串行流化床内气体串混特性

串行流化床反应器间的气体串混是影响化学链燃烧过程的关键因素之一,采用串行流化床冷态试验装置,通过改变各反应器入口流化数,考察反应器间的串混量及串混率。反应器之间的气体串混路径可能有空气反应器和燃料反应器之间的气体串混、燃料反应器内气体向旋风分离器串混、隔离器气体在空气反应器和燃料反应器内的分布。结果表明,在空气反应器和燃料反应器之间加设隔离器能有效阻止两个反应器之间发生气体串混;燃料反应器内少许气体通过反应器内料腿向上串混到旋风分离器排气中,串混率约为2%,这使得该串行流化床化学链燃烧的理论碳捕集效率可以达到98%;燃料反应器流化风速对隔离器内气体在两个反应器的分布影响较小,采用水蒸气流化可避免隔离器气体向空气反应器和燃料反应器内串混所带来的影响。     

Fluid dynamic simulation in a chemical looping combustion with two interconnected fluidized beds

Flow behavior of gas and particles is simulated in a 2-D chemical-looping combustion (CLC) process with two interconnected fluidized beds. A Eulerian continuum two-fluid model is applied for both the gas phase and the solid phase. Gas turbulence is modeled by using a k-ε turbulent model. The kinetic stress is modeled using the kinetic theory of granular flow, while the friction stress is from the combination of the normal frictional stress model proposed by Johnson and Jackson (1987) and the frictional shear viscosity model proposed by Schaeffer (1987) to account for strain rate fluctuations and slow relaxation of the assembly to the yield surface. Instantaneous and local velocity, concentration of particles and granular temperature are obtained. Predicted time-averaged particle concentrations and velocities reflect the classical core-annular flow structure in the air reactor. Flow behavior of bubbles is predicted in the fuel reactor and pot-seal. Computed leakage qualitatively agrees with experimental data in the fuel reactor and pot-seal.     

基于3kW塔式串行流化床差异燃料的化学链燃烧解析

化学链燃烧反应器具有广泛的燃料适应性，可同时兼顾气、液、固多类型燃料的运行。本文依托耦合内构件的3kW塔式串行流化床反应器，分别开展异丙醇、污泥以及煤炭的化学链燃烧实验，探究燃料物化属性对化学链燃烧过程与反应器运行的影响，揭示面向目标燃料的反应器针对性设计、载氧体性能选择与流化操作策略，助力形成指向性强、碳捕集效率高与操作灵活的化学链燃烧技术。面对碳化程度低、有机质含量高的固体燃料，焦炭气化速率已非强化重点，如污泥在3kW塔式反应器910℃与150s停留时间内，可实现大于99%的CO₂捕集效率，化学链燃烧反应器应侧重改善可燃气体转化与旋风分离器对轻质焦炭颗粒的捕捉。当采用异丙醇等高CH₄含量的燃料时，Fe基矿石载氧体的反应性能不足，3kW反应器的额外耗氧率高达10%～19%，其中未燃尽CH₄对额外耗氧率的贡献占比超80%。化学链燃烧反应器需依据热解反应气的物化特性，选择或掺混功能性载氧体，以针对性改善气固转化。在煤等高碳化燃料的化学链燃烧过程中，焦炭气化是反应的限制性步骤，简化循环结构的3kW塔式反应器停留时间不足，仅可...     

Particle characterisation in chemical looping combustion

In a chemical looping combustion process, as the oxygen carrier circulates the system, it is subjected to morphological and compositional changes such as sintering, attrition and reaction between metal oxides and fuels. These changes may cause the deactivation of the oxygen carrier to decrease over time. This research work is carried out to investigate and characterise the iron oxide and copper oxide particles used in a chemical looping combustion system after 20 reduction–oxidation cycles with 5 different fuels, (i.e. Hambach lignite coal, Hambach lignite char, activated carbon, Taldinski bituminous coal and US bituminous coal). Oxygen carriers used in this study were subjected to analyses with X-ray diffraction (XRD), inductive coupled plasma mass spectrometry (ICP-MS), scanning electron microscope (SEM) and BET surface area and full isotherm analysis.XRD analysis on these particles showed that the reduced particles were reoxidised back to their original form with trace amounts of impurities such as silicon dioxide (SiO₂) on the iron oxide particles whereas similar impurities plus copper complexes such as copper aluminate were detected on the copper oxide particles. ICP-MS analysis on these particles revealed that the concentration of the core metal elements (iron, copper and alumina) decreased after 20 reaction cycles which in turn decreased the total concentration of the metal elements in the particles. BET surface area analysis on these particles indicated that the total surface area of these particles decreased by more than 50% of their original values. Full isotherm analysis on the copper oxide particles showed that the total pore volume of the particles decreased after 20 reaction cycles even though the pore sizes of the particles increased slightly. SEM analyses showed the iron oxide particles underwent severe attrition whereas the copper oxide particles showed signs of agglomeration due to the high operating temperature.     

Oxygen carriers for chemical looping combustion of solid fuels

A thermal analyzer-differential scanning calorimeter-mass spectrometer (TG-DSC-MS) was used to study oxygen carriers (OC) for their potential use for the application of chemical looping combustion (CLC) to solid fuels. Reaction rates, changes in reaction rates with repeated oxidation-reductions, exothermic heats during oxidation, and the effect of changing reduction gas compositions were studied. Oxidation rates were greater than reduction rates and reaction rates were reproducible through multiple oxidation-reduction cycles except where agglomeration occurred with powders. Iron oxide (Fe₂O₃ powder) and iron-based catalysts were found suitable for CLC of solid fuels having rapid reduction rates which increased with higher reducing gas concentrations. Fe₂O₃ powder was used to oxidize a high carbon coal char in an inert gas removing 88% of the carbon from the char. Other properties such as cost and durability indicated iron oxide OCs potential use for CLC of solid fuels.     

Characteristics of the NiO/hexaaluminate for chemical looping combustion

Chemical looping combustion technology has drawn much attention due to advantages such as no NO_x formation and simple CO₂ separation. The thermally stable oxygen carrier in the redox cycle at 1,000–1,400 K is necessary for the chemical lopping combustion. The thermally stable hexaaluminate can be a good candidate for the support material of the oxygen carrier. In this work, NiO/hexaaluminate has been developed in order to apply for chemical looping combustion. From the X-ray diffraction patterns, it was found that most of Ni existed in the form of NiO and NiAl₂O₄ in the obtained sample. The NiO supported on NiAl₂O₄ showed good characteristics in the reduction and oxidation reaction. The present work suggested that NiO/hexaaluminate is a promising material as oxygen carrier for the chemical looping combustion.     

A comparative study of reaction models applied for chemical looping combustion

Kinetic models applicable for chemical looping combustion in conjunction with relevant experimental studies investigating carrier material kinetics are reviewed. Based on a selection of experimental investigations from literature, where both data at different temperature levels and different gaseous reactant compositions are provided, a broad range of commonly used kinetic models is reviewed. The reaction rate as function of the degree of conversion is addressed which is important if kinetic models are applied within simulations on chemical looping combustion like particle based methods, multiphase CFD-approaches or macroscopic models. Results obtained indicate that most of the models tend to fail towards higher degrees of conversion where reaction rate is rapidly declining. As an alternative to commonly used models, several empirical models are proposed for the conversion rate. The new models perform well and might lead to improved large scale simulations.     

煤化学链燃烧载氧体研究进展

煤的化学链燃烧是清洁煤燃烧的重要技术之一。化学链中载氧体的使用可以避免煤和空气直接接触,从而避免氮氧化物等污染物的产生并提高能量转化效率。一般来说,煤的化学链燃烧有2种反应途径:煤气化化学链燃烧和氧解耦化学链燃烧;不同反应途径将极大影响载氧体组分以及结构设计。详细论述了2015-2020年煤化学链燃烧中固态金属载氧体的研究进展,包括铁基、锰基、铜基、镍基、硫酸钙以及其他复合金属载氧体。总结了不同金属载氧体的优缺点、反应路径、气-固和固-固反应机理、金属与载体的相互作用以及载氧体失活原理。铁基载氧体被广泛应用于气化化学链燃烧中,但单一铁基载氧体的反应速率较低。适量添加碱金属或碱土金属可以提升载氧体的反应活性。锰基载氧体在化学链燃烧中具有两面性:一方面可以在高温缺氧气氛中释放气态氧,另一方面也可以与还原性气体发生气-固反应。通过使用惰性载体以及碱金属添加剂可以提高锰基载氧体的机械强度和氧解耦能力。含铜载氧体具有出色的氧解耦能力和反应活性而被广泛关注,然而铜及其氧化物低熔点所带来的金属聚集导致载氧体的失活问题亟需克服。研究发现使用铁、锰和铜矿石制得的载氧体具有良好的反应性能。硫酸钙载氧体具有较好的反应活性,但煤的化学链燃烧时潜在的二氧化硫和硫化氢副产物需要引起重视。镍基载氧体虽然在煤的化学链燃烧中反应性能较好,但硫毒化、成本较高和环保性能不佳等缺点导致近年来镍基载氧体的研究较少。新型双金属或多金属载氧体可以同时结合2种金属的反应特性,从而显著提高载氧体的整体反应活性。基于载氧体的研究现状,对未来的发展方向提出了4点建议:结合2种煤的化学链燃烧机理设计新型氧解耦辅助化学链燃烧载氧体;发展新型材料和金属组分的载氧体;利用冶金工业废料制得载氧体;开发新型结构的载氧体。     

Hydrodynamic simulation of fuel-reactor in chemical looping combustion process

A multiphase CFD-based model with gas-solid hydrodynamics and chemical reactions is used to model flow behavior of gas and particles in the fuel reactor of chemical looping combustion process. The granular kinetic theory model is used to model the interaction of particle collisions. The friction stress of particles is considered to account for strain rate fluctuations and slow relaxation of the assembly to the yield surface. The reaction kinetics model of the fuel reactor is presented. The instantaneous mass fractions of both reactant and products are predicted, and the time averaged distributions are calculated in the fuel reactor. Simulated fuel reactor flows reveal a high weight fraction of unburned methane fuel in the flue gas along with CO₂ and H₂O. This behavior implies high fuel loss at the exit of the reactor and indicates the necessity to increase the residence time and improve mixing in the fuel reactor using circulating fluidized bed technology.     

无烟煤化学链燃烧过程燃料氮转化释放特性

基于赤铁矿石载氧体,在小型单流化床反应器上,开展煤挥发分和焦炭的化学链燃烧研究,探讨挥发分氮和焦氮在化学链燃烧过程中的转化特性。研究表明:燃料氮释放的中间产物HCN和NH₃与铁矿石载氧体具有较高的化学反应亲和性,易于被载氧体氧化生成N₂和NO。淮北无烟煤挥发分氮转化过程中,NO是唯一的氮氧化物,反应器出口中间产物NH₃的释放份额略高于HCN。在煤焦化学链燃烧还原过程中,部分燃料氮释放的中间产物HCN和NH₃被铁矿石氧化导致少量NO的生成,还原过程中无N₂O的释放;较高的还原反应温度加速了NO的生成。减少进入载氧体氧化再生过程的焦炭量可减少空气反应器NO和N₂O的生成。     

化学链燃烧耦合甲烷重整制液体燃料工艺

为探讨能量的高效利用,提出了化学链燃烧耦合甲烷重整制液体燃料工艺,并利用Aspen Plus软件进行工艺模拟。研究了重整单元进料甲烷/二氧化碳/水蒸气的摩尔比(M/C/S)、反应温度(T)以及费托合成气相循环比(R)对CO2转化率、合成气氢碳比、能量效率、费托合成火用损等系统性能指标的影响,并以能量效率最高为目标,对系统参数进行了优化。研究表明,当M/C/S=3/1/2、T=800℃、R=0. 9时,生成的合成气氢碳比为2. 1,系统的总能量效率和液体燃料生产效率最高,分别为57. 0%和50. 0%,系统能源节约率为9. 0%。     

化学链燃烧耦合甲烷重整制液体燃料工艺

为探讨能量的高效利用,提出了化学链燃烧耦合甲烷重整制液体燃料工艺,并利用Aspen Plus软件进行工艺模拟。研究了重整单元进料甲烷/二氧化碳/水蒸气的摩尔比(M/C/S)、反应温度(T)以及费托合成气相循环比(R)对CO2转化率、合成气氢碳比、能量效率、费托合成火用损等系统性能指标的影响,并以能量效率最高为目标,对系统参数进行了优化。研究表明,当M/C/S=3/1/2、T=800℃、R=0. 9时,生成的合成气氢碳比为2. 1,系统的总能量效率和液体燃料生产效率最高,分别为57. 0%和50. 0%,系统能源节约率为9. 0%。     

Transport phenomena in packed bed reactor technology for chemical looping combustion

Chemical looping combustion (CLC) is potentially the technology best suited for capturing CO₂ at low cost and efficiently providing a low energy option for the separation of CO₂ from flue gases. The process consists in the cyclic reduction and oxidation of metal oxide particles, which act as oxygen carriers. The particles are exchanged between two reactors, usually a circulating fluidised bed and a bubbling bed reactor, where the oxidation and reduction reactions occur, respectively. Noorman et al. (2007) explored a dynamically operated packed bed for CLC technology. Successive work undertaken by the same group (Noorman et al., 2009) has shown the feasibility of the concept, and expressions for the mass and heat front velocities were determined. In this work, the oxidation of the packed bed reactor is analysed as a problem presenting discontinuities which are sustained by transport processes and are indistinguishable from phase interfaces. Travelling mass and heat fronts arise as a consequence of the reaction kinetics; a specific problem is analysed, where the oxidation is modelled similarly to an adsorption problem and the mass front velocity is calculated for some limiting transport conditions. It is shown that the mass front velocity arises naturally when the Kotchine's procedure (Astarita and Ocone, 2002) is applied to the system. An interesting feature of the analysis presented here is that some general results can be obtained without making any specific assumption about the kinetics. The results obtained are indeed amenable to be extended to other processes where the reacting material is a bed of solid particles. The treatment presented can be implemented when small perturbations occur in the bed, thus giving useful information on predicting whether the unwanted changes in the process conditions are sustained or die out.     

Petroleum coke conversion behavior in catalyst-assisted chemical looping combustion

Efficiently using petroleum coke as fuel and reducing carbon emission meanwhile have become attractive in oil processing industry. The paper is focused on the application of Chemical Looping Combustion (CLC) with petroleum coke, with the purpose of investigating its combustion performance and effects of potassium. Some experiments were performed in a laboratory scale fluidized bed facility with a natural manganese-based oxygen carrier. Experimental results indicated that the coke conversion is very sensitive to reaction temperature. The present natural manganese-based oxygen carrier decorated by K has little effect on the improvement of coke conversion. XRD, SEM-EDX, and H₂-TPR were adopted to characterize the reacted oxygen carrier samples. After being decorated by K, the oxygen carrier's capacity of transferring oxygen was decreased. A calcination temperature above the melting point of K₂CO₃ (891 °C) shows better oxygen transfer reactivity in comparison to the one calcined at a lower temperature. The natural oxygen carrier used in the work has a high content of Si, which can easily react with K to form K(FeSi₂O₆). Further, irrespective of reaction temperature, the coke conversion can be significantly enhanced by decorating the coke with K, with a demonstration of remarkably shorter reaction time, faster average coke gasification rate and higher average carbon conversion rate.     

Petroleum coke conversion behavior in catalyst-assisted chemical looping combustion

Efficiently using petroleum coke as fuel and reducing carbon emission meanwhile have become attractive in oil processing industry. The paper is focused on the application of Chemical Looping Combustion (CLC) with petroleum coke, with the purpose of investigating its combustion performance and effects of potassium. Some experiments were performed in a laboratory scale fluidized bed facility with a natural manganese-based oxygen carrier. Experimental results indicated that the coke conversion is very sensitive to reaction temperature. The present natural manganese-based oxygen carrier decorated by K has little effect on the improvement of coke conversion. XRD, SEM–EDX, and H₂-TPR were adopted to characterize the reacted oxygen carrier samples. After being decorated by K, the oxygen carrier's capacity of transferring oxygen was decreased. A calcination temperature above the melting point of K₂CO₃ (891 °C) shows better oxygen transfer reactivity in comparison to the one calcined at a lower temperature. The natural oxygen carrier used in the work has a high content of Si, which can easily react with K to form K(FeSi₂O₆). Further, irrespective of reaction temperature, the coke conversion can be significantly enhanced by decorating the coke with K, with a demonstration of remarkably shorter reaction time, faster average coke gasification rate and higher average carbon conversion rate.     

10 kWth级串行流化床中木屑化学链燃烧试验

设计并建立了10 kW_th级串行流化床化学链燃烧反应器系统,以NiO/Al₂O₃为载氧体,在该系统上进行生物质（松木木屑）化学链燃烧分离CO₂的试验研究,探讨了燃料反应器温度T、水蒸气/生物质比率S/B对两个反应器（空气反应器和燃料反应器）气体产物组成以及燃烧效率的影响。试验结果表明,燃料反应器温度是影响生物质化学链燃烧过程的重要因素,随着温度的升高,燃料反应器气体产物中CO₂浓度不断上升,CH4浓度显著降低,CO浓度先升高而后迅速下降;较高的反应器温度有助于燃烧效率的提高。随着S/B的增加,燃料反应器气体产物中CO和CH₄浓度均会增大,CO₂浓度以及燃烧效率有所降低。在100 h的连续试验过程中,采用共沉淀法制备的NiO/Al₂O₃载氧体展现出良好的氧化-还原性能和较强的持续循环能力,是生物质化学链燃烧理想的载氧体。     

Migration and emissions of selenium during chemical looping combustion of coal

Selenium is one of the most volatile toxic elements in coal, and its emissions must be strictly controlled. Chemical looping combustion (CLC) is a clean and efficient technology for coal. Herein, the iron-based oxygen carrier (OC) was used as an adsorbent to study the migration and emissions of selenium during the CLC of coal. Due to the oxidation and adsorption of selenium by iron-based OC, most of the selenium was retained in OC or distributed in the CO₂ stream. The proportion of gaseous selenium released into the atmosphere was less than 10%—significantly lower than that from the traditional combustion process of coal, which had a value of 91.79%. The presence of OC increased the distribution phase of selenium, promoted the conversion of gaseous selenium to solid selenium, and reduced selenium emissions in flue gas. During CLC of coal, the fuel reactor (FR) temperature and the number of OC re-oxidation cycles played an important role in the emissions and retention of selenium. The increasing FR temperature increased the gaseous selenium in the CO₂ stream, reduced the particulate selenium absorbed by OC, and reduced the selenium emissions in the atmosphere. After 10 continuous CLC cycles, the selenium concentration in OC increased from 0.889 to 8.20 mg kg⁻¹. The continuous cycling of CLC could realize the enrichment of selenium from coal to OC. Furthermore, the migration and transformation mechanism of selenium during CLC was deduced by experiments and thermodynamic simulation. This research provides a suitable reference for reducing selenium emissions and developing CLC technology.     

Experimental and mechanistic study on chemical looping combustion of caking coal

Under high-temperature batch fluidized bed conditions and by employing Juye coal as the raw material,the present study determined the effects of the bed material,temperature,OC/C ratio,steam flow and oxygen carrier cycle on the chemical looping combustion of coal.In addition,the variations taking place in the surface functional groups of coal under different reaction times were investigated,and the varia-tions achieved by the gas released under the pyrolysis and combustion of Juye coal were analyzed.As revealed from the results,the carbon conversion ratio and rate were elevated significantly,and the vol-ume fraction of the outlet CO2 remained more than 92％ under the oxygen carriers.The optimized reac-tion conditions to achieve the chemical looping combustion of Juye coal consisted of a temperature of 900℃,an OC/C ratio of 2,as well as a steam flow rate of 0.5 g·min-1.When the coal was undergoing the chemical looping combustion,volatiles primarily originated from the pyrolysis of aliphatic-CH3 and-CH2,and CO and H2 were largely generated from the gasification of aromatic carbon.In the CLC process,H2O and CO2 began to separate out at 270 ℃,CH4 and tar began to precipitate at 370 ℃,and the amount of CO2 was continuously elevated with the rise of the temperature.     

Enrichment of iron from bauxite waste in chemical looping combustion

This work reports a method and findings related to the enrichment of iron from bauxite waste (red mud) using chemical looping combustion (CLC). According to the results from X-ray Diffraction, X-ray Fluorescence, and scanning electron microscope–energy-dispersive X-ray spectroscopy, uniformly distributed iron in the red mud particles migrated outward to the surface during the 148 redox cycles in a bubbling fluidized bed reactor, in which the size-reduced iron-oxide particles due to attrition are concentrated in filters. The concentrations of iron oxide in raw particles and attrition fines are 43 wt.% and 83–87 wt.%, respectively. Since the attrition in CLC is inevitable, this recycled iron oxide can be a valuable by-product to compensate for the cost of CLC, whereas the bed materials continue to participate in the CLC process. Moreover, the abundant bauxite waste can be processed in an eco-friendly manner for integrated power generation, carbon capture, and iron recovery by the proposed strategy in this work.     

含氮模型化合物用于化学链燃烧的氮氧化物释放特性

以谷氨酸、甘氨酸和苯丙氨酸作为生物质的含氮模型化合物,进行化学链燃烧实验,主要考察了反应温度、氨基酸种类、碱金属钾元素等对化学链燃烧还原反应过程中氮氧化物释放特性的影响。结果显示,挥发分氮的释放迅速,温度的升高有利于NO和NO₂的生成,N₂O的生成会出现波动。模型化合物的氮含量越高,可能越不利于氮向氮氧化物的转化。钾元素对苯丙氨酸的化学链燃烧过程中NO的释放抑制作用较强,而对其他氨基酸化学链燃烧过程中氮氧化物释放的影响则不太显著。