锡林浩特褐煤气化特性研究

利用同步热分析仪研究了制焦温度、气化温度以及升温速率等因素对煤焦气化特性的影响。研究结果表明:随着制焦温度的升高,煤焦的气化失重量减少,气化反应的时间延长,气化反应性略有降低。随着气化温度的提高,锡林浩特褐煤煤焦在相同时间内的碳转化率增加,煤焦的气化时间缩短,气化温度对煤焦的气化反应性有较大的影响。随着升温速率的增大,TG曲线、DTG曲线均向高温侧偏移。升温速率越大,相同温度时煤焦的碳转化率越低,气化反应速率达到峰值对应的气化温度随升温速率的增大而升高。随着升温速率的增大,煤焦气化反应活性变好,气化反应进行的更加剧烈。     

烟煤煤焦的CO2气化反应

采用TG-FTIR方法,在反应温度为950～1300℃时,研究了几种典型煤种及其在高温下慢速和快速热解煤焦的CO2气化反应特性.对4种原煤及其1200℃快、慢速热解条件下煤焦气化产物CH4和CO进行了实时检测和分析.同时对煤焦的孔隙结构和化学组成进行了分析.结果表明,各种热解煤焦的反应速率随气化温度的升高而增大,当达到最大值后随温度的升高而下降;4种煤焦的活化能随热解和气化温度的升高而增大;煤焦气化过程释放CH4和CO的特性与原煤的趋势相似,但原煤热解气化过程中释放CH4的质量浓度比不同热解速率制得煤焦的热解气化释放CH4的质量浓度高出2个数量级,快焦相比慢焦释放出更高质量浓度的CH4;各种煤焦的BET比表面积都较小(除神府慢焦外都小于2 ㎡/g);快焦的气化活性比慢焦的好.     

以纸浆黑液为催化剂高变质无烟煤热天平水蒸气催化气化动力学

以纸浆黑液为催化剂,用等温热重法研究4种高变质无烟煤常压纯水蒸气催化气化反应动力学．采用催化剂有效因子修正缩芯模型,测定温度为750～950℃反应控制时无烟煤碳转化率与时间的关系,并用修正缩芯模型和修正体积模型进行较好拟合,得出这4种无烟煤水蒸气催化气化的反应速率常数、活化能和指前因子,活化能范围为112．838～204．566kJ／mol．除灰含量最高的永安加筛煤以外,其他3种煤的反应速率常数都比加碳酸钠的高．     

钾盐对煤焦-CO_2气化反应特性的影响

利用法国Setaram公司生产的TGA92型热重分析仪,比较钾基、钙基、铁基催化剂对煤焦-CO2气化反应的影响,发现钾基催化剂催化效果最好.在反应温度900~1050℃范围内,利用自行建造的小型固定床试验装置研究了气化温度、钾盐催化剂含量、形成焦炭的原煤煤质对煤焦与CO2的气化反应活性的影响.试验结果表明,反应温度对气化过程影响显著,提高气化温度,煤焦与CO2的气化反应速率急剧增加,转化率显著提高;不同配煤比的原煤制得的焦炭,在气化过程中表现出不同的反应特性,弱黏结性的气煤表现出良好的抗碱能力.     

钾盐对煤焦-CO2气化反应特性的影响

利用法国Setaram公司生产的TGA92型热重分析仪，比较钾基、钙基、铁基催化剂对煤焦-CO2气化反应的影响，发现钾基催化剂催化效果最好．在反应温度900—1050℃范围内，利用自行建造的小型固定床试验装置研究了气化温度、钾盐催化剂含量、形成焦炭的原煤煤质对煤焦与CO2的气化反应活性的影响．试验结果表明，反应温度对气化过程影响显著，提高气化温度，煤焦与CO2的气化反应速率急剧增加，转化率显著提高；不同配煤比的原煤制得的焦炭，在气化过程中表现出不同的反应特性，弱黏结性的气煤表现出良好的抗碱能力。     

钠离子及灰分对煤焦CO_2气化反应性的影响

文章通过热重分析仪对原煤1、原煤2、原煤2脱灰、原煤2+Na Cl、原煤2+Na OH进行了热重试验,并计算了碳转化率和气化比速率。分析了煤中的钠离子和灰分对煤焦CO2气化反应活性的影响。结果表明:煤焦中的碳逐渐与气化剂反应时,煤中的钠熔融,富集在碳颗粒表面上,阻碍气化剂与煤焦内表面接触,使气化反应性降低。脱灰后外加碱金属煤的气化反应性大于脱灰煤,体现了碱金属钠对于煤焦CO2气化反应性的催化作用。当气化温度逐渐上升时,Na Cl、Na OH的催化效果越来越明显;在1 100℃在前,Na Cl的催化效果略高于Na OH,在1100℃之后,Na OH的催化效果高于Na Cl;因为气化温度过高时,以Na Cl形式存在的Na从煤焦中逸出,减弱了碱金属催化剂的催化效果。     

富氧气氛下水蒸气气化对煤焦燃烧的影响

采用自制的恒温高升温速率热重实验台,研究了富氧气氛下水蒸气气化对煤焦燃烧特性的影响,并使用低温氮吸附仪和环境扫描电子显微镜分析燃烧过程中煤焦孔隙结构。结果表明:在低氧浓度下,水蒸气气化作用对煤焦燃烧影响显著,可失重速率增大,燃尽时间提前,且随氧气浓度的增加而减弱;随着温度升高R0.5指数逐渐增加,当环境温度为1 000℃、水蒸气浓度为20%时,R0.5增长速度最大;煤焦燃烧过程中,加水后煤焦比表面积增大,孔隙结构丰富。     

反应温度对木屑炭水蒸气气化产物的影响

以木屑炭为原料,在固定床反应器中进行了水蒸气气化试验。试验在水蒸气流量为0.854 g/min,温度为800～1 000℃条件下,反应15 min。主要考查气化反应温度对碳转化率、合成气产率、燃气热值及燃气组成的影响。研究结果表明,在高温条件下木屑炭与水蒸气具有很高的反应活性,燃气产率为0.9～3 L/g;在气化温度为1 000℃时,碳转化率最高达到80%;燃气热值为8.9～9.4 MJ/m3,合成气(H2+CO)比例为68%～79%,H2/CO为4.02～6.32。     

准东高钠煤循环流化床煤气化特性

针对新疆准东高钠煤由于碱金属Na含量高而在直接燃烧时出现沾污严重的问题,基于0.25,t/d高碱煤热化学转化试验台,对准东高钠煤在不同煤气化反应温度下的气化指标(煤气成分、热值、冷煤气效率和碳转化率)特性进行了试验研究,并与对比煤种神木煤气化特性进行了对比分析.试验结果表明:准东高钠煤在循环流化床煤气化过程中运行平稳,随空煤比增加,煤气化反应温度升高,冷煤气热值降低,冷煤气效率先升高、后降低,在900,℃时达到最大,对于神华准东煤,其最大冷煤气效率为32.26%,,对于沙尔湖准东煤,其最大冷煤气效率为41.47%,,碳转化率则不断增大;与神木煤相比,准东高钠煤具有较高的煤气化反应活性,较高的冷煤气效率和碳转化率,在900,℃煤气化工况时,神华准东煤及沙尔湖准东煤冷煤气效率比神木煤分别高3.6%,和12.81%,,碳转化率分别高19.7%,和28.37%,.     

准东煤中钠元素赋存形态及洗煤对气化特性影响

为探究准东煤中钠元素赋存形态及洗煤对准东煤气化特性的影响,采用逐级洗煤法对准东煤进行洗煤处理。利用电感耦合等离子体质谱仪、离子色谱仪和X 射线衍射仪研究了准东煤中钠元素赋存形态及含量。利用热重分析仪研究了煤样的气化特性,并采用等转化率法计算气化反应动力学参数。结果表明：准东煤中钠元素主要以水溶钠为主,但并非以钠盐化合物晶体的形式存在于煤中。洗煤对煤样孔结构特性和矿物质含量均产生影响,矿物质含量较低时,气化特性主要由煤样的孔结构特性决定。随着洗煤程度加深,煤焦碳转化率达到90 %时所需的时间由5.35 min延长至12.02 min,气化反应活性指数逐渐降低,气化反应活化能由177.7～214.8 增大至203.5～252.4 kJ.mol-1。     

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℃.     

氧量对天然焦蒸汽气化特性的影响研究

在小型流化床(50mm、高1600mm)实验装置上对沛城煤矿天然焦-蒸汽气化反应进行实验研究,考察蒸汽中掺入氧气,共同作为气化介质对气化反应产气量、碳转化率、煤气热值和煤气组分等因素的影响,同时与ASPENPLUS软件对其气化过程的模拟结果进行了对比。实验中,天然焦试样量0.2kg/h,蒸汽量1.05kg/h,气化温度900℃,实验结果表明:气化介质中氧量明显影响天然焦蒸汽气化特性。随着氧含量的增加,初始阶段(0～0.2L/min)煤气产量提高了1.76倍,碳转化率提高了1.94倍,两者均显著增加;随着氧量的进一步增加(0.2～1.0L/min),其增加幅度趋缓,产气量增加1.16倍,碳转化率增加1.34倍。煤气中有效气体(H2+CO+CH4)的体积分数和煤气热值均持续减少,有效气体份额从76.9%下降到54.3%,煤气热值从9.01MJ/m3减少到6.34MJ/m3,而CO2体积分数增加明显,从23.1%增加到37.3%。Aspen模拟结果与实验结果基本一致,具有实际指导意义。     

Rapid pyrolysis and CO2 gasification of anthracite at high temperature

Anthracite could be burnt efficiently at high temperature utilizing oxy-coal technology. To clarify the effects of temperature and atmosphere on char porosity characteristics, char morphology, fuel-N conversion, and reducing products release, rapid pyrolysis and CO₂ gasification of anthracite was carried out in a high temperature entrained-flow reactor to simulate the condition in a pulverized coal furnace. Developed pore structure was formed in the gasification chars, which could be contributed to charCO₂ reaction at high temperatures. More mesopores were formed in internal carbon skeleton and retained against collapse and coalescent for gasification chars than pyrolysis chars. Compared with pyrolysis char, smoother and denser surface was observed in gasification char with the irregular bulges disappeared due to the destruction of external carbon skeleton. Char-N could be oxidized to NO in CO₂ atmosphere and then reduced to N₂ by (CN) on the char surface. Char-N release was greatly promoted due to gasification reaction along with poly-condensation at high temperature; and the preact release of char-N would result in a larger portion of NO_x reduction in the following reduction zone with the oxygen-staging combustion technology compared with that in air-staging combustion. Complementally, homogeneous reduction in NO_x emission would play a minor effect for anthracite in oxy-coal combustion because of the deficiency of CH₄ and HCN, especially at high temperature.     

赤泥-铜矿石复合载氧体用于煤化学链气化性能研究

煤化学链气化制合成气是一种资源利用率高、环境污染低、节能环保的新型气化技术,而高效载氧体的设计开发是化学链气化技术的关键。本文以铜矿石和赤泥为原料采用挤出滚圆法制备R-Cu-10M（蒙脱石质量分数为10%）复合金属载氧体,实现载氧体颗粒内粉末的物理均匀混合、颗粒一次成型以及活性组分间的协同效应。围绕反应温度、氧煤比、水蒸气输入量三个关键操作变量,测试了R-Cu-10M载氧体与褐煤气化反应特性。表征结果表明,R-Cu-10M载氧体具有较好的还原性,赤泥与铜矿石中Cu-Fe金属间的协同效应有助于晶格氧释放以及还原性的提升。R-Cu-10M载氧体与褐煤发生气化反应的最佳温度为950℃,在氧煤比为3∶1、水蒸气通量为0.08 mL/min的最优工况下,合成气产量可以达到50 mmol/g载氧体,合成气选择性和碳转化率分别为75.9%和71.2%。     

Kinetic characteristics of in-situ char-steam gasification following pyrolysis of a demineralized coal

This study aims to examine the char-steam reactions in-situ, following the pyrolysis process of a demineralized coal in a micro fluidized bed reactor, with particular focuses on gas release and its kinetics characteristics. The main experimental variables were temperatures (925 °C?1075 °C) and steam concentrations (15%–35% H₂O), and the combination of pyrolysis and subsequent gasification in one experiment was achieved switching the atmosphere from pure argon to steam and argon mixture. The results indicate that when temperature was higher than 975 °C, the absolute carbon conversion rate during the char gasification could easily reach 100%. When temperature was 1025 °C and 1075 °C, the carbon conversion rate changed little with steam concentration increasing from 25% to 35%. The activation energy calculated from shrinking core model and random pore model was all between 186 and 194 kJ/mol, and the fitting accuracy of shrinking core model was higher than that of the random pore model in this study. The char reactivity from demineralized coal pyrolysis gradually worsened with decreasing temperature and steam partial pressure. The range of reaction order of steam gasification was 0.49–0.61. Compared to raw coal, the progress of water gas shift reaction (CO + H₂O ? CO₂ + H₂) was hindered during the steam gasification of char obtained from the demineralized coal pyrolysis. Meanwhile, the gas content from the char gasification after the demineralized coal pyrolysis showed a low sensitivity to the change in temperature.     

Experimental simulate on hydrogen production of different coals in underground coal gasification

Research on hydrogen production from coal gasification is mainly focused on the formation of CO and H₂ from coal and water vapor in high-temperature environments. However, in the process of underground coal gasification, the water gas shift reaction of low-temperature steam will absorb a lot of heat, which makes it difficult to maintain the combustion of coal seams in the process of underground coal gasification. In order to obtain high-quality hydrogen, a pure oxygen-steam gasification process is used to improve the gasification efficiency. And as the gasification surface continues to recede, the drying, pyrolysis, gasification and combustion reactions of underground coal seams gradually occur. Direct coal gasification can't truly reflect the process of underground coal gasification. In order to simulate the hydrogen production laws of different coal types in the underground gasification process realistically, a two-step gasification process (pyrolysis of coal followed by gasification of the char) was proposed to process coal to produce hydrogen-rich gas. First, the effects of temperature and coal rank on product distribution were studied in the pyrolysis process. Then, the coal char at the final pyrolysis temperature of 900 °C was gasified with pure oxygen-steam. The results showed that, the hydrogen production of the three coal chars increased with the increase of temperature during the pyrolysis process, the hydrogen release from Inner Mongolia lignite and Xinjiang long flame coal have the same trend, and the bimodality is obvious. The hydrogen release in the first stage mainly comes from the dehydrogenation of the fat side chain, and the hydrogen release in the second stage mainly comes from the polycondensation reaction in the later stage of pyrolysis, and the pyrolysis process of coal contributes 15.81%–43.33% of hydrogen, as the coal rank increases, the hydrogen production rate gradually decreases. In the gasification process, the release of hydrogen mainly comes from the water gas shift reaction, the hydrogen output is mainly affected by the quality and carbon content of coal char. With the increase of coal rank, the hydrogen output gradually increases, mainly due to the increasing of coal coke yield and carbon content, The gasification process of coal char contributes 56.67–84.19% of hydrogen, in contrast, coal char gasification provides more hydrogen. The total effective gas output of the three coal chars is 0.53–0.81 m³/kg, the hydrogen output is 0.3–0.43 m³/kg, and the percentage of hydrogen is 53.08–56.60%. This study shows that two-step gasification under the condition of pure oxygen-steam gasification agent is an efficient energy process for hydrogen production from underground coal gasification.     

Modelling and experimental investigations on gasification of coarse sized coal char particle with steam

The steam gasification characteristics of coal char produced two sub-bituminous coals of different origin have been investigated through modelling and experiments. The gasification experiments are carried out in an Isothermal mass loss apparatus over the temperature range of 800–900 °C using a gas mixture of 65% steam and 35% N₂. A fully transient single particle gasification model, based on the random pore model, is developed incorporating reaction kinetics, heat and mass transport inside the porous char particle and the gas film. Stefan-Maxwell equation and Knudson diffusion are incorporated in the multi-component diffusion of species and pore diffusion. The model is validated with the experimental data of the present authors as well as that reported in the literature. The particle centre temperature is found to increase, then decrease and increase again to reach the reactor temperature finally, and the trend is more prominent for the larger particles. The pore opening phenomenon is more evident in SBC2 char, leading to a final char porosity of 0.65 vis-à-vis 0.52 in SBC1 and making it more reactive. Temporal evolution of contours of carbon conversion and concentration of other gaseous species like steam, H₂O, H₂, CO and CO₂ in the particle are computed to investigate the gasification process. A higher temperature is found to favour both the rate peak and the total production of H₂ for both the chars. The total H₂ production from SBC2 char is found to be 0.0189 mol and 0.0236 mol at 800 and 850 °C, while the same for SBC1 char is0.0232 mol and 0.0290 mol respectively. The reaction follows the shrinking core model at the outset, shifting to the shrinking reactive core model subsequently.     

Detailed kinetic analysis and modelling of the dry gasification reaction of olive kernel and lignite coal chars

The dry gasification process of solid fuels is a promising pathway to mitigate and utilize captured CO₂ emissions toward syngas generation with tailored composition for several downstream energy conversion and chemical production processes. In the present work, comprehensive kinetic analysis and reaction modelling studies were carried out for olive kernel and lignite coal chars gasification reaction using pure CO₂ as gasifying agent. Chars reactivity and kinetics of the gasification reactions were thoroughly examined by thermogravimetric analysis at three different heating rates and correlated with their physicochemical properties. The reactivity of olive kernel char, as determined by the mean gasification reactivity and the comprehensive gasification characteristic index, S, was almost three times higher compared to that of the lignite coal char. It was disclosed that the fixed carbon content and alkali index (AI) have a major impact on the reactivity of chars. The activation energy, E_a, estimated by three different model-free kinetic methods was ranged between 140 and 170 kJ/mol and 250–350 kJ/mol for the olive kernel and lignite coal chars, respectively. The activation energy values for the lignite coal char significantly varied with carbon conversion degree, whereas this was not the case for olive kernel char, where the activation energy remained essentially unmodified throughout the whole carbon conversion range. Finally, the combined Malek and Coats-Rendfrem method was applied to unravel the mechanism of chars-CO₂ gasification reaction. It was found that the olive kernel char-CO₂ gasification can be described with a 2D-diffusion mechanism function (D2) whereas the lignite coal char-CO₂ gasification follows a second order chemical reaction mechanism function (F2).     

木屑炭水蒸气催化气化制取合成气研究

以木屑炭为原料,K2CO3作为催化剂,以固定床气化炉为实验设备,进行水蒸气催化气化木屑炭的探究。考察木屑炭水蒸气气化的炭转化率、产氢率、气体组成体积分数和H2/CO比值随K2CO3催化剂质量分数(0~8%)、水蒸气流量(0.15~0.35 g/(min·g))、气化温度(800~950℃)变化的规律。实验结果表明:K2CO3催化剂可显著提升碳转化率及产氢率,K2CO3质量分数为8%时,碳转化率和产氢率分别达到86.3%和125.6 g/kg,同时合成气中CO体积分数显著增加,H2/CO比值降至2.43。增加水蒸气流量,合成气中H2含量显著增大,H2/CO比值随之增大。温度可有效促进炭气化过程,950℃时碳转化率和产氢率分别达到84.3%和127.1 g/kg,但合成气中CO体积分数增大,H2/CO比值降至2.48。实验得到H2/CO比值在2.43~5.16范围的合成气。气化反应温度在900℃、水蒸气0.2 g/(min·g)、K2CO3质量分数3%时,碳转化率可达80.4%,产氢率109.6 g/kg,合成气中(H2+CO)体积分数82.4%,同时H2/CO比值高达3.05。     

CO_2气氛下劣质煤气化及动力学特性实验研究

利用综合热分析仪以非等温热重法研究了升温速率及粒径对于两种劣质煤粉在CO2气氛下气化反应特性的影响规律,考察了灰分对于两种劣质煤气化反应性的影响,并采用均相反应模型(HM),利用Freeman-Carroll法计算拟合得到各条件下气化反应动力学参数。结果表明:两种劣质煤CO2气化反应级数都是1.0级。反应条件对两种煤样的反应活化能产生了相似的影响:CO2气氛下,在900～1 300℃的样品气化反应区间,当其它条件不变时,随着煤样粒径由150～400μm减小到0～75μm,两种劣质煤样表观活化能呈明显下降趋势;而随着升温速率由30℃/min降至10℃/min,两种煤样反应活化能则在上升。在不同样品粒径及升温速率下,两种煤粉的气化活化能和对应的指前因子之间存在着动力学补偿效应。