热解燃烧链条炉低NOx排放特性的数值模拟

利用Fluent软件,对功率为1.4 MW的新型热解燃烧链条炉的NOx排放特性进行了数值模拟,其中,煤热解产生的还原性可燃气简化为CH4,采用添加元素N的乙烯-空气混合物模拟链条炉排半焦层燃烧及其生成的NO. 数值计算结果表明,在过量空气系数为1.2、再燃比为30%的燃烧条件下,热解燃烧比传统燃烧可降低NO排放14.6%. 热解燃烧链条炉由于热解气的再燃作用,在炉膛中形成一局部还原区,可较有效地降低NOx排放,证明了热解燃烧技术的可行性. 增大再燃比和减小炉排前段风室配风量可提高出口NO还原率,减小炉膛前拱长度和前后拱间距会使NO还原作用增强.     

Efficient and cost effective reburning using common wastes as fuel and additives

Potential substitutes of natural gas and lignite fly ash as NO and HCN reducing agents, respectively, for heterogeneous reburning were examined in a bench-scale apparatus equipped with a simulated reburning and a burnout furnace. Selection of NO reducing agent is based on fuel volatility and nitrogen functionality. HCN reducing agent selection is based on literature data. A wide range of waste materials and industrial by-products show overall NO reduction efficiency up to 88% at reburning stoichiometric ratio 0.90 or 0.95. Mixed fuel containing scrap tire and Fe₂O₃ is particularly effective. Though its cost is constrained by the energy-intensive operation of grinding the tire, the estimated raw-material cost is better than that of natural gas reburning and highly competitive against SCR. A first-level approximation study of the selectivities of nitrogen species to form NO in burnout zone reveals the importance of HCN and char nitrogen reaction mechanisms.     

废轮胎的燃料特性及用于燃煤锅炉再燃脱硝

再燃脱硝技术是燃烧过程中控制燃煤锅炉氮氧化物排放的有效方法。首先分析讨论了常用再燃脱硝的燃料,即天然气和煤粉的局限性,然后详细地讨论了废轮胎作为再燃燃料的可行性和优点,并介绍了作者有关废轮胎再燃脱硝的研究结果。当废轮胎与电厂褐煤灰组成混合燃料用于再燃脱硝时,其脱硝效率可达到86%,当废轮胎与Fe₂O₃组成混合燃料用于再燃脱硝时,其脱硝效率可达到88%。废轮胎用于再燃脱硝,一方面有利于它的能源资源化处理,另一方面能够非常有效地减少燃煤NO_x的排放,具有重要的工程应用价值。     

铁基催化剂脱除NO气体的研究现状

对金属铁及其化合物在烟气脱硝过程中的催化作用的研究进展进行了综述。金属铁能够直接催化还原NO为N2,同时铁被氧化为铁的氧化物。当在烟气中补充一定量的还原气体CO,则CO通过还原铁的氧化物以保证金属铁和NO的连续反应,从而提高NO的脱除效率。在典型的模拟烟气条件下铁丝网在900℃以上可达到90%以上的脱硝效率。Fe2O3能有效地还原再燃脱硝过程的中间产物HCN/NH3,从而大幅度提高再燃脱硝的效率。此外,Fe-ZSM-5分子筛也具有催化还原NO的性能。铁催化还原NO的微观反应机理尚需深入研究。     

An experimental parametric study of gas reburning under conditions of interest for oxy-fuel combustion

An experimental parametric study on the NO reduction efficiency by reburning under oxy-fuel conditions has been performed through the gas-phase interactions between different gas mixtures and NO in a CO₂ atmosphere, under flow reactor conditions in the 800-1800 K temperature range. The study provides a wide amount of experimental data on reburning under oxy-fuel conditions to be further used in modeling studies. A higher NO reduction is attained in a N₂ atmosphere compared to CO₂ under fuel-rich and stoichiometric conditions, although the efficiency is similar in both atmospheres under fuel-lean conditions. The formation of HCN in a fuel-rich environment is higher in N₂ than in CO₂ but comparable for other stoichiometries. The influence of the main parameters of the process under oxy-fuel conditions has been found to present similar trends to those observed in literature for reburning in air. A significant NO reduction can be obtained at moderately high temperatures, fuel-rich conditions, high values of the reburn fuel/NO ratio, sufficiently high residence times and low water vapor contents. C₂H₆ has been detected to act as a better reburn fuel as CH₄, whereas CO itself is unable to reduce NO.     

尿素法SNCR对大型电站煤粉锅炉运行影响的工业试验

在660MW超临界W火焰锅炉上开展了工业试验,研究了尿素法选择性非催化还原脱硝（SNCR）投运对锅炉热效率、NOx排放、SCR入口烟道截面NOx分布及炉内烟气温度的影响。结果表明：SNCR系统喷入炉内的水汽化吸热是导致锅炉热效率降低的主要原因,喷入炉内水流量增加1.0t/h,锅炉热效率降低约0.05个百分点;稀释水流量影响尿素溶液在炉内的雾化和分配效果,在尿素用量相同条件下适当增加稀释水流量,SNCR脱硝效率会显著提高;相对于试验负荷下约2400t/h的烟气流量,SNCR喷入炉内的尿素溶液流量相对较少（占0.2%～0.5%）,因此,对炉内烟气温度影响并不明显。在一定范围内调整稀释水和尿素溶液流量对SCR入口烟道截面NOx分布的影响并不明显,但是过低的稀释水流量会影响炉内尿素混合效果,进而影响SCR入口NOx浓度在烟道截面深度方向上分布的均匀性。     

Application of gaseous fuel reburning for controlling nitric oxide emissions in boilers

An experimental study was performed on a 36 kW_th down-fired furnace in order to obtain a wider and more detailed knowledge of the influence of the key parameters on the gaseous fuel reburning process when typical Chinese coals served as the primary fuel. The experimental results show that both above 50% nitric oxide reduction and low carbon loss can be obtained when reburn zone residence time is about 0.6 s–0.9 s, gaseous reburn fuel percent is about 10%–15% and average excess air coefficient of reburn zone is about 0.8–0.9. According to the optimizational reburning operating parameters, a 350 MW_e coal-fired boiler was retrofitted for reburning application. The retrofitted boiler had about 0.7 s reburn zone residence time and about 2 s residence time after the burnout air was injected. The results of the demonstration on the full-scale boiler showed that the nitric oxide emission was about 235 mg/Nm³ (O₂ = 3%, dry) from the retrofitted boiler and above 60% nitric oxide reduction efficiency could be achieved with no adverse effects on the boiler operability when the coke-oven gas used as the reburn fuel. This successful demonstration project filled the gaps in the gaseous fuel reburning application on 300 MW_e grade unit boiler in China and showed that the values of the optimizational reburning parameters obtained from experiments could be successfully applied to the designing, retrofitting and optimizing for the gaseous fuel reburning process.     

以热平衡角度浅析注汽锅炉富氧燃烧节能效率

简要介绍了富氧燃烧技术在油田注气锅炉上的应用及其制取方法;根据已知锅炉参数和燃料特性计算出正常空气和富氧空气燃烧两种情况下的助燃剂量与烟气量;从热平衡角度对富氧燃烧节能效率和燃料节约率进行了理论计算。由计算可知应用富氧燃烧后助燃剂量、烟气量、燃料消耗量、排烟热损失均有不同程度的降低;排烟热损失是影响富氧燃烧节能效率的主要因素,由此提出降低排烟热损失进而提高节能效率的措施,从而为富氧燃烧技术的应用提供参考意见。     

Detailed measurements in a laboratory furnace with reburning

This article presents a detailed experimental characterization of the reburning process in a large-scale laboratory furnace. Natural gas, pine sawdust and pulverized coal were used as reburn fuels. Initially, the study involved the collection of in-flame combustion data, without reburning, in order to define appropriate locations for the injection of the reburn fuels. Next, flue-gas data were obtained for a wide range of experimental conditions using the three reburn fuels and, subsequently, detailed measurements of local mean O₂, CO, CO₂, HC and NO_x concentrations, and gas temperatures have been obtained in the reburn zone for three representative furnace operating conditions, one for each reburn fuel studied. The flue-gas data revealed that the sawdust reburning leads to NO_x reductions comparable or even higher than those attained with natural gas reburning, while coal reburning yields much lower NO_x reductions. The detailed data obtained in the reburn zone indicates that the reburning process remains active throughout all the reburn zone in the cases of natural gas and sawdust reburning, while in the case of coal reburning its relatively low volatile matter content is insufficient to establish an effective reburn zone. In the cases of the sawdust and coal reburning the burnout levels remain approximately constant, regardless of the NO_x emissions reduction, with the sawdust reburning leading to higher particle burnout performance than the coal reburning.     

Formation and reduction of nitric oxide in fixed-bed combustion of straw

Mechanisms of nitric oxide (NO) formation and reduction in fixed-bed combustion of straw have been modeled mathematically and verified experimentally. The model for the straw combustion and nitrogen chemistry consists of sub-models for evaporation, pyrolysis, tar and char combustion, nitrogen conversion, and energy and mass conservation. Twenty chemical reactions are included, of which 12 belong to the fuel nitrogen reaction network. Volatile nitrogen is assumed to be NO, NH₃, HCN and HNCO, and char nitrogen is converted to NO during char oxidation. The model predictions are in qualitative agreement with the measurements during the ignition phase, i.e. when the combustion front passes through the un-burnt fuel. The yield of NO can be reduced considerably by using a low primary air flow due to the longer gas residence in the fixed-bed, while the NO exhaust concentration is insensitive to the bed temperature. The NO exhaust concentration initially reaches a maximum and then decreases towards a stable value after the straw bed is ignited. Variations of NO, NH₃, HCN, and HNCO concentrations in the ignition flame front indicate that a large quantity of NO can be reduced in the thin flame front zone. The developed model is further validated by separate experiments in which NO or NH₃ was added at the middle through tubes or at the bottom of the bed with the primary air flow. Both the simulations and measurements showed that the variation of the NO exhaust concentration is small as compared with the injected NO or NH₃ concentration. According to the simulations and experiments, it is proposed that flue gas recirculation may be a very effective method of reducing NO emissions from flue gas in the fixed-bed combustion of straw. Calculations indicated that about 20% of the flue gas may be recirculated without significantly affecting the combustion behavior.     

Characteristics of sodium compounds on NO reduction at high temperature in NOx control technologies

Characteristics of sodium compounds additives on NO reduction at high temperature were investigated in a tube stove and a drop tube furnace. Sodium carbonate, sodium hydroxide and sodium acetate were chosen as Na additives to research the effect on NO reduction. It was found that sodium compounds could reduce NO emission and promoted NO reduction efficiency during pulverized coal combustion, coal reburning and urea-SNCR process. Adding sodium carbonate into crude coal gained 3.2%–34.8% of NO reduction efficiency on different combustion conditions during the coal combustion process. NO reduction efficiency was affected by sodium content and coal rank. Na additive performed NO reduction effect in whole Shenhua coal combustion process and in char rear combustion of Gelingping coal. Adding sodium hydroxide into the reburning coal increased NO reduction efficiency of the reburning technology. NO reduction efficiency was increased to 82.7% from 50.0% when the weight ratio sodium to the reburning coal was 3% and the ratio of the supplied air to the theoretical air of reburning fuel was 0.6. Sodium carbonate, sodium hydroxide and sodium acetate performed the promotion of NO reduction efficiency in urea-SNCR. Sodium acetate promoted NO reduction efficiency best while sodium hydroxide promoted worst at 800 °C. Sodium additives as SNCR promoter performed much better at lower temperature than at higher temperature, and they promoted NO reduction weakly in urea-SNCR when the temperature was greater than 900 °C.     

NO reduction capacity of four major solid fuels in reburning conditions - Experiments and modeling

The combustion of solid fuels in the rotary kiln and in the calciner of a cement plant generates fuel and thermal NO. This NO can be reduced inside the reducing zone of the calciner. This occurs in two different ways: homogeneous reduction by hydrocarbons and heterogeneous reduction by char. The purpose of this paper is to identify the relative contribution of volatile matters or char on the NO reduction process, which largely depends on the nature of the solid fuel used for reburning.Experiments were undertaken in an Entrained Flow Reactor (EFR), at three temperatures: 800, 900 and 1000 °C. Four major fuels used in the cement production process were studied: a lignite, a coal, an anthracite and a petcoke. Specific experiments were undertaken to determine (i) their devolatilisation kinetics and the gas species released. A wide range of species influencing the NO chemistry was carefully analyzed. Then, (ii) the char oxidation and (iii) the char NO reduction kinetics were characterized. Finally, (iv), the “global” NO reduction capability of each fuel was quantified through experiments during which all phenomena could occur together. This corresponds to the situation of an industrial reactor in reducing conditions. Anthracite and petcoke reduce only very small quantities of NO whereas lignite and coal reduce, respectively, 90% and 80% of the initially present 880 ppm of NO (at 1000 °C after 2 s).The four types of experiments described above were then modeled using a single particle thermo-chemical model that includes heterogeneous reactions and detailed chemistry in the gas phase. This model reveals that both NO reduction on char and NO reduction by volatiles mechanisms contribute significantly to the global NO reduction. After short residence times (several tenth of a second), gas phase reactions reduce NO efficiently; after long residence times (several seconds) the char reduces larger quantities of NO.     

Waste tyre rubber as a secondary fuel for power plants

Approximately 1 billion waste tyres are generated worldwide each year, with the US producing 300 million and the EU 260 million tyres, representing an enormous waste management problem. At the same time, increasingly stringent emission control targets are being imposed on electric power generating plants. The development of science and technology for clean coal combustion is crucial for a sustainable environment which is dependent on a mix of energy production systems. In this pilot scale study we have shown that tyre rubber can be fired with pulverised coal and may have a role to play in co-firing configurations in full scale power plant boilers as wastes are beginning to feature in ‘fuel switching’ scenarios for CO₂ mitigation. Utilisation of waste tyres in a coal combustion plant can, in one step, reduce NO emissions and recover energy from waste tyres, efficiently. Therefore, through this process, a problem waste stream is effectively utilised to help solve a major environmental pollution problem. We present data demonstrating reburning and co-firing configurations utilising waste tyre rubber. Low levels of NO emission (up to 80% reduction at reburning fuel fractions <12%th) can be achieved, when using a lower volatile South African coal as the primary fuel. The results for tyre reburning are compared with the performance of a suite of reburning fuels with differing volatile hydrocarbon contents. Direct co-firing of tyre with coal can also reduce NO levels but the degree of reduction is dependent on the reactivity of the coal and the prevailing combustion conditions in the primary zone of the mixed fuel flame.     

沉降炉中生物质热解产物的脱硝特性

利用连续沉降炉模拟白酒糟循环流化床解耦燃烧再燃区的反应气氛,研究各因素对半焦、焦油和热解气脱硝效率(比脱硝效率)的影响. 结果表明,反应温度由800℃升至1050℃,热解产物比脱硝效率均增大;半焦和焦油达到最佳比脱硝效率所需的停留时间为3.4 s;随反应气中NO浓度由400′10-6(j)增加到1000′10-6(j),热解产物比脱硝效率均呈降低趋势,但NO绝对还原量却呈增加趋势;随反应气中O2浓度增加,半焦比脱硝效率增大,热解气比脱硝效率降低,焦油比脱硝效率呈先增加后减少的趋势,在O2浓度为1.6%(j)时达最大,为60.1%. 在本研究的反应条件下,焦油比脱硝效率最好,热解气次之,半焦效果较差.     

水蒸气对煤粉再燃还原NO的影响

在兖州烟煤煤粉再燃还原NO的固定床反应器试验中加入不同量的水蒸汽,研究了水蒸汽对煤粉再燃还原NO的影响。结果表明,水蒸汽的加入加快了煤粉再燃还原NO的速度,但单位质量煤粉的还原效果随水蒸汽量的增加而降低,原因是水蒸汽同时也加速了煤粉的燃尽。水蒸汽加快了CO和CO2生成速度以及O2消耗速度,在挥发分为主的反应阶段促进CO2的生成更明显,而在焦炭为主的反应阶段促进CO的生成更明显,但单位质量煤粉的CO2生成量和O2消耗量均降低、CO生成量增加。煤粉再燃的燃尽时间随水蒸汽量的增加而缩短,比如当水蒸汽量为2%时,燃尽时间缩短了25.9%,当水蒸汽量为4%时,燃尽时间缩短了47.8%。在再燃区加入一定量的水蒸汽,既能改善煤粉对NO的还原效果,又能提高煤粉的燃尽率。工程应用要根据煤质特点、主燃区NO浓度、再燃煤粉比例、再燃区过量空气系数、经济性评价等因素进行试验确定最佳水蒸汽量。     

焦炉煤气再燃降低NOx排放技术研究

焦炉煤气是炼焦工业的副产品,通常未得到有效利用.利用Chemkin软件柱塞流模型研究了利用焦炉煤气作为再燃气体脱硝的可行性.NOx脱除率主要受再燃区温度、氧气浓度、再燃燃料比等因素的影响.在适当的操作参数下,利用焦炉煤气再燃脱硝,NOx脱除率能达到60%以上,具有工业实用价值.焦炉煤气再燃脱硝会引起炉膛内局部还原性气氛增强、炉膛温度分布改变、燃烧效率下降等影响,需采取相应措施消除.     

Optimisation of NOx reduction in advanced coal reburning systems and the effect of coal type

The advanced reburning process for NO_x emission control was studied in a down-fired 20 kW combustor by evaluating the performance of 15 pulverised coals as reburning fuels. The proximate volatile matter contents of the coals selected ranged from around 4 to 40 wt% (as received) with elemental nitrogen contents from around 0.6 to 2.0 wt%. The effects of reburn fuel fraction, reburning zone residence time, ammonia agent injection delay time (relative to the reburn fuel and burnout air injection points) and the nitrogen stoichiometric ratio are reported in detail and the optimum configurations for advanced reburning, established as a function of operating condition and coal type. The experimental results show that advanced reburning can reduce NO_x emissions up to 85%. The maximum benefits of advanced reburning over conventional reburning were observed at the lower reburn fuel fractions (around 10%). The results demonstrate that under advanced reburning conditions equivalent or higher levels of NO_x reduction can be achieved while operating the reburn zone closer to stoichiometric conditions compared with conventional reburning operating at high reburn fuel fractions (20-25%). Thus the practical problems associated with fuel-rich staged operation can be reduced. The effect of coal properties on the advanced reburning performance was also investigated. As with conventional reburning, the fuel nitrogen content of the coal used was found to have little influence on the NO_x reduction efficiency except at the highest reburn fuel fractions. There was, however, a strong correlation between the effectiveness of advanced reburning and the volatile content of the reburning fuels, which not only depended on the reburn fuel fraction, but also the mode (rich or lean) of advanced reburning operation. These parameters are mapped out experimentally to enable the best operating mode to be selected for advanced reburning as a function of the reburning fuel fraction and volatile content.     

分解炉空气分级燃烧及NOx排放特性研究

随着我国经济的飞速发展,作为重要基础材料的水泥产品需求量极大且趋于稳定。水泥生产过程中的NOx排放与燃煤火电厂和汽车尾气产生的NOx排放已成为空气污染的主要来源,而分解炉是降低水泥生产工艺中NOx排放的有效设备。笔者在引入高温烟气的模拟分解炉内进行空气分级燃烧试验,研究配风位置、配风比例以及石灰石/煤比例对分解炉内燃烧和NOx排放特性的影响规律。试验稳定过程中,高温烟气发生装置的给煤量和配风量保持不变。此时,高温烟气发生装置的时间平均温度为911℃,其产生的高温烟气温度稳定在750℃左右,高温烟气中NOx主要以NO和N2O的形式存在,其浓度分别为261.49×10^-6和12.96×10^-6。该股高温烟气将模拟实际回转窑产生的烟气进入分解炉内。在分解炉的上部区域(距离顶部0~2 000 mm区域)的温度为800~1 000℃,与实际分解炉运行温度一致,排放烟气中NOx主要以NO和N2O形式存在。随着中间配风位置的下移,煤粉燃烧放热区域下移,而顶部区域的石灰石吸热量变化较小,则原有热量平衡被打破且原有吸热量高于现有放热量,导致顶部区域内燃烧温度降低。此时,还原气氛中煤粉燃烧和石灰石分解反应时间均变长,导致NOx的还原反应更加充分。但石灰石分解产生的氧化钙(CaO)作为中间产物会促进NO的生成反应,其反应时间增加也促进了NO的生成;另一方面,石灰石作为催化剂参与焦炭和挥发分还原NO的反应过程,分解炉顶部区域的温度下降使得该还原反应变弱。综上,NO的最终排放浓度是以上反应的综合结果。随着配风位置的下移,该变化对NO的生成作用更加明显,故NO的排放浓度逐渐升高。当一级风量与二级风量的配风比例降低时,分解炉上部区域的煤粉燃烧份额减少和石灰石分解量降低,而分解炉下部区域的煤粉燃烧份额增加和未分解的石灰石份额增加,但石灰石的吸热增加量高于燃烧增加份额的放热量,因此分解炉内整体温度均降低。分解炉内NO浓度是由石灰石催化的氧化过程和还原过程综合决定的。一级风量变小时,尾部CO浓度随之增加,烟气中NO浓度呈现降低的趋势。当石灰石/煤比例增加时,分解炉内沿程温度逐渐下降。随着石灰石给粉量增加,分解炉内石灰石受热分解产生的CaO浓度增加,CaO催化NO还原反应更剧烈,从而NO浓度逐渐降低。而石灰石给粉量增加和分解炉温度降低的过程导致尾部的CO浓度升高。     

Kinetic model for natural gas reburning

Kinetics of natural gas reburning is modeled on the basis of GRI3.0 and the method of Gear. The calculation results indicate that the model agrees with experiments. HCN, NH_i and HCCO play an important role in the reburning system. Injecting NH₃ and increasing the fraction of HCCO in the reburning system will promote NO reduction. Injecting natural gas at the places wherein the fraction of NO is highest is a benefit to de-NOx. There exists an optimal value of ratio of natural gas: NO for reburning system. The influences of temperature, excess oxygen ratio and pressure are also discussed in the reburning system.     

沉浸式汽化器壳程流体传热实验与数值模拟

沉浸式汽化器广泛应用于LNG接收站调峰系统,其中壳程水浴流动传热特性是影响汽化器换热效率的关键因素。为此,利用可视化实验研究与数值模拟两种手段研究了初始水位高度、烟气进气量和进气温度对水浴传热系数的影响规律。研究结果表明：壳程水浴能够吸收烟气携带的显热和水蒸汽冷凝释放的潜热,排烟温度与水浴平衡温度基本相当;水浴在大量换热气泡诱导作用下,通过围堰溢流形成的循环水流能有效冲刷管壁,减薄流动边界层,起到强化传热作用;初始水位高度和进气量匹配关系影响水浴溢流情况,溢流后水浴传热系数明显增加;燃料量和空气量配比情况影响烟气温度和水浴湍流动能,水浴湍流动能较小时,即使烟气进气温度增加水浴传热系数反而减小。本研究可以为沉浸式汽化器的设计提供参考。