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℃.     

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.     

炭化气氛对黑液煤浆及不同煤种气化反应特性的影响

煤气化前阶段的炭化气氛(温度、时间)影响到煤焦的气化反应特性.采用不同的炭化温度和炭化时间制备了黑液水煤浆、普通水煤浆以及其他5种煤的焦样,得到了各种煤焦气化反应的碳转化率;同时,通过扫描电子显微镜分析手段鉴别焦炭表面孔隙分布情况.试验结果表明,相同炭化气氛下得到的7种不同煤焦中,黄陵煤焦的气化活性最高,说明煤化程度越高反应性越低;由于黑液中有机物和无机物钠盐的影响,黑液水煤浆焦的气化特性高于普通水煤浆焦和新汶煤焦.煤焦的气化反应性,不仅与煤阶有关,还和煤焦中含氧官能团和无机化合物的含量有关,同时煤浆中外在添加的无机物组分也影响到煤焦的气化活性.     

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。     

Imbert式气化器生物质气化综合试验研究

以木块为原料,利用Imbert式气化器进行气化试验,研究了在气化器底部加设木炭层以及不同的还原区温度对产出气成分的影响规律。结果表明：加设木炭层使产出气中CO2含量略有减少,CO含量略有增加,气体品质没有明显的改善,但是可以降低气化器出气口气体的温度;还原区温度为800～900℃时,可以获得较好的产出气品质。     

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。     

石油焦的气化反应特性

针对3种不同的石油焦，在热天平上考察了不同的化学反应条件，包括温度、压力和气氛等因素对气化反应的影响．研究结果发现，在水蒸气气氛下石油焦具有良好的气化反应活性，而在二氧化碳气氛下石油焦气化反应进行得相当缓慢，相同条件下的C-H2O反应速率是C-CO2反应速率的十几倍，在60％水蒸气的实验温度条件下，每升高50℃，平均气化反应速率提高1倍；1000℃时，水蒸气分压对平均气化反应速率的影响不均匀，分压增加，影响减小．随着反应的不断进行，气化反应速率存在最大值，而出现最大值时的转化率不受反应温度和压力的影响，而与气化介质有关．根据实验结果，分析得到了3种石油焦在水蒸气条件下反应速率与温度、水蒸气分压和转化率的关系式，并得到了3种石油焦气化反应的活化能。     

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。     

煤粉加压气化炉操作参数对气化特性的影响

采用基于平衡态模型的气流床气化炉煤气组分预测程序,分析研究了气化压力、氧煤比以及蒸汽煤比等操作参数对气化温度、煤气组分、碳转化率和气化效率的影响规律。研究结果表明:气化压力对气化特性指标影响甚微,而氧煤比和蒸汽煤比的影响较为显著。随氧煤比的增加,气化温度升高,碳转化率升高,气化效率先升高再降低,CO浓度先增加后降低。CH_4的体积浓度可用于预测气化温度。在蒸汽煤比较低时,提高蒸汽煤比可增加H_2的浓度,提高碳转换率和气化效率,但进一步提高蒸汽煤比仅会降低气化炉内的气化温度,提高H_2O和CO_2浓度。对于所研究的煤种,合理的氧煤比应在0.7左右,合理的蒸汽煤比在0.1左右。     

生物质气流床气化制取合成气的试验研究

利用一套小型生物质层流气流床气化系统,研究了稻壳、红松、水曲柳和樟木松4种生物质在不同反应温度、氧气/生物质比率(O/B)、水蒸汽/生物质比率(S/B)以及停留时间下对合成气成分、碳转化率、H2/CO以及CO/CO2比率的影响.研究表明4种生物质在常压气流床气化生成合成气最佳O/B范围为0.2～0.3(气化温度.1300℃),高温气化时合成气中CH4含量很低,停留时间为1.6s时其气化反应基本完毕.加大水蒸汽含量可增加H2/CO比率,在S/B为0.8时H2/CO比率都在1以上,但水蒸汽的过多引入会影响煤气产率.气化温度是生物质气流床气化最重要的影响因素之一.     

Method of gasification in IGCC system

A coal gasifier is designed to operate at the temperature range of 1200–1300 °C. The 1200 °C sets the lower limit to the carbon reforming efficiency of the high temperature reformer, and the 1300 °C is the lower limit of the fluid temperature of coal slags, below which they may be collected as non-fluid slag. The gasifier is connected to two syngas burners where a portion of product syngas is combusted with O₂ gas and produce ultra hot H₂O and CO₂ gases, these two gases enter into the gasifier and maintain the gasifier temperature at above 1200 °C and reform carbon into syngas. The temperature of the gasifier is controlled by the flow of O₂ gas into the syngas burner, where O₂ gas is completely consumed and none left to enter into the gasifier. This removes any possibility of forming oxidated products, and compressed CO₂ gas spray coal powder into the gasifier column and non-fluid slag is collected at the bottom. A higher level integration of oxidation–reduction cycle is shown for a IGCC system, wherein the exhaust gas of syngas turbine drives the reduction reaction of coal gasification.

A smooth and uniform temperature control within the gasifier assures high efficiency of carbon reforming and quality of product syngas. Conventional Lurgi gasifier relies on its large heat capacity and accumulating coal slag along the inner walls of the gasifier has made the gasifier bigger, lately as large as a three story building. The gasifier of the present design is constructed much smaller in its size, but with greater reforming efficiency.     

Physicochemical properties and gasification reactivity of the ultrafine semi-char derived from a bench-scale fluidized bed gasifier

Zhundong coalfield is the largest intact coalfield worldwide and fluidized bed gasification has been considered as a promising way to achieve its clean and efficient utilization.The purpose of this study is to investigate the physieochemical properties and gasification reactivity of the ultrafine semi-char,derived from a bench-scale fluidized bed gasifier,using Zhundong coal as fuel.The results obtained are as follows.In comparison to the raw coal,the carbon and ash content of the semi-char increase after partial gasification,but the ash fusion temperatures of them show no significant difference.Particularly,76.53％ of the sodium in the feed coal has released to the gas phase after fluidized bed gasification.The chemical compositions of the semi-char are closely related to its particle size,attributable to the distinctly different natures of diverse elements.The semi-char exhibits a higher graphitization degree,higher BET surface area,and richer meso-and macropores,which results in superior gasification reactivity than the coal char.The chemical reactivity of the semi-char is significantly improved by an increased gasification temperature,which suggests the necessity of regasification of the semi-char at a higher temperature.Consequently,it will be considered feasible that these carbons in the semi-char from fluidized bed gasifiers are reclaimed and reused for the gasification process.     

Analysis of char-slag interaction and near-wall particle segregation in entrained-flow gasification of coal

The fate of carbon particles during entrained-flow gasification of coal in the slagging regime is analyzed. More specifically, the study addresses the relevance of segregation of carbon particles in a near-wall region of the gasifier to coal conversion. Segregation of carbon particles is analyzed considering the effects of turbulence- and swirl-promoted particle migration toward the wall, interaction of the impinging particles with the wall ash layer, coverage of the slag layer by refractory carbon particles, accumulation of carbon particles in a dense-dispersed phase near the wall of the gasifier. Operating conditions of the gasifier and slag properties may be combined so as to give rise to a variety of conversion regimes characterized by distinctively different patterns of carbon particles segregation.A simple 1D model of an entrained-flow gasifier has been developed based on the conceptual framework of carbon particle segregation. The model aims at providing a general assessment of the impact of the different patterns of carbon particle segregation on the course and extent of carbon gasification. A sensitivity analysis with reference to selected model parameters is performed to identify key processes controlling carbon segregation and their impact on the gasifier performance.     

煤质对水煤浆气化性能的影响研究

煤质与气流床气化炉的匹配性至关重要,其不但影响气化炉的运行条件,也影响气化性能。本文选择了10种来自新疆和陕西北部的煤样进行了工业分析、元素分析、灰组成分析、灰熔点分析以及成浆性测试,并筛选出适合水煤浆气化的煤样。同时借助Aspen Plus软件对适合水煤浆气化的煤样在相同的煤浆浓度、碳转化率及操作压力条件下开展煤质对水煤浆气化性能影响的模拟分析。结果表明煤中灰含量越高,冷煤气效率和有效气含量越低,比氧耗和比煤耗越高;煤中O/C质量比和H/C质量比的增加也会导致冷煤气效率和有效气含量降低,比氧耗和比煤耗增加。因此从水煤浆气化经济性考虑,建议水煤浆气化煤质灰含量小于9.0wt%,煤中O/C质量比小于0.173,H/C质量比小于0.065。     

Catalytic coal gasification for SNG manufacture

Exxon Research and Engineering Company is engaged in research and development on catalytic coal gasification (CCG) for the production of substitute natural gas (SNG). the catalysts being studied are the basic and weak acid salts of potassium. the use of a gasification catalyst allows the gasifier temperature to be reduced, reduces the tendency for swelling and agglomeration of caking coals and promotes gas phase methanation equilibrium. These features of the catalyst are utilized in a novel processing sequence which involves separation of product gas into methane (SNG) and a CO/H₂ stream which is recycled to the gasifier. the predevelopment phase of research on this process concept was completed in early 1978 and included bench-scale research on catalyst recovery and kinetics, the operation of a 6 in diameter × 30 ft long fluid bed gasifier and supporting engineering studies. As part of the engineering programme, a conceptual design has been developed for a pioneer commercial CCG plant producing SNG from Illinois No. 6 bituminous coal. the paper reviews the status of research and development on the CCG programme and describes the conceptual design and economics for the commercial scale CCG plant.     

Exergetic evaluation of biomass gasification

Biomass has great potential as a clean, renewable feedstock for producing modern energy carriers. This paper focuses on the process of biomass gasification, where the synthesis gas may subsequently be used for the production of electricity, fuels and chemicals. The gasifier is one of the least-efficient unit operations in the whole biomass-to-energy technology chain and an analysis of the efficiency of the gasifier alone can substantially contribute to the efficiency improvement of this chain. The purpose of this paper is to compare different types of biofuels for their gasification efficiency and benchmark this against gasification of coal. In order to quantify the real value of the gasification process exergy-based efficiencies, defined as the ratio of chemical and physical exergy of the synthesis gas to chemical exergy of a biofuel, are proposed in this paper. Biofuels considered include various types of wood, vegetable oil, sludge, and manure. In this study, exergetic efficiencies are evaluated for an idealized gasifier in which chemical equilibrium is reached, ashes are not considered and heat losses are neglected. The gasification efficiencies are evaluated at the carbon-boundary point, where exactly enough air is added to avoid carbon formation and achieve complete gasification. The cold-gas efficiency of biofuels was found to be comparable to that of coal. It is shown that the exergy efficiencies of biofuels are lower than the corresponding energetic efficiencies. For liquid biofuels, such as sludge and manure, gasification at the optimum point is not possible, and exergy efficiency can be improved by drying the biomass using the enthalpy of synthesis gas.     

Development of a high‐temperature two‐stage entrained flow gasifier model for the process of biomass gasification and syngas formation

This paper presents development of the Mitsubishi Heavy Industries (MHI) gasifier utilizing an analogy between a model with coal feedstock and the model with torrefied woody biomass. A computational fluid dynamics (CFD) model was primarily developed for coal gasification, and the simulation results were validated with similar published work and experimental measurements. The model was extended for the woody biomass to predict the gasifier performance under the gasification process. The results were used to compare the effect of fuel type on the gasifier performance and gaseous product compositions. The second‐level injection nozzles were modified tangentially, and the flow characteristics, species yields, and temperature were evaluated. The possibility of reducing the gasifier length from 13 to 8 m is also evaluated for different total length. The results revealed that using woody biomass leads to a decrease in the mole fraction of CO and H₂ at the gasifier outlet compared with coal. An opposite trend was observed for CO₂ and CH₄ compositions. The contributions of modified second‐level nozzles to the total gas composition and exit temperature only account for less than 3%. Reducing the gasifier length from 13 to 8 m increased the exit temperature from 1289 to 1340 K, but the changes in the exit gas composition were less than 2%. The new design of the MHI gasifier can reduce the investment costs by reducing the gasifier length as well as using biomass instead of coal.     

Gasification of preheated coal: Experiment and thermodynamic equilibrium calculation

A new process integrating a circulating fluidized bed (CFB) reactor and an entrained bed reactor was proposed for gasification of preheated coal. The CFB reactor as a preheater was successfully used in clean coal combustion. In this study, gasification of preheated coal was tested in a bench-scale test rig, which consisted of a CFB preheater and a down flow bed (DFB) gasifier. The effects of operating parameters of the preheater and gasifier were revealed via thermodynamic equilibrium calculations. A stable preheating process was obtained in the CFB preheater at the O₂/C molar ratio of 0.31 and higher gasification reactivity was gained in preheated char owing to the improvement in intrinsic reactivity, specific surface area and total pore volume. Effective gasification of preheated char was achieved in the DFB gasifier at 1100 °C and the total O₂/C molar ratio of 0.67, meanwhile the CO + H₂ yield and carbon conversion increased. Thermodynamic equilibrium calculations revealed when the gasification reaction rates varied little above 1100 °C and the same carbon conversion was achieve in gasifier, lowering the temperature would lead to an increase in cold gas efficiency and a decrease in O₂ demand.     

Regulation of chemical properties of ash and kinetic model construction of Lu’an coal gasification

The objective of this study was to enhance the suitability of Lu’an coal for gasification in large entrained-flow gasifiers currently used by the Lu’an Group Mining Company in its 1.8 million ton per annum coal-based oil synthesis demonstration project. The effect of coal blending and flux addition on the ash fusion temperature (AFT) and gasification reactivity was investigated. CaO, Fe₂O₃, and MgO decreased the AFT of Lu’an coal by 150°C, 73°C, and 68°C, respectively, by a flux addition of up to 7%. Within the range of the experimental investigation, the AFT of Lu’an coal decreased by 3°C for each 1% of Shenmu coal addition. The gradual reduction of mullite and the formation of fayalite and hessonite in blended coal ash decreased the AFT. The addition of a fluxing agent significantly increased the reaction activity of the char, with Fe₂O₃ exhibiting the largest catalytic effect on char gasification. Blending with Shenmu char significantly increased the gasification reactivity. The random pore model best describes the gasification process of Lu’an char, and a kinetic equation for the process was developed on the basis of this model.