟了某二甲苯塔再沸炉在役油气联合燃烧器燃烧和NOx排放特性,分析了其NOx排放浓度较高的原因,提出了新型低NOx燃气分级燃烧器的改造方案,并数值模拟了新型燃烧器空气预热温度Tair、过剩空气系数α和主辅喷枪燃气质量分率Rp对辐射室壁面热通量、出口温度、火焰高度和炉膛出口NOx排放浓度的影响。针对在役燃烧器的模拟结果与现场运行数据吻合良好,说明所选模型能够正确模拟炉膛内部的流动、辐射、燃烧和NOx生成过程。新型燃烧器模拟结果表明,增加Tair会增加辐射壁面热通量,同时也会增加NO的排放;辐射壁面热通量随α增加而降低,NOx排放浓度随α增加而增加;Rp对炉内传热和NOx排放的影响并不明显。当Tair = 220℃、α = 1.05及Rp= 0.24时,新型燃烧器在模拟范围内达到最佳运行工况,辐射壁热通量为37.45kW/m2,NOx排放浓度为12.1μL/L。     

水煤浆MILD燃烧数值模拟研究

为解决水煤浆常规燃烧存在的运行稳定性差等问题,以IFRF炉为研究对象,采用数值模拟方法尝试对水煤浆燃料进行了MILD燃烧研究。结果表明,在燃料输入功率不变的条件下,水煤浆MILD燃烧相对于常规旋流燃烧,流场的回流区域更大,烟气循环更加强烈,整体的炉膛温度更低,分布更加均匀,峰值温度最高降低了227 K,燃烧反应速率更慢,燃烧反应区面积存在区域更大,整个炉膛基本处于低氧氛围下,尾部烟气中的NO_x排放降低了50%以上。此外,水煤浆浓度的改变对炉膛流场几乎没有影响,但可以降低炉膛整体温度以及尾部烟气中NO_x排放。     

Development of a catalytic combustor for a heavy-duty utility gas turbine

Catalytic combustion is an attractive technology for gas turbine applications where ultra-low emission levels are required. Recent tests of a catalytic reactor in a full scale combustor have demonstrated emissions of 3.3 ppm NO_x, 2.0 ppm CO, and 0.0 ppm UHC. The catalyst system is designed to only convert about half of the natural gas fuel within the catalyst itself, thus limiting the catalyst temperature to a level that is viable for long-term use. The remainder of the combustion occurs downstream from the catalyst to generate the required inlet temperature to the turbine.

Catalyst development is typically done using subscale prototypes in a reactor system designed to simulate the conditions of the full scale application. The validity of such an approach is best determined experimentally by comparing catalyst performance at the two size scales under equivalent reaction conditions. Such a comparison has recently been achieved for catalysts differing in volume by two orders of magnitude. The performance of the full scale catalyst was similar to that of the subscale unit in both emission levels and internal temperatures. This comparison lends credibility to the use of subscale reactors in developing catalytic combustors for gas turbines.     

低NOx燃气燃烧技术研究进展

气体燃料具有易于点火、燃烧迅速、燃烧完全等特点,且氮、硫、灰分低,因此燃烧后产生的污染物相对较少,属于较清洁的燃料,且国家燃气补贴政策的实施,使气体燃料燃烧近年来有很好的发展前景。但随着国家对大气污染物的控制更加严格,控制气体燃料燃烧过程中NOx的生成至关重要。笔者介绍了不同种类NOx的产生机理及影响因素,并基于NOx的产生机理提出控制措施,分析目前应用较广泛的燃气燃烧技术的低氮原理及应用现状,最后提出燃气燃烧器应用的展望。燃气燃烧过程中主要以热力型NOx及快速型NOx为主,温度和过量空气系数是影响NOx生成的主要影响因素。燃烧温度高于1 500℃时,热力型NOx呈指数型增长,温度是影响NOx生成的最重要因素。根据NOx产生机理,低NOx燃烧技术的实质是降低最高燃烧温度,控制燃烧区燃料浓度以及氧浓度,缩短烟气在高温区的停留时间,破坏NOx生成的最佳条件,最终抑制NOx的生成。低NOx燃烧技术一定程度降低了NOx的生成,但又会破坏整个燃烧进程,对燃烧和放热过程造成不利影响,降低了燃烧效率和传热效率,因此如何解决这些矛盾是亟需解决的问题。在实际应用中,应根据需求选择合适的燃烧技术,同时可将不同燃烧技术相结合起到稳燃、低氮的效果。应用较广泛的燃气燃烧技术主要是阶段型燃烧技术、烟气再循环燃烧技术、无焰燃烧技术等,其中催化燃烧技术发展前景较好,目前已应用于多个领域,其催化剂的热稳定性和寿命问题是限制其工业上广泛应用的核心问题。     

CH4掺混H2的燃烧数值模拟及掺混比合理性分析

本工作针对天然气掺氢燃烧技术在燃气锅炉的最佳掺混比开展数值模拟研究,以小火焰燃烧器为研究对象,计算了在空气氛围、恒定过氧系数、不同甲烷掺混氢气比条件下,掺氢比对燃料燃烧温度、燃烧速率、主要污染物排放浓度的影响。其中燃烧机理采用GRI-MECH 3.0简化机理,该反应包含24个基元反应,涉及17种组分。计算结果表明,随掺氢比增加,燃烧温度上升、燃烧反应速率加快,炭烟和CO的浓度与排放总量均降低,NOx的浓度上升但排放总量先减小后增大。结合我国城镇燃气的燃料互换性规范及工业污染物排放标准,得出最佳掺氢比为23%。     

低浓度甲烷流向变换催化燃烧反应研究

将制备的整体式催化剂应用于小型流向变换催化燃烧反应系统上,在甲烷初始浓度为0.2%,气量为30 L·min-1,换向半周期为10 min的工况条件下考察了不同预热温度对甲烷催化燃烧活性的影响以及反应系统床层轴向温度分布情况。结果表明,随着预热温度升高,甲烷催化燃烧活性呈现升高的趋势,同时,在催化剂中添加助剂元素Pt可以提高催化剂催化活性;催化剂的预热温度对反应器床层温度分布影响较大,特别是反应系统的催化段。     

Test results of a catalytic combustor for a gas turbine

A catalytically assisted low NO_x combustor has been developed which has the advantage of catalyst durability. Combustion characteristics of catalysts at high pressure were investigated using a bench scale reactor and an improved catalyst was selected. A combustor for multi-can type gas turbine of 10 MW class was designed and tested at high-pressure conditions using liquefied natural gas (LNG) fuel. This combustor is composed of a burner system and a premixed combustion zone in a ceramic type liner. The burner system consists of catalytic combustor segments and premixing nozzles. Catalyst bed temperature is controlled under 1000°C, premixed gas is injected from the premixing nozzles to catalytic combustion gas and lean premixed combustion is carried out in the premixed combustion zone. As a result of the combustion tests, NO_x emission was lower than 5 ppm converted at 16% O₂ at a combustor outlet temperature of 1350°C and a combustor inlet pressure of 1.33 MPa.