基于钾盐修饰Fe基载氧体的化学链燃烧研究

采用典型的钾盐和惰性载体对Fe基载氧体进行修饰,在热重和小型流化床反应器上,采用CO/N2对其还原活性和化学链燃烧特性进行测试,考察了钾盐种类、反应温度对和惰性载体种类的影响。结果表明：钾盐修饰（KCl、K2SO4和K2CO3）能提高载氧体还原反应速率,并以K2CO3效果最好,最大还原反应速率提高约30%,载氧体完全还原时间由50 min缩短到25 min,主要归因于K2CO3修饰促进形成高活性的Fe-K-O化合物及发达的孔隙结构;对于K2CO3修饰Fe基载氧体,SiO2和高岭土载体易与K2CO3发生烧结,造成活性下降,TiO2与载氧体反应生成复杂的化合物,其氧化过程变慢,影响整个进程,而Al2O3载体展现了最好的反应活性,随着反应循环的增加其活性略有下降并趋于稳定,9个循环后CO2捕集效率高达98.0%     

Thermodynamic analysis of H2 production from CaO sorption‐enhanced methane steam reforming thermally coupled with chemical looping combustion as a novel technology

In this novel paper, a technique for hydrogen production route of CaO sorption‐enhanced methane steam reforming (SEMSR) thermally coupled with chemical looping combustion (CLC) was presented (CLC‐SEMSR), which perceived as an improvement of previous methane steam reforming (MSR) thermally coupled with CLC technology (CLC‐MSR). The application of CLC instead of furnace achieves the inherent separation of CO₂ from flue gas without extra energy required. The required heat for the reformer is provided by thermally coupling CLC. The addition of CaO sorbents can capture CO₂ as it is formed from the reformer gas to the solid phase, displacing the normal MSR equilibrium restrictions and obtaining higher purity of H₂. The Aspen Plus was used to simulate this novel process on the basis of thermodynamics. The performances of this system examined included the composition of reformer gas, yield of reformer gas (Y_Rg), methane conversion (α_M), the overall energy efficiency (η), and exergy efficiency (φ) of this process. The effects of the molar ratio of CaO to methane for reforming (Ca/M) in the range of 0–1.2, the molar ratio of methane for combustion to methane for reforming (M(fuel)/M) in the range of 0.1–0.3, and the molar ratio of NiO to methane for reforming (Ni/M) in the range of 0.4–1.2 were investigated. It has been found to be favored by operating under the conditions of Ca/M = 1, M(fuel)/M = 0.2, and Ni/M = 0.8. The most excellent advantage of CLC‐SEMSR was that it could obtain higher purity of H₂ (95%) at lower operating temperature (655 °C), as against H₂ purity of 77.1% at higher temperature (900 °C) in previous CLC‐MSR. In addition, the energy efficiency of this process could reach 83.3% at the optimal conditions. Copyright © 2014 John Wiley & Sons, Ltd.     

Chemical looping steam reforming of ethanol without and with in-situ CO2 capture

Chemical looping steam reforming (CLSR) of ethanol using oxygen carriers (OCs) for hydrogen production has been considered a highly efficient technology. In this study, NiO/MgAl₂O₄ oxygen carriers (OCs) were employed for hydrogen production via CLSR with and without CaO sorbent for in-situ CO₂ removal (sorption enhanced chemical looping steam reforming, SE-CLSR). To find optimal reaction conditions of the CLSR process, including reforming temperatures, the catalyst mass, and the NiO loadings on hydrogen production performances were studied. The results reveal that the optimal temperature of OCs for hydrogen production is 650 °C. In addition, 96% hydrogen selectivity and a 'dead time' (the reduced time of OCs) less than 1 minute is obtained with the 1 g 20NiO/MgAl₂O₄ catalysts. The superior catalytic activity of 20NiO/MgAl₂O₄ is due to the maximal quantity of NiO loadings providing the most Ni active surface centers. High purity hydrogen is successfully produced via CLSR coupling with CaO sorbent in-situ CO₂ removal (SE-CLSR), and the breakthrough time of CaO is about 20 minutes under the condition that space velocity was 1.908 h^?1. Stability CLSR experiments found that the hydrogen production and hydrogen selectivity decreased obviously from 207 mmol to 174 mmol and 95%–85% due to the inevitable OCs sintering and carbon deposition. Finally, stable hydrogen production with the purity of 89%～87% and selectivity of 96%～93% was obtained in the modified stability SE-CLSR experiments.     

Investigation of hydrogen and power co-generation based on direct coal chemical looping systems

This paper evaluates hydrogen and power co-generation based on direct coal chemical looping systems with total decarbonization of the fossil fuel. As an illustrative example, an iron-based chemical looping system was assessed in various plant configurations. The designs generate 300–450 MW net electricity with flexible hydrogen output in the range of 0–200 MW_th (LHV). The capacity of evaluated plant concepts to have a flexible hydrogen output is an important aspect for integration in modern energy conversion systems. The carbon capture rate of evaluated concepts is almost total (>99%). The paper presents in details evaluated plant configurations, operational aspects as well as mass and energy integration issues. For comparison reason, a syngas-based chemical looping concept and Selexol^®-based pre-combustion capture configuration were also presented. Direct coal chemical looping configuration has significant advantages compared with syngas-based looping systems as well as solvent-based carbon capture configurations, the more important being higher energy efficiency, lower (or even zero) oxygen consumption and lower plant complexity. The results showed a clear increase of overall energy efficiency in comparison to the benchmark cases.     

Inhibition of carbon deposition using iron ore modified by K and Cu in chemical looping hydrogen generation

Chemical looping hydrogen generation based on iron is an innovative method to produce high purity hydrogen and capture CO₂ simultaneously. However, carbon deposition of iron ore limits the development. The iron ore modified by K and Cu was employed to suppress the carbon deposition. Experiments were carried out to investigate the effects of the additive amount on carbon deposition and hydrogen purity via carbon release characteristics in a batch fluidized bed. The carbon deposition ratio decreased monotonically with the increasing amount of potassium, but the excess copper loading led to a rise in the ratio of carbon deposition instead. The carbon deposition ratio decreased by up to 84% after adding K and Cu, which is speculated to be closely related to the weight ratio of Fe on the oxygen carrier surfaces. The experimental results at different temperatures demonstrated that 850°C was suitable for the inhibition of carbon deposition and sintering. In addition, the mechanism of inhibition of carbon deposition was proposed in detail and illustrated that it was correlated to the covering of active sites and the reactivity enhancement. Moreover, the carbon deposition ratio of the modified oxygen carrier maintained stable during the cyclic experiments. Therefore, it is feasible to employ the iron ore modified by K and Cu as oxygen carrier to suppress carbon deposition in the chemical looping hydrogen generation.     

Thermo‐economic investigation: an insight tool to analyze NGCC with calcium‐looping process and with chemical‐looping combustion for CO2 capture

In this work, three kinds of natural gas‐based power generation processes for CO₂ capture and storage, that is, natural gas‐combined cycle with pre‐combustion decarburization (NGCC‐PRE), NGCC‐PRE with calcium‐looping process, and NGCC‐PRE with chemical‐looping combustion (NGCC‐CLC), are analyzed by Aspen Plus. The effects of two decisive variables (i.e., steam‐to‐natural gas (S/NG) ratio and oxygen‐to‐natural gas (O/NG) ratio) on the thermodynamic performances of individual process, such as energy and exergy efficiencies, are investigated systematically. Based on simulation outcomes, all the three processes are favored by operating at S/NG = 2.0 and O/NG = 0.65. Furthermore, comparisons of individual system efficiencies and exergy destruction contributor are herein involved. The results show that the highest system efficiencies and lowest exergy destruction are achieved in the NGCC‐CLC process. In addition, capital investment, dynamic payback period, net present value, and internal rate of return are used for deciding the economic feasibility and surely are involved in this work for comparison purpose. Copyright © 2016 John Wiley & Sons, Ltd.     

生物质化学链气化联合燃气轮机发电系统模拟

使用Aspen Plus软件对以Fe_2O_3为载氧体的生物质化学链气化系统进行模拟,分析温度、压力、载氧体与生物质摩尔比、水蒸气与生物质摩尔比等因素对合成气制备的影响;对不同生物质的气化条件进行优化;将气化制得的合成气通入M701F燃气轮机中发电,考察系统的发电效率。结果表明:常压下,不同生物质气化的优化温度均在740℃左右,此时制备的合成气冷煤气效率较高;提高反应压力有利于系统热量自平衡,但合成气的冷煤气效率降低;载氧体与生物质摩尔比的优化值与生物质中氧碳摩尔比呈负相关,且达到优化值时,气化环境中氧碳摩尔比在1.25左右;水蒸气通入气化系统后冷煤气效率可提高15.00%～20.00%,主要原因为H_2的产量显著增加,通入水蒸气后的气化环境的氧碳比在1.4左右时,制备合成气的冷煤气效率较高;系统的发电效率在30.00%～37.00%,高于生物质发电效率。     

Hydrogen and electricity co-production plant integrating steam-iron process and chemical looping combustion

In this paper, steam-iron process (Fe looping) and NiO-based chemical looping combustion (Ni looping) are integrated for hydrogen production with inherent separation of CO₂. An integrated combined cycle based on the Fe and Ni loopings is proposed and modeled using Aspen Plus software. The simulation results show that at Fe-SR 815 °C, Fe-FR 815 °C, Ni-FR 900 °C and Ni-AR 1050 °C without supplementary firing, the co-production plant has a net power efficiency 14.12%, hydrogen efficiency 33.61% and an equivalent efficiency 57.95% without CO₂ emission. At a supplementary firing temperature of 1350 °C, the net power efficiency, hydrogen efficiency and the equivalent efficiency are 27.47%, 23.39% and 70.75%, respectively; the CO₂ emission is 365.36 g/kWh. The plant is attractive because of high-energy conversion efficiency and relatively low CO₂ emission; moreover, the hydrogen/electricity ratio can be varied in response to demand. The influences of iron oxide recycle rate, supplementary firing temperature, inert support addition and other parameters on the system performance are also investigated in the sensitive analyses.     

Hydrogen production from fossil fuels with carbon capture and storage based on chemical looping systems

This paper analyzes innovative processes for producing hydrogen from fossil fuels conversion (natural gas, coal, lignite) based on chemical looping techniques, allowing intrinsic CO₂ capture. This paper evaluates in details the iron-based chemical looping system used for hydrogen production in conjunction with natural gas and syngas produced from coal and lignite gasification. The paper assesses the potential applications of natural gas and syngas chemical looping combustion systems to generate hydrogen. Investigated plant concepts with natural gas and syngas-based chemical looping method produce 500 MW hydrogen (based on lower heating value) covering ancillary power consumption with an almost total decarbonisation rate of the fossil fuels used.The paper presents in details the plant concepts and the methodology used to evaluate the performances using critical design factors like: gasifier feeding system (various fuel transport gases), heat and power integration analysis, potential ways to increase the overall energy efficiency (e.g. steam integration of chemical looping unit into the combined cycle), hydrogen and carbon dioxide quality specifications considering the use of hydrogen in transport (fuel cells) and carbon dioxide storage in geological formation or used for EOR.     

Parametric study of chemical looping combustion for tri‐generation of hydrogen,heat, and electrical power with CO2 capture

In this article, a novel cycle configuration has been studied, termed the extended chemical looping combustion integrated in a steam‐injected gas turbine cycle. The products of this system are hydrogen, heat, and electrical power. Furthermore, the system inherently separates the CO₂ and hydrogen that is produced during the combustion. The core process is an extended chemical looping combustion (exCLC) process which is based on classical chemical looping combustion (CLC). In classical CLC, a solid oxygen carrier circulates between two fluidized bed reactors and transports oxygen from the combustion air to the fuel; thus, the fuel is not mixed with air and an inherent CO₂ separation occurs. In exCLC the oxygen carrier circulates along with a carbon carrier between three fluidized bed reactors, one to oxidize the oxygen carrier, one to produces and separate the hydrogen, and one to regenerate the carbon carrier. The impacts of process parameters, such as flowrates and temperatures have been studied on the efficiencies of producing electrical power, hydrogen, and district heating and on the degree of capturing CO₂. The result shows that this process has the potential to achieve a thermal efficiency of 54% while 96% of the CO₂ is captured and compressed to 110 bar. Copyright © 2005 John Wiley & Sons, Ltd.     

Evaluation of syngas-based chemical looping applications for hydrogen and power co-generation with CCS

This paper evaluates hydrogen and power co-generation based on coal-gasification fitted with an iron-based chemical looping system for carbon capture and storage (CCS). The paper assess in details the whole hydrogen and power co-production chain based on coal gasification. Investigated plant concepts of syngas-based chemical looping generate about 350–450 MW net electricity with a flexible output of 0–200 MW_th hydrogen (based on lower heating value) with an almost total decarbonisation rate of the coal used.     

Bauxite waste with low Fe2O3 and high Na concentration as a promising oxygen carrier in chemical looping combustion

Development of a cost-effective oxygen carrier (OC) for chemical looping combustion (CLC) technology remains an important task to be accomplished. Bauxite waste red mud from the United States has shown promise as an OC, but bauxite waste from China has not been evaluated extensively although huge quantities of it exists. In comparison, the Chinese bauxite waste usually contains low Fe₂O₃ and high Na concentration. Hence, the purpose of this study was to evaluate a typical red mud (from Zibo, China) with low Fe₂O₃/Na mass ratio for its potential as a cost-effective OC during CLC processing. Parametric reactor testing was accomplished with a focus on OC reactivity during CLC, and evaluations were accomplished of morphologies, elemental concentrations, and mechanical strengths before and after reaction testing; special attention was paid to the stability of Na. These results showed that Zibo red mud (a) used as an OC during CLC had satisfactory reactivity particularly after pre-calcination at 1250°C, (b) had high contents of Na that were stable and uniformly distributed during reaction testing and formed NaAlSiO₄ during sample calcination and reaction testing, and (c) showed high mechanical strengths that were similar to those of other oxygen carriers. Considering that huge amounts of this inexpensive Zibo red mud are located within areas near aluminum processing plants, it may become a promising material as an OC for CLC processing.     

Evaluation of hydrogen production with iron-based chemical looping fed by different biomass

In this study, the iron-based chemical looping process driven by various biomasses for hydrogen production purposes is studied and evaluated thermodynamically through energy and exergy approaches. The overall system consists of some key units (combustor, reducers and oxidizer) a torrefier, a drying chamber, an air separation unit, a heat exchanger, and auxiliary units as well. The biomasses considered are first dried and torrified in the drying chamber and sent to reactors to produce hydrogen. The exergy and energy efficiencies of the iron based chemical looping facility are investigated comparatively for performance evaluation. The maximum exergy destruction and entropy production rates are calculated for the torrefaction process as 123.15 MW and 4926 kW/K respectively. Under the steady–state conditions, a total of 8 kg/s hydrogen is produced via chemical looping process. The highest energy efficiency is obtained in the looping of rice husk with 86% while the highest exergy efficiency is obtained in the looping using sugarcane bagasse with 91%, respectively.     

Assessment of calcium-based chemical looping options for gasification power plants

This paper evaluates various calcium-based chemical looping concepts to be applied in Integrated Gasification Combined Cycle (IGCC) plants for decarbonised energy vectors poly-generation (with emphasis on power generation and hydrogen and power co-generation). Two calcium-based chemical looping configurations were analysed. The first concept is based on post-combustion capture using the flue gases resulted from the power block (combined cycle gas turbine). The second concept is based on pre-combustion capture, the calcium-based chemical looping systems being used simultaneous to capture carbon dioxide (by sorbent enhanced water gas shift) and to concentrate the syngas energy in the form of hydrogen-rich gas.     

Chemical looping hydrogen production using activated carbon and carbon black as multi-function carriers

The application of a chemical looping process for methane thermo-catalytic decomposition using activated carbon (AC) as a catalyst has been recognized as an advanced process for continuous high-purity H₂ production in the carbon constrained world due to its low CO₂ formation. AC is able to provide reasonable kinetics, however, it suffers from fast deactivation. Deep regeneration of spent AC catalyst using steam is able to eliminate catalytic deactivation, and this process sacrifices part of the catalyst. The catalytic performance of AC and carbon black (CB) catalysts exhibit opposite deactivation behavior with time. AC provides a better activity, but it deactivates quickly. Though the catalytic activity of CB is low, its activity not only can be maintained, but also shows an increase during the test. Our approach for AC modification was inspired by analyzing the factors that lead to the different performance. Results indicate that the catalytic performance of AC and CB exhibit opposite deactivation behavior with time, and the deposited carbon on their surfaces are in different shape, orientation, and chemical structure. The outward growing cone-like graphene layers and tubular-shaped nanostructures are key factors that help maintain the catalyst's porosity and activity; and the cause of different deposit carbon may be attributed to the irregular, cross-linking graphene layers of AC and the spherical bent graphene layers of CB.     

The calcium looping cycle for large-scale CO2 capture

The reversible reaction between CaO and CO₂ is an extremely promising method of removing CO₂ from the exhaust of a power station, generating a pure stream of CO₂ ready for geological sequestration. The technology has attracted a great deal of attention recently, owing to a number of its advantages: the relatively small efficiency penalty which it imposes upon a power station (estimated at 6–8 percentage points, including compression of the CO₂); its potential use in large-scale circulating fluidised beds (a mature technology, as opposed to the vastly upscaled solvent scrubbing towers which would be required for amine scrubbing); its excellent opportunity for integration with cement manufacture (potentially decarbonising both industries) and its extremely cheap sorbent (crushed limestone).     

Metal modified hexaaluminates for syngas generation and CO2 utilization via chemical looping

Chemical looping CH₄CO₂ reforming (CLDR) is an emerging technology for the generation of Fischer-Tropsch ready syngas and CO₂ utilization, which is strongly dependent upon the improvement in the design of efficient oxygen carriers (OCs). In this present work, different metal additives (Si, Zr and Ce ions) were introduced into Fe-based hexaaluminates and used OCs for CLDR. The microstructure and reactivity of BaFe_2.8M_0.2Al₉O₁₉ (M = Fe, Si, Zr, and Ce) OCs were found greatly influenced by the metal additives and CH₄/CO₂ redox treatment. Pure Fe and Ce doped OCs showed the co-existence of both β-Al₂O₃ and MP hexaaluminate phases, while the introduction of Si and Zr in the hexaaluminate structure led to the phase transformation from β-Al₂O₃ into MP. During the CH₄/CO₂ redox process, large amounts of Fe species in both BaFe_2.8Si_0.2Al₉O₁₉ and BaFe_2.8Zr_0.2Al₉O₁₉ OCs were gradually stabilized in sintering FeAl₂O₄ with low oxygen-storage capacity, which resulted in low CH₄ reactivity and weak cyclic stability. However, Ce-doped BaFe_2.8Ce_0.2Al₉O₁₉ OC showed good reactivity and stability during the 10 redox cycles with CH₄ conversion of 93%, H₂/CO ratio of ∼2, high syngas yield of 2.2 mmol/g, and high CO₂ activation ability of 0.95 mmol/g, which was associated with the preservation of hexaaluminate main phase, the formation of CeFe_xAl_1-xO₃ and the abundant oxygen vacancies.     

Characteristics of biomass gasification using chemical looping with iron ore as an oxygen carrier

Experiments regarding to biomass gasification using chemical looping (BGCL) were carried out in a fluidized bed reactor under argon atmosphere. Iron ore (natural hematite) was used as an oxygen carrier in the study. Similar to steam, a performance of oxygen carrier which provided oxygen source for biomass gasification by acting as a gasifying medium was found. An optimum Fe₂O₃/C molar ratio of 0.23 was determined with the aim of obtaining maximum gas yield of 1.06 Nm³/kg and gasification efficiency of 83.31%. The oxygen carrier was gradually deactivated with reduction time increasing, inhibiting the carbon and hydrogen in biomass from being converted into synthesis gas. The fraction of Fe²⁺ increased from 0 to 47.12% after reduction time of 45 min, which implied that active lattice oxygen of 49.75% was consumed. The oxygen carrier of fresh and reacted was analyzed by a series of characterization methods, such as X-ray diffraction (XRD), Scanning electron microscopy (SEM), and Energy-dispersive X-ray spectroscopy (EDX).     

Thermodynamic analysis of a membrane-assisted chemical looping reforming reactor concept for combined H2 production and CO2 capture

There is great consensus that hydrogen will become an important energy carrier in the future. Currently, hydrogen is mainly produced by steam reforming of natural gas/methane on large industrial scale or by electrolysis of water when high-purity hydrogen is needed for small-scale hydrogen plants. Although the conventional steam reforming process is currently the most economical process for hydrogen production, the global energy and carbon efficiency of this process is still relatively low and an improvement of the process is key for further implementation of hydrogen as a fuel source. Different approaches for more efficient hydrogen production with integrated CO₂ capture have been discussed in literature: Chemical Looping Combustion (CLC) or Chemical Looping Reforming (CLR) and membrane reactors have been proposed as more efficient alternative reactor concepts relative to the conventional steam reforming process. However, these systems still present some drawbacks. In the present work a novel hybrid reactor concept that combines the CLR technology with a membrane reactor system is presented, discussed and compared with several other novel technologies. Thermodynamic studies for the new reactor concept, referred to as Membrane-Assisted Chemical Looping Reforming (MA-CLR), have been carried out to determine the hydrogen recovery, methane conversion as well as global efficiency under different operating conditions, which is shown to compare quite favorably to other novel technologies for H₂ production with CO₂ capture.