Experimental Study on Coal Multi-generation in Dual Fluidized Beds

An atmospheric test system of dual fluidized beds for coal multi-generation was built.One bubbling fluidized bedis for gasification and a circulating fluidized bed for combustion.The two beds are combined with two valves:one valve to send high temperature ash from combustion bed to the gasification bed and another valve to sendchar and ash from gasification bed to combustion bed.Experiments on Shenhua coal multi-generation were madeat temperatures from 1112 K to 1191 K in the dual fluidized beds.The temperatures of the combustor are stableand the char combustion efficiency is about 98%.Increasing air/coal ratio to the fluidized bed leads to theincrease of temperature and gasification efficiency.The maximum gasification efficiency is 36.7% and thecalorific value of fuel gas is 10.7 MJ/Nm3.The tar yield in this work is 1.5%,much lower than that of pyrolysis.Carbon conversion efficiency to fuel gas and flue gas is about 90%.     

Ash deposition and sodium migration behaviors during combustion of Zhundong coals in a drop tube furnace

Zhundong coalfield is one super-large coalfield recently discovered in China. However, the utilization of Zhundong coal in power plants has caused serious ash-related issues mainly due to its high-sodium feature. The ash deposition problem on convection heat exchanger surfaces is still particularly difficult to resolve and its mechanism has yet to be fully understood. This study deals with the ash deposition and alkali metal migration behaviors on convection heat exchanger surfaces between 400 and 800 °C during combustion of Zhundong coal using a lab-scale drop tube reactor. Experimental results show that the sodium content in ash deposit of Zhundong coals increases obviously as the deposition temperature decreases from 800 to 600 °C, while it is almost unchanged below 600 °C. The contents of iron and calcium in ash deposits exhibit nonmonotonic variations as the deposit probe temperature varies between 400 and 800 °C. Quartz and calcium sulfate are main crystalline phases in ash deposit of Zhundong coals. Calcium is inclined to present as calcite and lime at low deposition temperature, while high temperature facilitates calcium sulfation. Sodium of crystalline phase is found as albite and sodium sulfate at low deposition temperature. Both condensation of gaseous alkali metals and formation of low-melting minerals were responsible for the ash deposition phenomenon on convection heat exchanger surfaces involved in combustion of Zhundong coal. The sodium content in ash deposit decreases considerably with the increasing combustion temperature while the case of iron variation is opposite due to its low-volatility. In addition, the Na content in ash deposits increases obviously with the access air ratio reduced from 1.2 to 1.05, but the local weakly reducing atmosphere leads to less iron within ash deposits. Clarification of sodium migration and evaluation of ash deposition behaviors during combustion of Zhundong coal is helpful for a better exploration of the functional mechanism of ash deposit and then large-scale utilization of high-sodium coals.     

Bench-scale bubbling fluidized bed systems around the world - Bed agglomeration and collapse: A comprehensive review

Thermochemical conversion by gasification process is one of the most relevant technologies for energy recovery from solid fuel, with an energy conversion efficiency better than other alternatives like combustion and pyrolysis. Nevertheless, the most common technology used in the last decades for thermochemical conversion of solid fuel through gasification process, such as coal, agriculture residues or biomass residues are the fluidized bed or bubbling fluidized bed system. For these gasification technologies, an inert bed material is fed into reactor to improve the homogenization of the particles mixture and increase the heat transfer between solid fuel particles and the bed material. The fluidized bed reactors usually operate at isothermal bed temperatures in the range of 700–1000 °C, providing a suitable contact between solid and gas phases. In this way, chemical reactions with high conversion yield, as well as an intense circulation and mixing of the solid particles are encouraged. Moreover, a high gasification temperature favours carbon conversion efficiency, increasing the syngas production and energy performance of the gasifier. However, the risk of eutectic mixtures formation and its subsequent melting process are increased, and hence the probability of bed agglomeration and the system collapse could be increased, mainly when alkali and alkaline earth metals-rich biomasses are considered. Generally, bed agglomeration occurs when biomass-derived ash reacts with bed material, and the lower melting temperature of ash components promotes the formation of highly viscous layers, which encourages the progressive agglomerates creation, and consequently, the bed collapse and system de-fluidization. Taking into account the relevance of this topic to ensure the normal gasification process operating, this paper provides several aspects about bed agglomeration, mostly for biomass gasification systems. In this way, chemistry and mechanism of bed agglomeration, as well as, some methods for in-situ detection and prediction of the bed agglomeration phenomenon are reviewed and discussed.     

Transformation characteristics of Na and K in high alkali residual carbon during circulating fluidized bed combustion

In this study, the transformation characteristics of sodium (Na) and potassium (K) during combustion of Zhundong coal gasification fly ash in circulating fluidized bed (CFB) reactors were investigated by examining gasification fly ash (TCf) from a 0.1-MW CFB test system. Experimental results indicated that TCf was rich in Na and K, with water-soluble and insoluble Na the main Na forms. Insoluble K was the major K form in TCf, accounting for 70.6% of total K. Reactor bed temperature exerted important effects on Na release during combustion such that, as bed temperature increased, the proportions of Na in bottom and circulating ash decreased while the Na in fly ash increased. Hydrochloric acid-soluble and insoluble Na in ash accounted for a large fraction of total Na. However, insoluble K was the principle K form in ash and bed temperature showed little influence on K release and distribution in ash during combustion. With decreased flue gas temperature, the Na content in deposition ash initially increased, then decreased, and eventually stabilized, while the K content in deposition ash was basically unchanged. Agglomeration of ash particles occurred during combustion, being more apparent at higher gas temperatures, and the agglomerates were rich in Na, K, sulfur (S), chlorine (Cl), and calcium (Ca). Deposition ash Na was mainly contained NaCl and Ca/Na sulfates. The enrichment of these salts as well as of Ca sulfate in ash was the main cause of ash agglomeration and deposition.     

Experiments on chemical looping combustion of coal with a NiO based oxygen carrier

A chemical looping combustion process for coal using interconnected fluidized beds with inherent separation of CO₂ is proposed in this paper. The configuration comprises a high velocity fluidized bed as an air reactor, a cyclone, and a spout-fluid bed as a fuel reactor. The high velocity fluidized bed is directly connected to the spout-fluid bed through the cyclone. Gas composition of both fuel reactor and air reactor, carbon content of fly ash in the fuel reactor, carbon conversion efficiency and CO₂ capture efficiency were investigated experimentally. The results showed that coal gasification was the main factor which controlled the contents of CO and CH₄ concentrations in the flue gas of the fuel reactor, carbon conversion efficiency in the process of chemical looping combustion of coal with NiO-based oxygen carrier in the interconnected fluidized beds. Carbon conversion efficiency reached only 92.8% even when the fuel reactor temperature was high up to 970 °C. There was an inherent carbon loss in the process of chemical looping combustion of coal in the interconnected fluidized beds. The inherent carbon loss was due to an easy elutriation of fine char particles from the freeboard of the spout-fluid bed, which was inevitable in this kind of fluidized bed reactor. Further improvement of carbon conversion efficiency could be achieved by means of a circulation of fine particles elutriation into the spout-fluid bed or the high velocity fluidized bed. CO₂ capture efficiency reached to its equilibrium of 80% at the fuel reactor temperature of 960 °C. The inherent loss of CO₂ capture efficiency was due to bypassing of gases from the fuel reactor to the air reactor, and the product of residual char burnt with air in the air reactor. Further experiments should be performed for a relatively long-time period to investigate the effects of ash and sulfur in coal on the reactivity of nickel-based oxygen carrier in the continuous CLC reactor.     

A proposed scheme for coal fired combined cycle and its concise performance

For IGCC, the primary investment is too high due to the demand of high gasification efficiency. For PFBCC, the thermal efficiency is too low due to the relatively low turbine inlet temperature and the hot working medium of the gas turbine is not easy to clean. A new scheme is proposed for coal fired combined cycle to overcome the main drawbacks of IGCC and PFBCC. The research targets are developing a new cycle construction of coal fired combines cycle to raise the efficiency and reduce the primary investment. Actually, the new scheme is a synthesis of some existing proposals. It adopts partial gasification to reduce the primary investment of the gasification equipment. The un-gasified surplus solid is then feed to a pressurized fluidized bed boiler, but adopting Curtiss Wright type external combustion to lower the ash content in the working medium. The gas fuel from the partial gasifier is combusted in a top combustor to further increase the working medium temperature. An extremely concise performance estimation method for the new scheme and its equations is proposed in order to easily understand the basic physical meaning of the new system. Some typical calculations based on this concise method are given. Then, a more detailed computation is accomplished with Aspen Plus code. The basic feasibility of this scheme is proven to be favorable. The efficiency is higher than the existing coal fired IGCC plants. The advantage of the new scheme comes from the better utilization of coal energy. Almost all the energy of coal is first utilized in the top cycle, and then the bottom cycle, just like the gas fueled combined cycle does. The primary investment is lower than the ordinary IGCC due to the lack of air separation unit and the adoption of partial gasification. The ash content is much lower than that of the existing PFBCC plants. If no any harmful ash in working medium is required, the atmospheric fluidized bed can be applied rather than the pressurized fluidized bed. A similar proposal with atmospheric fluidized bed and its performance estimation are also given. However, its efficiency will be lower than the pressurized fluidized bed scheme.     

煤的气化反应活性对常压固定床气化的影响

简要介绍了煤的气化反应活性及其影响因素,提出了根据煤的气化反应活性界定气化用煤灰熔融性温度指标的方法,并就煤的气化反应活性对常压固定床气化炉内氧化层、还原层、干馏层、干燥层及炉出煤气温度的影响进行了系统分析。     

流化床部分煤气化实验研究

在一台小型流化床部分煤气化气化炉上,以空气和水蒸气为气化剂,在不同操作条件下(给煤量、流化风量和蒸气量),进行了三种不同煤种的气化实验。研究结果表明,床温随给煤量和蒸汽量的增加以及流化风量的减小而降低;在一定范围内。煤气中CO含量随给煤量、流化风量和蒸汽量的增加以及煤化程度的降低而升高;煤气中H2含量随给煤量和煤化程度的升高以及流化风量和蒸汽量的减小而降低;CH4含量随给煤量的增加而增加,随流化风量、蒸汽量和煤化程度的升高而降低。另外,煤化程度升高,生成煤气的热值减小。     

Kinetics study for sodium transformation in supercritical water gasification of Zhundong coal

Zhundong coal (ZDC) has attracted much attention due to its high alkali metal content which can lead to a series of problems such as furnace slagging and ash fouling. Supercritical water gasification (SCWG) become a better choice for ZDC coal utilization because of its unique chemical and physical properties. The transformation mechanism of alkali metals during SCWG process was different from conventional ways of coal utilization. Systematic research about it could hardly be found. In this study, ZDC was used to explore sodium transformation mechanism and kinetics during supercritical water gasification under typical conditions. We got four kinds of sodium including the water-soluble fraction (L1), the carboxylic matrix-associated fraction (L2), the macromolecular organic group-associated fraction (L3), and the inorganic silicate mineral fraction (L4) through sequential extraction method after SCWG. A reaction pathway of sodium transformation in supercritical water gasification was proposed. A quantitative kinetic model for describing sodium transformation mechanism was developed. Finally, it was found that, L1 played an important role in catalytic process and mineral in coal weaken the catalytic process by combining with L1. L2 and L3 served as the two important intermediate products in the coal gasification, which explained the catalytic mechanism of sodium. L3 showed better reactivity. Sodium finally tended to deposit in the form of NaSiAlO₄ (L4) which was stable and environmentally friendly. All of these could provide basis for high-efficiency utilization of ZDC and the design of a reactor.     

空气鼓风流化床煤部分气化炉煤气成分与热值试验

在内径100mm，高4．2m的常压流化床气化炉试验装置上进行试验，考察了气化炉温度，空煤比，汽煤比等影响因素对煤气成分和热值的影响，并对其气化机理进行了分析。结果表明，流化床煤部分气化炉内存在较佳气化温度，汽煤比和空煤比区域。图7表3参4     

生物质气化影响因素分析

阐述了生物质定义、特点及生物质气化原理，综述了生物质在流化床气化中，气化剂、原料粒径、温度、压力、原料前处理等操作条件对生物质气化产品组成的影响，讨论了煤与生物质共气化的协同作用，指出了生物质流化床气化的技术关键。     

流化床部分煤气化影响因素研究

在流化床部分气化炉上系统研究了流化风量、给煤量、水蒸气量、床层温度、静止床层高度、煤种、催化剂等因素对煤气成分和热值的影响,研究结果表明:流化风量、给煤量、水蒸气量、静止床层高度对煤气成分的影响较为复杂,4者都存在最佳范围;床层温度是影响煤气成分的主要因素,煤气热值与温度成正比;增加床层高度,有利于H2、CO生成和CH4分解;烟煤的煤气中含有的可燃成分(H2、CO、CH4)含量比无烟煤高,优质烟煤比劣质烟煤更适合于气化;Ca、Na、K等碱土金属化合物对煤气化具有催化作用,且Na2CO3和K2CO3的催化能力比CaO强。     

Effects of oxy-fuel condition on morphology and mineral composition of ash deposit during combustion of Zhundong high-alkali coal

Zhundong coalfield is a super-large coal reserve, with high-alkali feature exacerbating ash deposition. Oxy-fuel combustion technology could propel the clean utilization of Zhundong high-alkali coal. While the ash deposition behavior of high-alkali coal under oxy-fuel condition has yet to be sufficiently investigated. The present study compared the differences of ash deposits between oxy-fuel and air combustion, and also examined the effects of oxygen content on ash deposition mechanism, employing a drop-tube furnace equipped with a specially designed sampling probe and some analysis methods, such as X—ray diffraction equipment, simultaneous thermal analyzer, etc. Experimental results indicated that ash deposition was weaker, with fewer contents of sodium chloride, calcium sulphate and less agglomeration ash in oxy-fuel atmosphere compared to the air case with same oxygen content. The content of the ash particle distributed in the range of 0–40 μm was up to 60% under oxy-fuel condition. The first weight loss of ash deposits, around 850 °C, was put down to the decomposition of carbonate and the second one, about 1150 °C, was ascribed to the decomposition of the sulphate minerals in the thermal process. Ash deposition worsened with more large particles (>120 μm), as the oxygen content rose. Sodium chloride content reached 9.7% with 50% oxygen content. The present study not only focuses on the morphology and chemical components, but also probes into the thermal volatility of ash deposits, which benefits the further understanding of the ash deposition mechanism and utilization of Zhundong high-alkali coal during oxy-fuel combustion.     

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。     

准东煤灰熔融特性试验研究

将神华准东煤（神华煤）和天池能源准东煤（天池煤）与碱沟煤按照不同质量掺混比进行混合并制得灰样,将NaCl、CaO、Al2O3和SiO2按不同添加比例加入神华煤和天池煤并制成灰样,对上述混合灰样的熔融特性进行研究.结果表明：碱沟煤掺混2种准东煤后,随着准东煤质量掺混比的增大,混合灰各个灰熔点特征温度先降低后升高;随着灰样中Na含量增加,准东煤灰样的变形温度显著降低,软化温度、半球温度和流动温度先降低后趋于不变;当灰样中Na含量达到一定比例后,NaCl对准东煤灰熔融特性的影响明显减弱;CaO对准东煤灰熔点的影响较复杂,可以降低也可以提高灰熔点;随着Al2O3添加比例的增加,准东煤灰熔点先升高后急剧降低;随着SiO2添加比例的增加,神华煤灰样的变形温度先升高后降低,而天池煤灰样的变形温度逐步升高,其他3个特征温度均逐渐降低.     

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.     

煤基化学链燃烧串行流化床的冷态试验研究

采用“湍动床＋快速床”作为煤基化学链燃烧（CLC）系统的空气反应器（AR）,鼓泡床作为燃料反应器（FR）,设计了流动密封阀和旋风分离器,分别用于隔绝2个反应器之间的气氛和进行气固分离,在冷态试验装置上分析研究了CLC系统的压力分布、固体循环流量、气体泄漏率及煤灰与循环载体的分离效果．结果表明：该串行流化床反应器之间气氛隔绝性良好,气体泄漏率较低,固体循环流量达到甚至超过设计标准,FR二级旋风分离器的分离效率接近100％,FR中煤灰进入AR的质量分数小于1．55％,煤灰分离效果良好;装置可以长时间连续稳定运行,且操作气速范围较广,自行设计建造的循环流化床作为煤基化学链燃烧试验装置是可行的．     

循环流化床锅炉飞灰残碳的生成及其处理

循环流化床燃烧技术因其众多的优点得到广泛应用,但是在运行中普遍存在着飞灰含碳量远远高于预期的问题。影响飞灰含碳量的主要因素包括:煤指标、煤的结构和焦炭反应活性、给煤粒径以及循环流化床的结构和其它运行参数等。目前,降低飞灰含碳量的方法有:飞灰再循环、加强二次风刚性和调整床压降等。实验表明,在低风速条件下,可以将飞灰中的残碳充分燃尽。另外,高压静电分离和飞灰水活化团聚也都为飞灰残碳的利用提供了新思路。