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。     

煤中固有矿物质在热解过程中对氮释放的影响

采用管式炉固定床反应器,考察了平朔煤( PS)、神木煤( SM)和阳城煤( YC)三种不同变质程度的煤种在热解过程中的HCN和NH3 释放规律,主要讨论煤中所固有的矿物质在这一过程中对氮分配的影响.结果表明:不同变质程度的煤种脱除矿物质后,均表现为热解过程中的NH3释放量减少,其减少程度与灰分的性质有关;而HCN的释放与煤中矿物质的关系却受煤变质程度的影响;同时矿物质对不同形态氮的分配也有明显的作用.     

流化床煤燃烧过程不同气氛下的气态氮释放特征

利用微型流化床反应装置,结合快速过程质谱仪,在850~940℃操作温度下,研究了三种不同粒度分布烟煤和无烟煤在热解、气化和燃烧反应条件下四种主要气态氮产物HCN、NH₃、NO和NO₂的释放规律。结果表明,微型流化床可以实时检测挥发分氮和焦炭氮的动态释放序和类型,热解、气化和燃烧反应气氛的改变主要影响HCN和NH₃的释放量。热解产物的气态氮主要是来自于挥发分,燃烧反应的HCN和NH₃的释放量与温度有明显关系,而气化反应的各类气态氮释放量随温度变化波动不大。煤颗粒尺寸和温度变化对烟煤和无烟煤中各类气态氮释放量产生影响比较复杂,其中NH₃的释放特性是区分挥发分N释放和半焦N释放的重要特征。     

发生炉造气过程中NO_x及前驱体生成的探讨

结合煤气发生炉的造气原理和过程,对煤氮在发生炉热解、还原、燃烧过程中的转化以及NOx与前驱体的生成进行了定性的分析。指出发生炉热解、气化过程中,煤氮一部分转化为焦油;一部分以NH3、HCN、N2形式转化为煤气;另外一部分残存于灰渣中。通过分析,说明一段式发生炉、两段式发生炉和干馏式发生炉三种炉型在气化过程中,NH3、HCN和N2的生成量基本没有差异;NH3和HCN主要来源于气化过程;而热解过程次之,但干馏式发生炉在煤的热解过程中NH3和HCN的生成量最少。     

Loy Yang褐煤热解过程中HCN和NH3形成的主要影响因素

引　言热解是煤燃烧和气化的初始步骤 ,作为煤有机成分之一的N在煤热解过程中将随挥发分的释放而转化为NH3、HCN和少量的HNCO等气态NOx 前驱物、N2 以及焦油N和焦N[1,2 ] ,这些NOx 前驱物及焦N在后续的燃烧、气化过程中将转化为NOx/N2 O或者N2 [3,4 ] .煤燃烧过程中释放的NOx/N     

基于铁基载氧体的煤化学链气化还原过程中氮元素迁移行为

采用热重-质谱-红外联用技术（TG-MS-FTIR），Ar气氛下对煤进行化学链气化实验，实时分析还原过程热解阶段和水蒸气气化反应阶段的过程中固体质量变化和生成气体成分。使用X射线光电子能谱对固相产物进行表面元素分析，探究化学链气化还原过程不同阶段固相产物中氮赋存形态的变化。研究结果表明：载氧体对化学链气化还原过程不同阶段含氮气体释放均有影响。热解阶段载氧体促进自由基的生成，加速了一次热解阶段含氮气体的释放，高温下，载氧体促使NH₃转化为HCN；气化阶段载氧体的加入使半焦的石墨化程度降低，含氮气体释放速率增加。对固相产物中氮的赋存形态而言，载氧体会抑制热解阶段吡咯型氮的分解与转化，高温下，半焦的石墨化和有序化程度降低的同时，镶嵌在煤大分子里面的质子化吡啶裸露出来，质子化吡啶含量降低，吡啶型氮和吡咯型氮的含量大大提升。     

固体热载体煤热解过程中氮的迁移

在固体热载体煤热解实验装置上考察了石英砂、燃烧灰和气化半焦为热载体对煤热解过程中氮迁移的影响。固体热载体煤热解过程中,热解温度升高有利于煤中挥发分析出,可以促进煤中含氮官能团发生断键,利于氮的脱除。快速热解可促进煤中氮脱除生成HCN和NH_3。分别以石英砂、燃烧灰和气化半焦为热载体,研究表明:热载体中矿物质可促进焦油氮分解;通过气化半焦和脱矿物质气化半焦为热载体研究发现,气化半焦为热载体时,高比表面积和孔结构可延长在其表面停留时间,对焦油氮分解起主要作用。     

矿物质对煤转化过程中含氮物迁移的影响

综述了煤本身所固有的矿物质和外来添加物在煤热解、气化过程中的作用,主要针对煤中氮的形态变化和迁移规律进行了讨论.煤中的含氮物在热解气化过程中以HCN、NH3 N2等形式释放于气相产物之中,还是以大分子杂环化合物形式残留于煤焦和焦油之中,煤中固有的矿物质和添加剂对其在各形态间的分配比例具有较大影响.含Fe、Ca等金属元素的化合物是对含氮物迁移转化存在明显作用的代表性物质,同时对Fe、Ca在煤氮催化转化生成N2中的可能机理和在氮氧化物形成之前进行其前驱体的抑制进行了分析.     

干馏式发生炉冷煤气站氮化物的形成与脱除

结合干馏式发生炉的结构特点对其气化过程中煤氮的转化及NH 3和HCN的生成进行了简要阐述,指出NH 3主要来源于气化过程,而热解过程次之,煤气中的HCN主要来源于干馏段内的低温干馏热解。同时分析了干馏式发生炉冷煤气站利用"浓缩蒸发法"处理含酚废水和煤气湿法脱硫过程中,脱除煤气中的NH 3和HCN的原理和过程,指出利用"浓缩蒸发法"处理含酚废水过程中,可以将煤气中的部分NH3和HCN氧化成NO,然后再还原成N 2;煤气湿法脱硫过程中,其中的NH 3溶于脱硫液与煤气中的H 2S发生脱硫反应,从而达到脱除煤气中一部分NH 3的效果。     

LoyYang褐煤热解过程中HCN和NH3形成的主要影响因素

引言 热解是煤燃烧和气化的初始步骤,作为煤有机成分之一的N在煤热解过程中将随挥发分的释放而转化为NH3、HCN和少量的HNCO等气态NOx前驱物、N2以及焦油N和油N[1,2],这些NOx前驱物及焦N在后续的燃烧、气化过程中将转化为NOx/N2O或者[3,4].     

The fate of fuel-nitrogen during gasification of biomass in a pressurised fluidised bed gasifier

The distribution of fuel-nitrogen in gases, tar and char from gasification of biomass in a pressurised fluidised bed gasifier was investigated. Four species of biomass: birch, Salix, Miscanthus and Reed canary grass were gasified at 0.4 MPa and 900 °C. Oxygen-enriched nitrogen was used as fluidising agent. As a reference, gasification of Daw Mill coal was also carried out under the same experimental conditions. The experimental results illustrate that both the nature of the original fuels and the chemical structure of the nitrogen in the fuel have influence on the distribution of fuel-nitrogen in gases (NH₃, HCN, NO), tar and char under the employed experimental conditions. The present work also shows that the types of nitrogen heterocyclic compounds (NHCs) in the tar from different kinds of biomass are the same and the major compound is pyridine. However, the distribution of the various NHCs in the tar from the four species of biomass varies: the higher the content of fuel-nitrogen, the higher the concentration of two-ring NHCs in the tar. An effective method for extracting NHCs from the acidic absorption of the product gas was introduced in the present work. The method makes use of solid phase extraction (SPE) by a silica-based C₁₈ tube to extract the NHCs which subsequently were analysed by gas chromatography (GC) with flame ionisation detection (FID). The recovery and reproducibility of the SPE technique for NHCs is discussed.     

Formation of HCN and NH3 during coal macerals pyrolysis and gasification with CO2

Three coal macerals with high purities were separated from Pingshuo gas coal. The formation rules of HCN and NH₃ during macerals pyrolysis and gasification were investigated. Experiments were carried out in a tubular quartz reactor at atmospheric pressure. The reactor allowed coal particles to be heated up rapidly and held for a prespecified period of time at a peak temperature. The amount of HCN and NH₃ were quantified by ion chromatography. The influence of temperature and macerals type on the formation rules of HCN and NH₃ was discussed. Results showed that the formation of HCN was mainly due to the thermal cracking of volatile, and NH₃ formed both from the thermal cracking of volatile and the cracking of nascent char. The HCN yield increased with an increase in pyrolysis temperature. For three coal macerals (liptinite, vitrinite and inertinite), the yield of HCN depended not only on their volatile contents but also nitrogen-containing functional groups, in which more pyrrole-type nitrogens would form more amount of HCN at lower temperature. The yield of NH₃ depended on the ability of forming ‘H’ radical. Under the experiment condition in this study, inertinite could convert more nitrogen into NH₃ than vitrinite and liptinite. The yield of HCN during gasification was almost the same as that during pyrolysis, the yield of NH₃ during gasification was little higher than that during pyrolysis.     

Effects of volatile–char interaction on the formation of HCN and NH3 during the gasification of Victorian brown coal in O2 at 500 °C

In a coal gasifier interactions between volatiles and char are significant. The partly reducing conditions in a gasifier would mean the presence of high concentration of partial oxidation products and radicals surrounding the char particles. Currently, little is known about the effects of in situ volatile–char interactions on the conversion of char-N. This study examines the effect of in situ volatile–char interactions on the formation of HCN and NH₃ during the low temperature (500 °C) gasification of Loy Yang brown coal in oxygen. Two novel reactor systems were used. The reactor configurations allowed the quantification of HCN and NH₃ from char-N gasification, volatile-N oxidation and volatile–char interactions separately. Our results indicate that volatile–char interactions can have drastic effects on coal-N conversion during gasification by providing an important source of the radicals for the formation of HCN and NH₃ from char-N during gasification in 4% or 8% O₂ at 500 °C. In the presence of radicals and O₂, N-containing structures in the nascent char can be easily broken down to give HCN and NH₃ during the gasification of the char. In the absence of O₂, some of the nascent char-N structures may stabilise into structures less favourable for the formation of HCN and NH₃ and more favourable for the formation of other N-containing species such as NO_x.     

Formation of NOx precursors during the pyrolysis of coal and biomass. Part VIII. Effects of pressure on the formation of NH3 and HCN during the pyrolysis and gasification of Victorian brown coal in steam

Effects of pressure on the formation of HCN and NH₃ during the pyrolysis and gasification of Loy Yang brown coal in steam were investigated using a pressurised drop-tube/fixed-bed reactor. The NH₃ yield increased with increasing pressure during both pyrolysis and gasification. Increasing pressure selectively favours the formation of NH₃ at the expenses of other N-containing species. The changes in the yield of NH₃ with increasing pressure were mainly observed in the feeding periods both during pyrolysis and gasification and were closely related to the formation and subsequent cracking of soot both as a result of intensified thermal cracking of volatile precursors inside the particles and as a result of volatile-char interactions after the release of volatiles. While the corresponding HCN yield during pyrolysis showed little sensitivity to changes in pressure, the HCN yield during gasification in steam showed some increases with increasing pressure. Our data indicate that the direct hydrogenation of char-N by H radicals, favoured by the presence of steam, is the main route of NH₃ formation during pyrolysis and gasification. The direct conversion, either through hydrogenation or hydrolysis, of HCN into NH₃ on char surface during the pyrolysis and gasification of brown coal is not an important route of NH₃ formation.     

Releases of NO and its precursors from coal combustion in a fixed bed

Experiments have been carried out to investigate the emissions of nitrogen species including NO and its precursors during temperature-programmed coal combustion by TG/EGA method. Experimental results show that the conversion ratio of fuel nitrogen to NO is the highest, followed by that of fuel nitrogen to HCN and the conversion ratio to NH₃ is negligibly small. Nitrogen is retained in the char and released mainly as NO at the later stages of coal combustion. HCN and NO are both primary products from coal char oxidation. Coal rank, heating rate, indigenous minerals and external additives are the major influential factors of the nitrogen species release. Higher rank coals with higher fuel ratio have higher NO releases. HCN release decreases as fuel ratio increases for most coals. The fuel nitrogen conversion to NO increases and the fuel nitrogen conversion to HCN decreases with the increase of heating rate, which may imply that the char nitrogen prefers to react with oxygen to form NO instead of HCN while coal char is combusted at higher temperatures. Different metallic additives show different effects on nitrogen species emission and the effects of indigenous minerals on nitrogen release can be qualitatively estimated by ash analyses.     

水煤浆气流床气化过程中氮的迁移

在四喷嘴对置式气流床气化炉中,考察了水煤浆在不同氧碳比气化条件下HCN、NH₃、NO和N₂的轴径向浓度。结果表明：氮污染物(HCN、NH₃、NO)在喷嘴平面处即产生并浓度最高,其主要来源于煤粒快速热解时析出的挥发分,远离喷嘴平面时三者浓度大幅降低并大多转化为N₂,且氧碳比增高有利于N₂的生成,气化室出口处浓度N₂>HCN>NH₃>NO;流场分布使气化室出口附近径向浓度基本一致,而其上部各平面位置靠近炉壁处浓度较低;煤浆中的适量水分有利于HCN和NH₃生成,但过量水分不利于挥发氮析出,使HCN、NH₃和NO生成量降低。     

低阶煤热解-气化-燃烧TBCFB系统模拟及优化

三塔式循环流化床（TBCFB）是基于低阶煤分质转化利用理念开发的新型工艺系统,包含热解、气化及燃烧三个主反应器。提出了采用半焦颗粒代替石英砂作为循环热载体的新工艺,并使用Aspen Plus建立了基于半焦颗粒的TBCFB系统模拟流程,寻求系统内物料转化和能量利用的适宜操作条件。结果表明,只需燃烧40%的热解半焦,即可满足低阶煤在600℃热解和60%的热解半焦在800.9℃进行水蒸气气化所需热量;与石英砂或高温灰相比,利用热容较高的半焦颗粒作为循环介质可以显著降低热载体循环量,与原煤质量比仅为5.5。综合气化产物组成、低热值和冷煤气效率等指标,适宜的水蒸气与反应半焦质量比为1.5。上述模拟结果对半焦循环TBCFB新技术的工业应用具有一定指导意义。     

平顶山高灰熔融性温度煤的气化反应性研究

介绍了平顶山地区有代表性的7种煤样在800℃～1 200℃下,其脱灰煤焦-CO2气化反应活性的实验,主要考察了煤种、灰含量及粒径对煤焦反应性的影响,实验结果表明:煤种对煤焦-CO2气化反应有明显影响;煤中灰分对煤焦气化反应的影响主要表现在两个方面,一是灰成分对煤焦气化反应的催化作用,二是灰熔融性影响煤焦气化排渣行为。脱灰既可以除去煤焦中具有催化作用的矿物质,又可以增大煤焦的内表面积。     

NOx precursors evolution during coal heating process in CO2 atmosphere

The pyrolysis/gasification experiments of Xuzhou bituminous coal (XZ) and Longyan anthracite (LY) were carried out in a tube furnace under Ar or CO₂ atmosphere, and the effect of CO₂ on the evolution of NO_x precursors, NH₃ and HCN, was studied using a Fourier transform infrared (FTIR) spectrometer. Results show that CO₂ influences NH₃ and HCN evolution process in two main ways: one is blocking the contact of the N-sites and the H-radicals by absorbed on the coal matrix surface at low temperature, and the other is opening the N-sites from the coal matrix by gasification at high temperature. For both XZ and LY coals, CO₂ atmosphere suppresses NH₃ yield and enhances HCN yield due to the gasification effect compared with that in Ar atmosphere. But the impact is not the same. The HCN/NH₃ ratio is elevated in CO₂ atmosphere compared with that in Ar atmosphere.