高硫煤-CuO化学链燃烧特性及硫演化热力学研究

以贵州六枝高硫煤为研究对象,通过热重实验对该典型高硫煤和CuO氧载体的化学链燃烧特性及其与空气直接接触时的燃烧特性加以定性分析和定量评估。为探索煤中硫的演化及其与CuO氧载体作用对CuO氧化活性的影响,进一步采用HSC Chemistry软件,分析了氧载体过量系数Φ对煤中硫分布的影响。研究表明:相比于空气下煤直接燃烧,CuO与六枝煤化学链燃烧的着火温度高,可燃指数和综合燃烧特性指数小,显示CuO氧载体更低的反应活性;在热力学平衡状态下,当0Φ≤1.25及Φ1.25时,系统中硫组分分别以固相Cu_2S和气相SO_2形式存在。基于上述研究结果,提出了一种煤化学链燃烧系统中同时进行脱硫和CO_2捕集的新方案。     

3 MWth化学链燃烧装置设计方法

反应器系统是以煤为燃料的化学链燃烧系统的基础组成部分,是提供载氧体反应的场所,可将载氧体以合适的速率在不同的反应器之间传输,实现气固分离和不同性质颗粒的分离。因此,设计、研究反应器系统是实现以煤为燃料的化学链燃烧的根本前提。本文对反应器系统中的空气反应器、燃料反应器、炭分离器及整体的循环特性进行研究,总结建立了以煤为燃料的化学链燃烧反应器系统的设计方法,在此基础之上设计了3 MW_th的化学链燃烧示范装置,为以煤为燃料的化学链燃烧热态系统的建造与运行奠定了基础。     

基于铜基氧载体的生物质化学链氧解耦

在热重分析仪上研究了铜基、铁基氧载体与木屑反应的失重情况,考察了失重率与失重速率,使用铜基氧载体时,失重率和最大失重速率均比使用铁基时的大,说明生物质的化学链氧解耦燃烧利用比生物质化学链燃烧利用效率更高;当木屑与无烟煤按质量比1∶1掺混,其失重率和失重速率介于单独使用木屑和单独使用无烟煤之间,因此,在以煤为燃料时,适当掺混一些生物质,将有利于煤的燃烧;通过扫描电镜(SEM)观察了反应前后铜基氧载体的微观形貌,发现与木屑和无烟煤反应后的氧载体孔结构增加,在1,000,℃高温下有烧结现象.     

基于铁矿石载氧体加压煤化学链燃烧的试验研究

在反应温度为970℃、压力范围为0.1～0.6 MPa的条件下,以铁矿石为载氧体,采用固定床反应器,对煤化学链燃烧进行了试验研究,考察了加压对燃料反应器内水蒸气气氛下煤化学链燃烧的反应特性.结果表明:加压能加快煤水蒸气气化速率,加强水气转换反应,并对煤气组分产生影响,使CO浓度降低,CO2和H2浓度升高;加压后还原反应烟气中不再含有H2,CO和CH4的浓度也变得很低,说明加压可提高还原反应中煤气的转化率;随着压力的升高,碳转化率先升高后又降低,存在着一个中间压力值,使碳转化率最高.     

煤基化学链燃烧技术的NiO/NiAl_2O_4氧载体研究

直接以煤为燃料的化学链燃烧技术首先需要解决的关键问题是高性能氧载体.通过溶胶-凝胶法制备了几种不同NiO含量、不同烧结温度和不同煅烧时间的NiO/NiAl2O4氧载体,并对其物化性质进行了表征.实验结果表明,超过850℃时NiO/NiAl2O4与神府煤焦的还原反应快速进行,而60%(质量分数)NiO含量、1 300 ℃烧结6 h的NiO/NiAl2O4氧载体具有更好的还原反应性;在与煤焦/空气的单循环还原/氧化反应中,NiO/NiAl2O4表现出良好的循环反应性.实验结果证明基于NiO/NiAl2O4氧载体、燃用固体燃料煤焦的化学链燃烧技术是可行的.     

燃煤化学链燃烧技术的研究进展

燃煤化学链燃烧技术在实现煤炭高效利用的同时有效降低了CO_2的捕集能耗,是当前具有发展前景的第二代碳捕集技术。现有的研究主要从宏观层面评价燃煤化学链燃烧系统的反应性能,而从"结构与反应性"的角度进行综合评价的研究很少。围绕煤、载氧体和反应器三大系统核心,分析了煤种及其附属产物(煤灰、硫和氮)对燃煤化学链燃烧系统反应性能的影响;基于现有的载氧体开发类型及提高煤气化速率的载氧体改性方法,提出廉价、高效载氧体的规模化制备是未来载氧体研发的重点和难点;探讨了各种类型反应器的结构对煤、载氧体颗粒混合和反应的影响,指出反应器开发过程中存在的主要问题及未来的发展方向。     

基于锰矿石载氧体的准东煤化学链气化特性

化学链气化利用循环载氧体为气化过程提供氧化剂,碱金属修饰载氧体能显著催化气化过程.本文以高钠准东煤为燃料,反应性高、稳定性好的锰矿石为载氧体,探究循环次数、比氧耗和温度对准东煤化学链气化特性的影响.结果表明,随着循环次数增加,碱金属Na逐渐沉积在锰矿石表面,载氧体无明显烧结,反应性能良好;比氧耗的变化会影响合成气各组分浓度,比氧耗为4、温度900℃时,有效气组分可达78.83%.     

Fe2O3为载氧体的煤/秸秆化学链燃烧循环特性研究

对煤、秸秆与Fe2O3以不同质量掺混比混合后化学链燃烧过程中载氧体还原/再生的多循环反应特性进行了研究,重点分析了固体燃料带入的灰分对化学链反应速率的影响以及秸秆的掺入对化学链反应的改善.结果表明：载氧体Fe2O3质量掺混比的增大有利于化学链反应的进行,燃烧起始反应温度降低;Fe2O3作为载氧体受灰分积累的影响较大,其可持续循环能力较差;煤中掺入秸秆改善了煤的化学链燃烧特性,提高了燃烧反应速率和载氧体的再生反应速率.     

化学链燃烧技术的研究进展

化学链燃烧技术是一种高效、清洁、经济的新型无火焰燃烧技术.介绍了化学链燃烧的基本概念及特点,总结了载氧体、化学链燃烧反应器及化学链燃烧系统分析的研究进展,并指出了化学链燃烧技术仍存在且亟待解决的问题.非金属载氧体、同体燃料化学链燃烧是该技术的最新研究热点,其中固体燃料化学链燃烧是未来研究的重要趋势.     

铜基氧载体化学链氧解耦的流化床实验研究

采用溶胶-凝胶法制备了CuO/CuAl2O4氧载体,在CO2气氛下和空气气氛下,分别研究了该氧载体的释氧和吸氧性能,研究结果表明,随着温度的升高,氧载体的释氧、吸氧速率不断升高.随后在N2气氛下研究了3种典型煤的化学链氧解耦燃烧过程,结果表明,煤中挥发分的含量直接影响燃烧过程的快慢,在氧解耦燃烧时,高挥发分的褐煤尾气中,CO2体积分数比无烟煤高15%左右,褐煤中碳的平均转化率为无烟煤的2～3倍.     

Reduction Kinetics of Fe-based Oxygen Carriers Using Syngas in a Honeycomb Fixed-Bed Reactor for Chemical-Looping Combustion

Chemical-looping combustion(CLC) is considered to be a vital method for utilizing hydrocarbon fuel with low carbon emissions. A honeycomb fixed-bed reactor is a new kind of reactor for CLC. However, the further application of the reactor is limited by the inadequacy of the kinetic equations for CLC. In this paper, the experimental studies on the kinetic of Fe-based oxygen carriers were carried out by the CLC experiments using syngas which was obtained from one typical type of coal gasification p...     

Pressurized chemical-looping combustion of coal with an iron ore-based oxygen carrier

Chemical-looping combustion (CLC) is a new combustion technology with inherent separation of CO₂. Most of the previous investigations on CLC of solid fuels were conducted under atmospheric pressure. A pressurized CLC combined cycle (PCLC-CC) system is proposed as a promising coal combustion technology with potential higher system efficiency, higher fuel conversion, and lower cost for CO₂ sequestration. In this study pressurized CLC of coal with Companhia Valedo Rio Doce (CVRD) iron ore was investigated in a laboratory fixed bed reactor. CVRD iron ore particles were exposed alternately to reduction by 0.4 g of Chinese Xuzhou bituminous coal gasified with 87.2% steam/N₂ mixture and oxidation with 5% O₂ in N₂ at 970 °C. The operating pressure was varied between 0.1 MPa and 0.6 MPa. First, control experiments of steam coal gasification over quartz sand were performed. H₂ and CO₂ are the major components of the gasification products, and the operating pressure influences the gas composition. Higher concentrations of CO₂ and lower fractions of CO, CH₄, and H₂ during the reduction process with CVRD iron ore was achieved under higher pressures. The effects of pressure on the coal gasification rate in the presence of the oxygen carrier were different for pyrolysis and char gasification. The pressurized condition suppresses the initial coal pyrolysis process while it also enhances coal char gasification and reduction with iron ore in steam, and thus improves the overall reaction rate of CLC. The oxidation rates and variation of oxygen carrier conversion are higher at elevated pressures reflecting higher reduction level in the previous reduction period. Scanning electron microscope and energy-dispersive X-ray spectroscopy (SEM-EDX) analyses show that particles become porous after experiments but maintain structure and size after several cycles. Agglomeration was not observed in this study. An EDX analysis demonstrates that there is very little coal ash deposited on the oxygen carrier particles but no appreciable crystalline phases change as verified by X-ray diffraction (XRD) analysis. Overall, the limited pressurized CLC experiments carried out in the present work suggest that PCLC of coal is promising and further investigations are necessary.     

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．     

Study of devolatilization during chemical looping combustion of large coal and biomass particles

Chemical Looping Combustion (CLC) is one of the emerging technologies for carbon capture, with less energy penalty. The present way of using pulverized coals in a fluidized bed (FB)-CLC have limitations like loss of unconverted char and gaseous combustibles, which could be mitigated by use of coarser fuel particles. Devolatilization time is a critical input for the effective design of FB-CLC systems, primarily when large fuel particles are used. The present study investigates the devolatilization time and the char yield of three coals of two shapes, namely, two high ash Indian coals and a low ash Indonesian coal and a wood (Casuarina equisetifolia) in the size range of +8–25 mm, at different fuel reactor temperatures (800–950 °C) of a hematite based CLC unit. The devolatilization times of single fuel particles during CLC are determined using a visual method called ‘Color Indistinction Method’. Indonesian coal has the longest devolatilization time among the fuels, and biomass has the least. Increasing the bed temperature enhances the rate of volatile release, whereas this effect is less pronounced in larger particles. Devolatilization of Indonesian coal is found to be strongly influenced by the changes in operating conditions. With the decrease in sphericity, a maximum of 56% reduction in devolatilization time is observed for the +20–25 mm slender particles of Indonesian coals when compared to the near-round particles. The maximum average char yields at the end of the devolatilization phase for coal and biomass are about 55–76% and 16% respectively. Char yield in coal particles increases with an increase in particle size, whereas biomass particles show relatively consistent yield across all experimental conditions. Increase in bed temperature reduces the char yields of coal up to 12% and in biomass up to 30%. High volatile Indian coal is the most influenced fuel by the changes in fuels shape. A correlation for determining devolatilization time under CLC environment is presented, and it successfully fits most of the experimental values within ±20% deviation for coals (R² = 0.95) and within ±15% deviation for biomass (R² = 0.97).     

Investigation of Coal Fueled Chemical Looping Combustion Using Fe_3O_4 as Oxygen Carrier：Influence of Variables

Chemical-looping combustion (CLC) is a novel combustion technique with inherent CO2 separation.Magnetite (Fe3O4) was selected as the oxygen carrier.Shenhua coal (Inner Mongolia,China),straw coke and natural coke were used as fuels for this study.Influences of operation temperatures,coal to Fe3O4 mass ratios,and different kinds of fuels on the reduction characteristics of the oxygen carrier were investigated using an atmosphere thermogravimetric analyzer (TGA).Scanning electron microscopy (SEM) was used to analyse the characteristic of the solid residues.Experimental results shown that the reaction between the coal and the oxygen carrier become strong at a temperature of higher than 800℃.As the operation temperature rises,the reduction conversion rate increases.At the temperatures of 850oС,900℃,and 950℃,the reduction conversion rates were 37.1%,46.5%,and 54.1% respectively.However,SEM images show that at the temperature of higher than 950℃,the iron oxides become melted and sintered.The possible operation temperature should be kept around 900℃.When the mass ratios of coal to Fe3O4 were 5/95,10/90,15/85,and 20/80,the reduction conversion rates were 29.5%,40.8%,46.5%,and 46.6% respectively.With the increase of coal,the conversion rate goes up.But there exist an optimal ratio around 15/85.Comparisons based on different kinds of fuels show that the solid fuel with a higher volatile and a more developed pore structure is conducive to the reduction reactivity of the oxygen carrier.     

Fueling power plants with high sulfur coal in compliance with emission standards

We compare the economics of the two most advanced strategies for meeting current SO₂ emission standards in power plants fueled with high sulfur coal. One strategy calls for converting high sulfur coals to clean synfuels before combustion. The other involves direct coal burning, followed by fuel gas desulfurization (FGD). Our results show that the FGD route is preferable.Advantages of FGD over the coal conversion route are the following. The total capital and operating costs for FGD are almost an order of magnitude lower, thermal efficiencies are higher, and utility requirements are lower. The FGD systems have been in operation since 1968 and, after initial problems, have been operated reliably and at availability acceptable to the utility industry. About 80% of existing power plants, according to one survey, can be retrofitted with FGD. Even with possible breakthroughs in coal-conversion technologies, it appears that FGD will remain the economically preferred route to desulfurization.     

The use of non-fossil derived hydrogen; a possible role for coal conversion

The paper summarises some results of a study on the use of non-fossil derived hydrogen in coal conversion processes carried out by the National Coal Board under two contracts to the European Communities.Under the first contract the study consisted of a technical and economic evaluation of the use of non-fossil derived hydrogen on three coal conversion processes. These are methanol synthesis, solid phase hydrogenation (hydrogasification) for substitute natural gas production, and liquid phase hydrogenation (liquefaction) for the manufacture of liquid fuels. The introduction of non-fossil derived hydrogen generally resulted in an increase in the conversion efficiency and carbon utilization, and a reduction in the number of component stages of the process. Economic evaluations were carried out to determine the price at which non-fossil derived hydrogen would have to be available for its use in coal conversion processes to be preferable to the conventional (self-contained) route. The manufacture of synthetic fuels from non-fossil derived hydrogen was also compared with the direct use of hydrogen. It was concluded that market conditions could exist in which the use of non-fossil derived hydrogen in coal conversion would be preferable to both conventional coal conversion and the direct use of the hydrdogen, irrespective of the coal price.At present the study is being extended under a second contract to include two further coal conversion processes. These are substitute natural gas production from synthesis gas (methanation) and the production of liquid fuels from synthesis gas by a Fischer-Tropsch synthesis route. The results of the technical and economic evaluations reinforce those of the first study. In addition there are available preliminary results of a comparison of the economics of overall systems of hydrogen production from nuclear power and electrolysis and utilization in coal conversion processes with conventional coal conversion technology.     

我国现代煤化工技术发展路线探讨

根据我国的能源状况分析了我国必须发展现代煤化工的理由：2005年我国能源生产和消费结构中,煤炭分别占73．3％和68．7％,煤炭现在是,将来仍然是我国能源的主力;我国原油进口量不断增加;传统的煤炭利用方式不仅效率低,而且造成了严重的环境污染。因此发展以煤气化为核心的生产洁净和可替代石油的能源和化工产品的现代煤化工已成为解决我国能源与环境问题的关键。介绍了我国有关的发展煤化工的政策和规划。分析了煤基甲醇路线是适合我国国情的现代煤化工技术路线．指出煤制油项目虽是国家能源安全的萤要组成部分,但要谨慎发展．     

Comparison of CuO and NiO as oxygen carrier in chemical looping combustion of a Victorian brown coal

Chemical looping combustion (CLC) is a novel process where an oxygen carrier, preferably oxides of metal, is used to transfer oxygen from the combustion air to the fuel. The outlet gas from the process reactor consists of CO₂ and H₂O, and concentrated stream of CO₂ is obtained for sequestration when water vapour is condensed. Chemical looping has been widely studied for combustion of natural gas; however its application to solid fuels, such as coal, is being studied relatively recently; no work has been done using Victorian brown coal which represents a very large resource, over 500 years at current consumption rate. In this study we carried out an experimental investigation pertaining to CLC of a Victorian brown coal from Loy Yang mine using NiO and CuO as oxygen carrier. The experiments were conducted using a thermogravimetric analyser (TGA) under CO₂ gasification environment with NiO and CuO. The reduction and re-oxidation of NiO in five repeated cycle operations were performed at 950 °C. However, the same cyclic operation for CuO was performed at 800 °C, as it was observed that at 950 °C CuO could not be re-oxidized to its original state due to sintering, which significantly altered the morphology. The extent of coal combustion and re-oxidation of metal oxides resulted in a 4.4-7.5% weight loss of NiO per cycle. No such weight loss was observed in case of CuO at 800 °C. The high reactivity of CuO was observed as compared to NiO during cyclic operation. The percentage of combustion at the end of the 5th cycle with CuO was 96% as compared to 67% with NiO. Fresh oxide particles and solid residues are characterized using SEM to understand surface morphological changes due to combustion. The energy dispersive X-rays (EDX) helped to get surface elemental information, albeit qualitative, of fresh and used metal oxide particles. The current study, for the first time, has generated practical information on the temperature range, approximate time, and percent combustion that can be achieved while using NiO and CuO as oxygen carriers during CLC with Loy Yang brown coal. Based on these results the ongoing work includes long duration experiments with Loy Yang and other Victorian brown coals.     

Evaluation of reaction mechanism of coal-metal oxide interactions in chemical-looping combustion

The knowledge of reaction mechanism is very important in designing reactors for chemical-looping combustion (CLC) of coal. Recent CLC studies have considered the more technically difficult problem of reactions between abundant solid fuels (i.e. coal and waste streams) and solid metal oxides. A definitive reaction mechanism has not been reported for CLC reaction of solid fuels. It has often been assumed that the solid/solid reaction is slow and therefore requires that reactions be conducted at temperatures high enough to gasify the solid fuel, or decompose the metal oxide. In contrast, data presented in this paper demonstrates that solid/solid reactions can be completed at much lower temperatures, with rates that are technically useful as long as adequate fuel/metal oxide contact is achieved. Density functional theory (DFT) simulations as well as experimental techniques such as thermo-gravimetric analysis (TGA), flow reactor studies, in situ X-ray photo electron spectroscopy (XPS), in situ X-ray diffraction (XRD) and scanning electron microscopy (SEM) are used to evaluate how the proximal interaction between solid phases proceeds. The data indicate that carbon induces the Cu-O bond breaking process to initiate the combustion of carbon at temperatures significantly lower than the spontaneous decomposition temperature of CuO, and the type of reducing medium in the vicinity of the metal oxide influences the temperature at which the oxygen release from the metal oxide takes place. Surface melting of Cu and wetting of carbon may contribute to the solid-solid contacts necessary for the reaction.