煤气化中NO_x及其前驱物释放规律研究

采用U型管反应系统,研究了氧浓度、气流速率和气化温度对神木煤气化过程中NO_x及其前驱物的释放规律.研究发现:气化时生成的HCN和NH_3总量比热解时大幅下降,表明O_2的引入抑制了H自由基的可获得性.随着氧浓度的增加,NO的收率先减后增,而NO_2收率几乎没有变化.氧浓度较低时,生成的高浓度CO阻止了挥发分氮向NO的转化.气流速率对含氮气相产物释放影响各不相同.低温气化产物以NO_2和HCN为主,NO_2主要来自进样期挥发分的缓慢氧化,而高温气化产物中的NH_3的生成主要来源于焦炭氮.     

程序升温气化过程中氮的释放规律研究

采用 U 型管反应系统研究了不同煤种在程序升温条件下在四种气氛中反应时燃料氮的释放规律.研究发现热解时主要的含氮产物为 HCN,如果煤中含有较多的氧,即使在惰性气氛下也会释放出 NO.没有检测到 NH3 的生成,证实NH3 来源于 HCN 在焦表面的二次反应.N2O 仅在有氧气氛中气化时生成,说明氧气是 N2O 生成的必要条件.气化时的总固定氮 TFN 高于热解时,且气化剂中 O2 含量越高则总固定氮 TFN 越高.     

内蒙煤UCG煤焦的物化特性及其对焦化废水的净化

借助煤炭地下气化模拟实验系统,采用富氧空气/水蒸气两阶段气化方法完成内蒙煤的地下气化实验,获取残留煤焦。采用SEM、FTIR、低温氮气物理吸附仪对煤焦的表面形貌、官能团和孔结构特性进行表征,通过淋滤实验研究煤焦对焦化废水的吸附,进而考察煤焦的吸附性能。结果表明,气化后残焦表面较为粗糙,有明显的孔隙裂隙,且保留部分含氧官能团;气化残焦的比表面积和孔容积分别达到133.87 m~2/g和0.118 cm~3/g,远大于原煤的20.19 m~2/g和0.045 cm~3/g;气化残留煤、焦对焦化废水均具有一定的净化作用,内蒙煤对TOC的脱除率随淋滤时间延长逐渐增大至62.8%,氨氮脱除率则逐渐减小至23.45%;残焦对废水中氨氮的脱除率也随时间延长而减小,但对有机污染物具有更高的吸附性能,TOC脱除率保持在70%以上。     

天然焦-H2O气化反应特性

在加压热重分析仪上研究了气化温度和催化剂种类对沛城煤矿天然焦-H2O的气化反应特性的影响,用扫描电镜(SEM)观察不同温度下焦样的孔隙结构,并计算了动力学参数.结果表明,气化温度是影响天然焦-H2O气化反应性的一个主要因素,随着温度的升高,天然焦的孔隙越发达,碳转化率明显增大;K基、Ni基、Fe基三种催化剂均能有效地促进气化反应,其中K基催化剂效果最好,其次是Ni基和Fe基催化剂;天然焦的活化能为Eα=147.25 kJ/mol.     

基于简单碰撞理论煤粉燃烧动力学模型的研究 -PARTⅠ:理论建模与热重实验

本文根据反应动力学的简单碰撞理论(SCT),建立了气固两相反应通用模型,进一步研究了煤焦燃烧和燃尽的统一动力学模型;粉煤悬浮燃烧时挥发分的析出模型也可包含在该模型中;该模型充分考虑了粉煤在热天平中与在炉内燃烧条件下氧气浓度和氧气可达比表面积变化规律的差异,并给出了计算活化能函数和氧气可达比表面积的新方法,可提高利用热天平获取的动力学参数对炉内煤粉燃烧速率预报的准确性。通过热重分析和已经报道的试验数据对模型的合理性进行了检验。     

TG-FTIR法研究低变质煤共热解过程气体的析出规律

采用热重-红外联用技术（TG-FTIR）对比研究了陕北低变质粉煤（SJC）与重油（HS）、焦煤（JM）、液化残渣（DCLR）共热解过程中气相产物的析出特性。研究表明,随热解温度升高,SJC与HS,JM,DCLR的共热解过程均可分为三个阶段。第一阶段表现为原料表面吸附物的释放,第二阶段发生解聚和分解反应,随温度继续升高,第三阶段形成更为稳定的半焦。在热解第二阶段中均存在煤与添加剂之间的协同效应,SJC作为主要的供氢体,热解产生的氢自由基与HS,JM,DCLR热解产生的小分子自由基碎片之间发生相互作用生成焦油和煤气。SJC和SJC+DCLR在450 ℃附近的温度区间内热解反应进行的更加充分,大部分N元素转移到了焦油组分中。热解过程气相产物中H₂O和酚类物质、含N杂环物质及CO的析出伴随着热解的整个温度区间,SJC+JM和SJC+HS热解过程含N物质的转移主要集中在400~650 ℃区间,CH₄和脂肪烃类物质的析出最高峰出现在450 ℃附近,而SJC+DCLR和SJC则出现在550 ℃。JM,HS及DCLR的添加可促使焦油中芳香族化合物的析出,SJC+JM与SJC+HS热解过程芳香族物质大量析出的温度区间在400~550 ℃。该研究结果为低变质粉煤的清洁转化与提质分级新技术的研究开发提供理论依据,对低变质煤的增值利用具有重要的意义。     

基于TGA-FTIR研究生物质热解过程中氮化物的生成

基于TGA-FTIR联用技术,考察了升温速率对生物质中氮热解转化成NH3和HCN的影响.结果表明,热解的升温速率影响生物质中氮转化的速率和转化的量,升温速率提高,NH3和HCN的生成量减小,NH3和HCN的起始释放温度及达到最大析出值的温度提高.慢速升温热解,HCN的析出与NH3的析出规律相似,但HCN的析出量明显小于NH3的析出量,生物质中氮主要以NH3的形式析出.     

O2/CO2气氛下石灰石煅烧及烧结特性研究

本文研究了在O2/CO2气氛下石灰石的煅烧和烧结特性.结果表明,空气气氛下煅烧所得CaO的孔隙率和比表面积均较O2/CO2气氛下的大,但O2/CO2气氛下煅烧所得CaO具有更大的最可几孔径.石灰石在O2/CO2气氛下1000℃煅烧时的产物具有最大的比孔容积和比表面积,且石灰石煅烧产物CaO的比孔容积和比表面积均随气氛中CO2浓度的增加而下降,在低CO2浓度下下降较为迅速,而在高CO2浓度下下降逐渐趋于平缓.在延长相同烧结时间的情况下,O2/CO2气氛下CaO孔结构受烧结影响的程度要比空气气氛下轻微.     

微波处理对模型焦脱除NO特性的影响

运用自制的微波电加热反应系统,进行了不同微波功率、温度和试验方式对模型焦脱除NO反应性能的影响研究。结果表明:一定程度的微波改性可以促进模型焦吸收NO;NO还原率随微波功率的增大先增大后减小;常温下改性时间为90s时,存在最佳改性功率480 W,该功率改性的模型焦NO还原率最高;常温下改性模型焦的NO还原率普遍高于同功率下的800℃改性模型焦的NO还原率.对部分模型焦进行压汞分析和XPS分析,结果表明,微波处理改变了模型焦的孔隙结构和表面官能团,比表面积和孔容积的增大以及表面含氧官能团的减少有利于NO的吸收。微波热效应和非热效应共同作用影响模型焦还原NO过程。恒温800℃下间歇施加微波方式的NO还原提高率远低于程序升温式。     

氧燃烧方式下重金属Se挥发行为的研究

在氧燃烧方式和空气燃烧方式下对Se的氧化物及其与CaO的混合物进行了热重红外实验,通过TG、DTG、DSC以及X射线衍射分析考察了升温速率、气氛和矿物质对重金属Se在燃烧过程中挥发行为的影响。实验结果显示:氧燃烧气氛下se02的挥发率以及释放总量较之空气气氛发生了较大变化,氧燃烧气氛下,Se化合物的释放总量比空气气氛下低;在同一气氛下,钙硒比越大,钙的固硒效果越明显;升温速率对SeO2挥发的影响较小,主要在于加速或推迟其挥发;氧燃烧方式有助于抑制重金属Se的释放。     

O_2/CO_2气氛燃煤半焦孔隙特性分析

在沉降炉上制备了不同燃烧气氛、不同燃尽程度的半焦,采用低温氮吸附仪和扫描电子显微镜测定了其孔隙结构和表面形态.结果表明,所取的半焦试样均具有完整且连续的孔结构体系;但在相同的操作条件下,O_2/CO_2气氛下半焦试样的孔结构参数及其分形维数均小于相同O_2浓度的O_2/N_2气氛下的情况;两种气氛下煤焦的燃尽过程中,孔隙结构参数(S_(BET)、V_(BJH)和d_(pore))随燃尽率的增加均呈减小趋势;SEM图像的定性分析结果与N_2吸附的定量测量吻合较好.研究结果为深入认识O_2/CO_2气氛下煤粉的孔隙结构与其燃烧特性的关系提供了基础.     

多相燃烧分形模型及其实验研究

本文提出了多相燃烧的分形模型．模型中认为在多相燃烧中内部孔洞体积与表面积存在分维指数关系，而且反应面积的增长为两种分形增长模式的叠加．结合孔洞合并的因素得到了描述煤多相反应速率的分形模型．该模型描述的反应速率先增加后减少的规律与实验结果十分相符．对五个煤种和其中两个煤焦样品进行了试验研究，在两个不同升温速率下得出的试验数据与理论计算相符．     

Effect of pore structure parameters of porous glass on luminescence properties of Eu/Dy co-doped high silica luminescence glass

The Eu²⁺/Dy³⁺ co-doped high silica luminescence glasses were prepared through sintering porous glasses which have adsorbed rare earth ions previously and the effect of pore structure parameters including average pore size, specific surface area, and pore volume on luminescence properties of high silica glass were analyzed by utilizing BET method and emission spectra. The results show that the pore parameters of porous glasses do not affect the shapes of emission spectra but affect the luminescence intensities of high silica glasses. The luminescence intensities of high silica glass increase when the specific surface area of porous glasses increases, which can be interpreted by mechanism of adsorption of rare earth ions onto porous glass. The average pore size and pore volume indirectly affect the luminescence intensities through influencing specific surface area of porous glass.     

Coalbed methane adsorption and desorption characteristics related to coal particle size

Effects of particle size on CH_4 and CO_2adsorption and desorption characteristics of coals are investigated at 308 K and pressures up to 5.0 MPa.The gas adsorption and desorption isotherms of coals with particle sizes ranging from 250 μm to 840 μm are measured via the volumetric method,and the Langmuir model is used to analyse the experimental results.Coal particle size is found to have an obvious effect on the coal pore structure.With the decrease of coal particle size in the process of grinding,the pore accessibility of the coal,including the specific surface area and pore volume,increases.Hence,coal with smaller particle size has higher specific surface area and higher pore volume.The ability of adsorption was highly related to the pore structure of coal,and coal particle size has a significant influence on coal adsorption/desorption characteristics,including adsorption capacity and desorption hysteresis for CH_4 and CO_2,i.e.,coal with a smaller particle size achieves higher adsorption capacity,while the sample with a larger particle size has lower adsorption capacity.Further,coal with larger particle size is also found to have relatively large desorption hysteresis.In addition,dynamic adsorption performances of the samples are carried out at 298 K and at pressures of 0.1 MPa and 0.5 MPa,respectively,and the results indicate that with the increase of particle size,the difference between CO_2 and CH_4adsorption capacities of the samples decreases.     

Air-activated carbons from almond tree pruning: Preparation and characterization

In this work the results obtained in the preparation and characterization of carbons made from almond tree pruning by non-catalytic and catalytic gasification (using K and Co) with air are analyzed and discussed. The main aim was to obtain high quality activated carbons at the lowest possible cost. The variables studied have been the temperature (190-260 °C) and the time (1-10 h) in non-catalytic gasification and the influence of the catalyst type (K and Co, 1 wt.% referred to cation, at 190 °C and 1 h) and the time (1-4 h) in catalytic gasification with Co at 190 °C. The air flow rate used in all the series was 167 cm³ min⁻¹. In non-catalytic gasification the reaction normalized rate versus the conversion degree was maintained until a conversion value of 10% for the experiment made at 260 °C since, at lower temperatures, this rate drops quickly for low conversion values. The N₂ adsorption isotherms for the carbons of this series resemble type I, although there is an increase of N₂ adsorbed volume at relatively high pressures. A temperature rise produced an increase of the carbon porosity and BET specific surface (116-469 m² g⁻¹). The activation time has a positive effect on the N₂ volume adsorbed by the carbons. The isotherms shapes were similar to those previously commented. A concentration equal to 1 wt.% was used to study the influence of the catalyst type. Under the studied experimental conditions, Co drives to a bigger porosity development than K, although with both catalysts a very similar pore size distribution is obtained. The activation time, in the gasifications catalyzed with Co, gives rise to a very important porosity development in the carbons. This produces a strong increase of the carbon specific surface area with very high values in the 4 h experiment, in which a BET specific surface of 959 m² g⁻¹ was obtained.     

Modeling char surface area evolution during coal pyrolysis: Effect of swelling and gasification at high pressures

In this paper, a previous model for char surface area change during atmospheric coal pyrolysis was modified to include the effect of particle swelling and gasification to predict the N₂ adsorption specific surface area of high-volatile bituminous char generated at high pressures with or without gasification. A correlation between the change of char surface area and P₀ΔV_P/m_cm (the ratio of the expansion work for particle swelling to the mass of metaplast cross-linked with coal matrix) was developed and analyzed. The number of the defect regions generated by gasification was considered in calculating adsorption sites quantitatively. Particle swelling opens (at P₀ΔV_P/m_cm<1350 J/kg) and then compresses (at 1350 J/kg <P₀ΔV_P/m_cm<10,000 J/kg) the space between metaplast clusters, making the N₂ adsorption specific surface area of char increase first and then decrease. After the gaps between metaplast clusters are filled, the specific surface area changes are minimal. Gasification generates new defect regions in clusters and reduces the clusters in char, making the specific surface area of char first increase and then decrease.     

基于离轴积分腔输出光谱对泰州大气NH3浓度观测与分析

氨(NH₃)是大气中活性氮最主要的还原形式, 是形成二次无机铵盐的重要气态前体物。在中国极度污染的条件下, 这些铵盐可占PM_2.5质量的40%～60%。NH₃污染不仅影响全球的光辐射强度, 而且会加剧大气光化学污染。目前, 城市地区氨气来源仍存在一定争议。为研究泰州地区NH₃污染情况, 并深入了解NH₃的来源。2018年6月6日至15日, 基于离轴积分腔输出光谱技术, 开展了夏季泰州地区大气NH₃浓度的连续观测。其他污染物浓度(如NH₃,NO_x,CO,NH+₄)同步进行测量。观测点位距离交通枢纽300 m, 观测期间NH₃的平均浓度为25.1±4.5 μg·m-3, 相比国内外其他城市, 该地区NH₃污染处于较高水平。白天与夜间NH₃浓度均值无明显差异, 但总体呈现白天降低夜晚升高的趋势。夜间温差大, 大气边界层较为稳定, 是污染物得以累积的原因之一; 晨间NH₃浓度急剧升高, 主要考虑为夜间沉积在水汽中的NH_x(气态NH₃与颗粒态NH+₄)的蒸发所带来。随着光照进一步增强, 环境水汽中NH_x的蒸发逐渐结束, 光化学反应过程逐渐占据主导, NH₃浓度上涨速度缓慢, 逐渐趋于平衡, 并在之后出现迅速下降。在湿度较大的夜间, NH_x的沉积过程更加明显。结合观测期间的气象参数以及与常规污染物的相关性, 讨论了泰州地区的污染物变化趋势及污染水平。结果表明, 大部分日期交通排放对泰州地区NH₃浓度影响较小, 仅6月7日早高峰期NH₃与NO_x,CO相关性较好, R2分别为0.740与0.911, 推测当日交通排放影响较大, 交通源是NH₃的重要局地源。进一步进行了后向轨迹分析, 比较了观测期间不同气团所导致的污染物浓度变化。结合观测结果分析可知, 观测点西北方向工业园区污染排放可能是导致6月10日夜间污染事件的重要原因。     

Effect of CO2 gasification reaction on oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, as is commonly employed, it is recognized that elevated CO₂ levels affect radiant transport, the heat capacity of the gas, and other gas transport properties. A topic of widespread speculation has concerned the effect of the CO₂ gasification reaction with coal char on the char burning rate. To give clarity to the likely impact of this reaction on the oxy-fuel combustion of pulverized coal char, the Surface Kinetics in Porous Particles (SKIPPY) code was employed for a range of potential CO₂ reaction rates for a high-volatile bituminous coal char particle (130 μm diameter) reacting in several O₂ concentration environments. The effects of boundary layer chemistry are also examined in this analysis. Under oxygen-enriched conditions, boundary layer reactions (converting CO to CO₂, with concomitant heat release) are shown to increase the char particle temperature and burning rate, while decreasing the O₂ concentration at the particle surface. The CO₂ gasification reaction acts to reduce the char particle temperature (because of the reaction endothermicity) and thereby reduces the rate of char oxidation. Interestingly, the presence of the CO₂ gasification reaction increases the char conversion rate for combustion at low O₂ concentrations, but decreases char conversion for combustion at high O₂ concentrations. These calculations give new insight into the complexity of the effects from the CO₂ gasification reaction and should help improve the understanding of experimentally measured oxy-fuel char combustion and burnout trends in the literature.