煤热解的孔隙结构特性

在同热解时间与相同粒度,不同热解终温的实验条件下,利用马弗炉热解龙坪煤获得煤焦试样;用N2气体吸附/脱附方法进行实验研究。实验结果表明:在此实验条件下,不同热解终温下煤焦颗粒试样大体上均是Ⅱ型等温线(或包含Ⅱ型等温线);煤焦的孔径较小,主要是微孔与小孔,且含有少量的中孔及大孔。在热解终温不断提高的实验条件下,孔的结构及种类变得复杂多样化,孔的比表面积及孔容积总体上呈现增加上升的趋势,表明提高热解终温有助于龙坪煤的热解。     

不同热解升温速率下制备所得生物焦的汞吸附性能

在管式炉中不同热解升温速率下制备了核桃壳生物焦,借助固定床反应器表征了生物焦的汞吸附性能,利用N2吸附/脱附装置和傅里叶变换红外光谱(FT-IR)分析仪分析了生物焦的孔隙结构及表面官能团,获得了生物焦对汞的吸附机理.结果表明:在相同吸附时间内,随着定温制备条件中热解温度和变温制备条件中热解终温的升高,生物焦对汞的吸附能力由强到弱依次为600℃、800℃、1 000℃和400℃;其中在定温制备条件下,当热解温度为600℃时,其累积汞吸附量达到最大,在300 min吸附时间内为2 942 ng/g;随着热解升温速率的升高,生物焦对汞的吸附能力先增强后减弱,当热解升温速率为10 K/min时,生物焦对汞的吸附性能最好;同时在生物焦对汞的物理吸附过程中,3～5 nm的介孔起主要作用,累积孔体积越大,累积汞吸附量越大,越利于生物焦对汞的吸附;在热解终温为600℃时,随着热解升温速率的升高,生物焦表面官能团的数量先增加后减少,与汞吸附性能实验结果一致,说明生物焦表面官能团会影响生物焦对汞的吸附性能.     

煤焦特性及其N_2O生成影响因素的实验研究

在流化床上进行了两种煤的热解及焦炭的燃烧实验,研究了煤种、粒径、热解条件对煤焦性质及Ｎ２Ｏ转化率的影响。研究结果表明：除粒径外,煤种和热解条件都对煤焦中Ｎ的Ｎ２Ｏ转化率有明显影响。     

褐煤焦吸附烟气中气态汞的实验研究

利用汞渗透管的汞蒸气发生装置和其他烟气成分模拟烟气条件,在小型固定床实验台上开展褐煤焦脱除Hg0的试验研究。结果表明:O2和HCl单独存在时均能够有效地促进单质汞在煤焦上的吸附,使煤焦的穿透率减少,吸附效率提高;SO2的存在会造成竞争吸附,抑制煤焦对Hg0的吸附;NO对煤焦吸附Hg0影响不大。随着入口汞浓度的增加,煤焦的穿透率增加;随着吸附反应温度的升高,煤焦的穿透增加,吸附效率降低。     

热解温度和时间对煤热解过程中汞析出的影响

采用国际通用的Ontario-Hydro法,对150目的煤粉在氮气气氛下不同热解温度和时间下进行的热解研究,测试结果表明：汞总释放率随时间呈现递增趋势,热解时间对汞的形态分布影响很小。汞总释放率随着温度的升高几乎呈线性关系增长,而且随着热解温度的升高,元素汞占总汞的比例先变大再变小。元素汞在热解过程中始终是气态汞的主要形态。不同的煤种对汞释放率有影响,变质程度较低的兖州煤汞的释放率较低,变质程度较高的大同和神华煤的释放率相对较高。     

煤焦特性及其NO2生成影响因素的实验研究

在流化床上进行了两种煤的热解及焦炭的燃烧实验，研究了煤种，粒径，热解条件对煤焦性质对Ｎ２Ｏ转化率的影响。研究结果表明：除粒径外，煤种和热解条件都对煤焦中Ｎ的Ｎ２Ｏ转化率有明显影响。     

再燃烧条件下煤焦结构其对NO还原的影响

在携带流反应装置中测量了再燃条件下煤粉在高温烟气环境中迅速热解时的质量损失,通过扫描电镜观察和分析了煤焦的显微结构;分析了煤种、热解温度、热解气氛和煤粉粒径等因素对煤粉热解特性的影响;探讨了煤焦形成条件对NO还原的影响.结果表明,随着煤的挥发分含量增加,煤的质量损失份额和煤焦还原NO的能力增加;热解温度升高,将导致煤焦还原NO能力下降;在一次燃烧区空气过量系数SR1＝1.0～1.2范围内,煤粉质量损失变化不大.     

煤热解过程中汞析出特性的研究

针对目前煤利用过程中汞的排放和污染状况,综述了煤热解过程中汞元素的析出和脱除规律的研究进展;分析了煤种、热解气氛、热解时间和温度对汞析出和汞形态转化的影响因素;阐述了利用煤热解进行燃烧前脱汞的应用前景。     

废橡胶和废纸热解过程NOx前驱体的生成

在固定床反应器中热解废橡胶和废纸,考察在不同热解终温和加热方式下NOx前驱体(HCN和NH3)的生成特性.研究结果表明,随着热解终温的升高,原料中的N转化为HCN和NH3的比例不断增加.以废橡胶为例,HCN和NH3的产率从400℃的0.5%分别增加到1000℃的7%和9%;加热方式对HCN和NH3的产率有明显的影响.实验条件下,非等温热解时,废橡胶在所有热解温度下HCN和NH3的产率均高于等温热解时的产率.     

稻秆热解及催化热解的试验研究

采用TGA-FTIR联用技术研究稻秆在催化与非催化条件下的热解行为.考察升温速率、热解终温、颗粒粒径及添加CaO对稻秆热解主要析出产物的影响.研究结果表明:升温速率对热解产物的影响比热解终温的影响大;粒径的减小有利于气体产物的析出;添加CaO,稻秆热解后焦炭产量明显增加,表面粗糙度提高,比表而积增大;加入催化剂CaO有利于减小CO2羧酸类及醛类的析出,促进CO及CH4的生成.     

Influence of pyrolysis pressure on structure and combustion reactivity of Zhundong demineralized coal char

The investigation on evolution of coal char structure during pressurized pyrolysis can reveal the combustion reactivity of coal char in thermal utilization at elevated pressure. In this study, Zhundong subbituminous coal was demineralized and a pressurized drop tube reactor (PDTR) was used to prepare coal char under different temperature and pressure conditions. The physicochemical structures of raw and demineralized coal chars were characterized by the application of nitrogen adsorption analyzer, automatic mercury porosimeter, and Fourier transform infrared spectroscopy (FTIR). The change mechanism of char infrared structure with pyrolysis pressure is revealed on the molecular level in this paper. The results show that the N₂ adsorption quantity of raw coal char increases with the increase of pyrolysis temperature, while that of demineralized coal char decreases. Because of the difference in molecular volume and steric hindrance between aliphatic and aromatic structure in char, the increasing pressure has less inhibition effect on the escape of the former than the latter. With the increase of pyrolysis pressure, the combustion reactivity of char is related to the infrared structure at 700 and 800 °C while to macropore structure at 900 and 1000 °C.     

浑源煤焦CO_2气化反应的影响因素及动力学特性分析

研究了热解温度、热解时间以及气化温度对浑源煤焦CO2气化反应的影响,并获得了气化反应的动力学模型.结果表明：浑源煤焦的气化活性随热解温度的提高而降低;每个热解温度都对应着一个最佳热解时间,且存在最佳热解时间随温度升高而缩短的趋势;提高气化温度能够显著提高煤焦的气化反应性能,气化温度对气化反应的影响大于热解温度的影响;低温度煤焦的气化活性随气化温度的提高而增加更为剧烈;900℃及以上的高温使活性点数增加,从而使煤焦间的活性差距分布均匀;浑源煤焦的气化反应适宜用体积模型来描述,所求取的动力学参数之间存在补偿效应,其等动力学温度约为1 199.6℃.     

制焦条件对稻秆与大同烟煤共气化特性影响的实验研究

在自行设计搭建的气化实验装置上进行不同制焦条件下稻焦-大同烟煤焦的混合焦样气化特性实验。对比不同工况下气化特性曲线发现:在本实验工况下,稻-煤焦样经机械掺混后的气化特性优于相同工况下浸渍混合后的气化特性;混合后制焦所得焦样气化特性优于先制焦后混合处理所得焦样的气化特性;煤和稻焦热解温度对混焦的气化特性影响不同,热解温度对生物质焦以及随后气化特性的影响大于对煤焦的影响;无论是稻焦还是煤焦,热解时间对混焦的气化特性影响均不明显。通过上述热解条件对稻-煤气化特性的影响,为煤与生物质共气化的工业应用提供指导。     

煤粉再燃过程对煤焦异相还原NO的影响

利用高温携带流反应装置,研究了煤种(包括褐煤、烟煤和贫煤)、再燃区内反应温度、煤粉粒径、一次燃烧区空气过量系数SR1和再燃区空气过量系数SR2对煤焦异相还原NO作用的影响,探讨了煤焦异相还原NO的机理.结果表明:随着SR2和煤粉粒径的减小以及再燃区反应温度的提高,煤粉NO还原效率增加;在相同的SR2下,随着煤中挥发分含量的提高,煤粉粒径的增加和再燃区反应温度的降低,煤焦异相还原NO贡献上升;对于相同再燃燃料份额:SR1=1.0和SR1=1.2时煤焦异相还原NO的贡献均大于SR1=1.1时的异相还原NO的贡献.     

Experimental investigation on the influence of the pyrolysis operating parameters upon the char reaction activity in supercritical water gasification

Supercritical water gasification of coal is a clean and efficient method for coal utilization which can convert coal into H₂ and CO₂. In order to further reduce costs, a novel two-step cascade utilization method was proposed in this study: conducting traditional pyrolysis first and then gasifying the pyrolysis char in supercritical water. The influences of different pyrolysis operating parameters on gaseous products and char gasification in supercritical water were investigated. Quartz tube reactors were used to ensure the complete collection of gaseous products in pyrolysis process. The experimental results showed that both carbon and hydrogen conversion efficiency increased with temperature, and the increasing trend became not obvious after reaction for 5 min. The thermo-gravimetric curves showed that volatilization removal process was completed at the pyrolysis time of 5 min and higher pyrolysis temperatures were beneficial to the subsequent gasification process. The result also showed that residual weight was 15%–20% of the initial weight. Hydroxyl radicals kept stable during pyrolysis process with the absorption peak intensity increasing first and then decreasing, and mineral substance disintegrated gradually as time increased. As pyrolysis temperature increased, the peak of CC double bonds decreased, turning into stable functional groups and carbonyl group increased. Dispersive pores occurred at the surface of coal as residence time increased with particle size decreasing, specific surface area and reactivity increasing. The results might be used for the design of a cascade utilization system based on coal gasification in supercritical water.     

Effect of middle-temperature pyrolysis on the surface hydrophobicity of sub-bituminous coal

Middle-temperature pyrolysis is widely used to convert sub-bituminous coal into gas/liquid products and the coal char, which benefits the utilization of low rank coal resources. However, the coal char usually contains high-ash content because the volatile components in coal release from coal particle forming gas/liquid products while most of high-ash mineral components remain in the coal char. Therefore, the upgrading of the coal char is usually required to meet the requirement of calorific value for burning. It is necessary to find out the effect of middle-temperature pyrolysis on the surface hydrophobicity of coal. In this study, the effects of pyrolysis temperature (700, 800, and 900°C) and pyrolysis time (30 and 90 min) on the surface hydrophobicity of sub-bituminous coal were comprehensively investigated. X-ray photoelectron spectroscopy (XPS), attachment time, and flotation tests were used to reveal the changes of surface hydrophobicity and floatability of sub-bituminous coal before and after middle-temperature pyrolysis. The XPS results indicated the content of hydrophilic oxygen-containing functional groups was reduced while the content of hydrophobic functional groups on coal surface was increased after the pyrolysis. The attachment time of coal particle-bubble was reduced while the flotation recovery of coal was increased after the pyrolysis. The surface hydrophobicity and floatability of sub-bituminous coal were enhanced by middle-temperature pyrolysis, which makes the upgrading of the coal char feasible.     

煤粉热解特性对其富氧气氛下着火机理的影响

利用非等温热重分析法对两种烟煤的热解特性及富氧下的燃烧特性进行研究.实验结果表明,煤粉中低温下的热解行为对其富氧气氛下的着火机理有明显影响.挥发分初析温度低、热解特性指数D大的煤,随着氧体积分数的增加,着火方式逐渐由非均相转变为均相.而挥发分初析温度高、D较小的煤,着火方式则无明显变化.热解活性高的煤,在着火机理转变后,着火温度显著降低,但燃尽温度基本不受影响.氧体积分数提高后两种煤粉的燃烧特性指数S都有所增大,但相同氧体积分数下不同煤种之间的S相差不多,说明着火机理的改变对S无明显影响.     

Effect of temperature on Lu’an bituminous char structure evolution in pyrolysis and combustion

In the process of pyrolysis and combustion of coal particles, coal structure evolution will be affected by the ash behavior, which will further affect the char reactivity, especially in the ash melting temperature zone. Lu’an bituminous char and ash samples were prepared at the N₂ and air atmospheres respectively across ash melting temperature. A scanning electron microscope (SEM) was used to observe the morphology of char and ash. The specific surface area (SSA) analyzer and thermogravimetric analyzer were respectively adopted to obtain the pore structure characteristics of the coal chars and combustion parameters. Besides, an X-ray diffractometer (XRD) was applied to investigate the graphitization degree of coal chars prepared at different pyrolysis temperatures. The SEM results indicated that the number density and physical dimension of ash spheres exuded from the char particles both gradually increased with the increasing temperature, thus the coalescence of ash spheres could be observed obviously above 1100°C. Some flocculent materials appeared on the surface of the char particles at 1300°C, and it could be speculated that β-Si₃N₄ was generated in the pyrolysis process under N₂. The SSA of the chars decreased with the increasing pyrolysis temperature. Inside the char particles, the micropore area and its proportion in the SSA also declined as the pyrolysis temperature increased. Furthermore, the constantly increasing pyrolysis temperature also caused the reactivity of char decrease, which is consistent with the results obtained by XRD. The higher combustion temperature resulted in the lower porosity and more fragments of the ash.