The reaction of NiO/NiAl2O4 particles with alternating methane and oxygen

The reduction and oxidation behaviour of oxygen carrier particles of NiO and NiAl₂O₄ has been investigated in a fluidized bed reactor as well as a thermogravimetric analyzer (TGA). The particles showed high reactivity and gas yield to CO₂ with methane in the temperature interval 750–950°C. In the fluidized bed the yield to CO₂ was between 90 and 99% using bed masses corresponding to 16–57 kg/MW_fuel. Complementary experiments in a TGA at 750 and 950°C showed a clear reaction of the NiAl₂O₄ with CH₄ at the higher temperature. There was methane released from the reactor at high degrees of solid oxidation, which is likely associated with the lack of Ni‐sites on the particles which can reform the methane. There was some carbon formation during the reduction, although the amount was minor when the gas yield to carbon dioxide and degree of oxidation of the solid was high. A simple reactor model using kinetic data from a previous study predicted the gas yield during the reduction in the fluidized bed experiments with reasonable accuracy. The oxygen carrier system investigated in this work shows high promise for use in a real CLC system, provided that the particle manufacturing process can be scaled up with reasonable cost.     

Comparison of iron-, nickel-, copper- and manganese-based oxygen carriers for chemical-looping combustion

For combustion with CO₂ capture, chemical-looping combustion (CLC) with inherent separation of CO₂ is a promising technology. Two interconnected fluidized beds are used as reactors. In the fuel reactor, a gaseous fuel is oxidized by an oxygen carrier, e.g. metal oxide particles, producing carbon dioxide and water. The reduced oxygen carrier is then transported to the air reactor, where it is oxidized with air back to its original form before it is returned to the fuel reactor. The feasibility of using oxygen carrier based on oxides of iron, nickel, copper and manganese was investigated. Oxygen carrier particles were produced by freeze granulation. They were sintered at 1300 °C for 4 h and sieved to a size range of 125-180 μm. The reactivity of the oxygen carriers was evaluated in a laboratory fluidized bed reactor, simulating a CLC system by exposing the sample to alternating reducing and oxidizing conditions at 950 °C for all carriers except copper, which was tested at 850 °C. Oxygen carriers based on nickel, copper and iron showed high reactivity, enough to be feasible for a suggested CLC system. However, copper oxide particles agglomerated and may not be suitable as an oxygen carrier. Samples of the iron oxide with aluminium oxide showed signs of agglomeration. Nickel oxide showed the highest reduction rate, but displayed limited strength. The reactivity indicates a needed bed mass in the fuel reactor of about 80-330 kg/MW_th and a needed recirculation flow of oxygen carrier of 4-8 kg/s, MW_th.     

The use of iron oxide as oxygen carrier in a chemical-looping reactor

Chemical-looping combustion (CLC) is a method for the combustion of fuel gas with inherent separation of carbon dioxide. This technique involves the use of two interconnected reactors, an air reactor and a fuel reactor. The oxygen demanded in the fuel combustion is supplied by a solid oxygen carrier, which circulates between both reactors. Fuel gas and air are never mixed and pure CO₂ can be obtained from the flue gas exit. This paper presents the results from the use of an iron-based oxygen-carrier in a continuously operating laboratory CLC unit, consisting of two interconnected fluidized beds. Natural gas or syngas was used as fuel, and the thermal power was between 100 and 300 W. Tests were performed at four temperatures: 1073, 1123, 1173 and 1223 K. The prototype was successfully operated for all tests and stable conditions were maintained during the combustion. The same particles were used during 60 h of hot fluidization conditions, whereof 40 h with combustion. The combustion efficiency of syngas was high, about 99% for all experimental conditions. However, in the combustion tests with natural gas, there was unconverted methane in the exit flue gases. Higher temperature and lower fuel flows increase the combustion efficiency, which ranged between 70% and 94% at 1123 K. No signs of agglomeration or mass loss were detected, and the crushing strength of the oxygen carrier particles did not change significantly. Complementary experiments in a batch fluidized bed were made to compare the reactivity of the oxygen carrier particles before and after the 40 h of operation, but the reactivity of the particles was not affected significantly.     

Reduction and oxidation kinetics of Mn3O4/Mg-ZrO2 oxygen carrier particles for chemical-looping combustion

The kinetics of reduction with methane and oxidation with oxygen of Mn₃O₄ supported on Mg-ZrO₂ prepared by freeze granulation has been investigated. The reactivity experiments were performed in a thermogravimetric analyzer (TGA) using different reacting gas concentrations and temperatures in the range of 1073-1223 K. The oxygen carrier particles showed high reactivity during both reduction and oxidation at all investigated temperatures. An empirical reaction model, which assumes a linear relation between time and conversion, was used to determine the kinetic parameters for reduction and oxidation, with chemical reaction being the main resistance to the reaction. The order of reaction found was 1 with respect to CH₄ and 0.65 with respect to O₂. The activation energy for the reduction reaction was 119 and for the oxidation reaction. The reactivity data and kinetic parameters were used to estimate the solid inventory in the air and fuel reactor of a CLC system. The optimum solid inventory obtained was at a value of ΔX_s=0.4. At these conditions, the recirculation rate of oxygen carrier between air and fuel reactor was per MW of fuel, which could be accomplished in an industrial reactor. The high reactivity of the Mn₃O₄/Mg-ZrO₂ with both methane and oxygen showed that this is a very promising oxygen carrier for CLC.     

Fe2O3 on Ce‐, Ca‐, or Mg‐stabilized ZrO2 as oxygen carrier for chemical‐looping combustion using NiO as additive

Oxygen‐carrier particles for chemical‐looping combustion have been manufactured by freeze granulation. The particles consisted of 60 wt % Fe₂O₃ as active phase and 40 wt % stabilized ZrO₂ as support material. Ce, Ca, or Mg was used to stabilize the ZrO₂. The hardness and porosity of the particles were altered by varying the sintering temperature. The oxygen carriers were examined by redox experiments in a batch fluidized‐bed reactor at 800–950°C, using CH₄ as fuel. The experiments showed good reactivity between the particles and CH₄. NiO was used as an additive and was found to reduce the fraction of unconverted CH₄ with up to 80%. The combustion efficiency was 95.9% at best and was achieved using 57 kg oxygen carrier per MW fuel. Most produced oxygen carriers appear to have been decently stable, but using Ca as stabilizer resulting in uneven results. Further, particles sintered at high temperatures had a tendency to defluidize. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Reactivity of a NiO/Al2O3 oxygen carrier prepared by impregnation for chemical-looping combustion

The reactivity of a Ni-based oxygen carrier prepared by hot incipient wetness impregnation (HIWI) on α-Al₂O₃ with a NiO content of 18 wt% was studied in this work. Pulse experiments with the reduction period divided into 4-s pulses were performed in a fluidized bed reactor at 1223 K using CH₄ as fuel. The number of pulses was between 2 and 12. Information about the gaseous product distribution and secondary reactions during the reduction was obtained. In addition to the direct reaction of the combustible gas with the oxygen carrier, CH₄ steam reforming also had a significant role in the process, forming H₂ and CO. This reaction was catalyzed by metallic Ni in the oxygen carrier and H₂ and CO acted as intermediate products of the combustion. No evidence of carbon deposition was found in any case. Redox cycles were also carried out in a thermogravimetric analyzer (TGA) with H₂ as fuel. Both tests showed that there was a relation between the solid conversion reached during the reduction and the relative amount of NiO and NiAl₂O₄ in the oxygen carrier. When solid conversion increased, the NiO content also increased, and consequently NiAl₂O₄ decreased. Approximately 20% of the reduced nickel was oxidized to NiAl₂O₄, regardless ΔX_s. NiAl₂O₄ was also an active compound for the combustion reaction, but with lower reactivity than NiO. Further, the consequences of these results with respect to the design of a CLC system were investigated. When formation of NiAl₂O₄ occurred, the average reactivity in the fuel reactor decreased. Therefore, the presence of both NiO and NiAl₂O₄ phases must be considered for the design of a CLC facility.     

Chemical-looping with oxygen uncoupling using CuO/ZrO2 with petroleum coke

Oxygen carrier particles of CuO/ZrO₂ were reacted with petroleum coke using chemical-looping with oxygen uncoupling (CLOU). The fuel was burnt in gas-phase oxygen released from the oxygen carrier particles during the fuel oxidation. The particles were then regenerated in 5-21% oxygen. In this process, the carbon dioxide from the combustion is inherently separated from the rest of the flue gases without the need for an energy intensive air separation unit. Copper oxide has thermodynamic characteristics that make it suitable as an oxygen carrier in CLOU. Particles were prepared by freeze granulation and were exposed cyclically with petroleum coke and oxygen in a laboratory fluidized bed reactor of quartz. The reaction temperature and oxygen concentration during the oxidation were varied. The average conversion rate of petroleum coke was a function of temperature and varied between 0.5%/s and 5%/s in the set-point temperature interval 885-985 °C. The conversion rate is considerably higher than rates obtained with the same fuel using iron-based oxygen-carrier in chemical-looping combustion. As for the regeneration with oxygen, the reduced particles reacted at low oxygen concentrations, with a considerable part of the reaction occurring near the thermodynamic equilibrium.     

Batch testing of solid fuels with ilmenite in a 10 kWth chemical-looping combustor

Batch experiments were conducted in a 10 kW_th chemical-looping combustor for solid fuels using ilmenite, an iron titanium oxide, as the oxygen carrier with two solid fuels: a petroleum coke from Mexico and a bituminous coal from South Africa. The purpose of these batch tests was to attain detailed information on fuel conversion, complementary to previous continuous operation of the unit. At steady-state, a fuel batch of typically 25 g was introduced in the fuel reactor and gas concentrations were measured at the outlet of both air and fuel reactors. The fuel reactor was fluidized with steam and the amount of bed material was typically 5 kg. The fuel introduced devolatilizes rapidly while the remaining char is gasified and the resulting syngases H₂ and CO react with the oxygen carrier. Operation involved testing at different fuel reactor temperatures from 950 to 1030 °C, and investigation of the influence of particle circulation between air and fuel reactors.The fuel conversion rate was increased at higher temperature: at 950 °C the instantaneous rate of conversion for petroleum coke averaged at 17.4%/min while at 1030 °C, the value was 40%/min. For the much more reactive South African coal, the averaged rate at 970 °C was 47%/min and increased to 101%/min at 1000 °C. For petroleum coke testing with particle circulation, the oxygen demand - defined as oxygen lacking to fully convert the gases leaving the fuel reactor - was typically 12-14% for the gasified char including H₂S, in line with previous experiments with the same unit and fuel. If only syngases are considered, the oxygen demand for char conversion was 8.4-11%. Similar or even lower values were seen for the char of South African coal. This is in line with expectations, i.e. that it is possible to reach fairly high conversion, although difficult to reach complete gas conversion with solid fuel. It was also seen that the volatiles pass through the system essentially unconverted, an effect of feeding the fuel from above. Moreover, the oxygen demand for char conversion decreased with increasing temperature. Finally, the CO₂ capture - defined as the proportion of gaseous carbon leaving the fuel reactor to total gaseous carbon leaving the system - decreased at higher particle circulation and a correlation between capture and circulation index was obtained.     

Multiphase CFD-based models for chemical looping combustion process: Fuel reactor modeling

Chemical looping combustion (CLC) is a flameless two-step fuel combustion that produces a pure CO₂ stream, ready for compression and sequestration. The process is composed of two interconnected fluidized bed reactors. The air reactor which is a conventional circulating fluidized bed and the fuel reactor which is a bubbling fluidized bed. The basic principle is to avoid the direct contact of air and fuel during the combustion by introducing a highly-reactive metal particle, referred to as oxygen carrier, to transport oxygen from the air to the fuel. In the process, the products from combustion are kept separated from the rest of the flue gases namely nitrogen and excess oxygen. This process eliminates the energy intensive step to separate the CO₂ from nitrogen-rich flue gas that reduce the thermal efficiency.Fundamental knowledge of multiphase reactive fluid dynamic behavior of the gas-solid flow is essential for the optimization and operation of a chemical looping combustor.Our recent thorough literature review shows that multiphase CFD-based models have not been adapted to chemical looping combustion processes in the open literature. In this study, we have developed the reaction kinetics model of the fuel reactor and implemented the kinetic model into a multiphase hydrodynamic model, MFIX, developed earlier at the National Energy Technology Laboratory. Simulated fuel reactor flows revealed 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, say by decreasing the fuel flow rate, or to recirculate the unburned methane after condensing and removing CO₂.     

Chemical - Looping with oxygen uncoupling using Mn/Mg-based oxygen carriers - Oxygen release and reactivity with methane

Chemical-looping combustion with oxygen uncoupling (CLOU) is a method for combustion of solid and gaseous fossil fuels, which enables easy separation of carbon dioxide from the gaseous product mixture. In contrast to the related chemical-looping combustion (CLC) technology where gaseous or gasified fuels react directly with oxygen carriers, CLOU processes require oxygen carrier materials to be able to release oxygen in the fuel reactor and to regenerate by re-oxidation in oxygen-rich atmosphere in the air reactor at elevated temperature. Oxygen uncoupling properties and reactivities for methane combustion of 12 oxygen carrier particles, produced from mixtures of manganese and magnesium oxides with optional addition of titanium dioxide or calcium hydroxide, are investigated in a quartz batch reactor at 810 °C, 850 °C, 900 °C and 950 °C. All investigated oxygen carriers have oxygen release characteristics. The addition of calcium hydroxide facilitates oxygen release and combustion of methane, whereas addition of titanium dioxide does not have a pronounced effect on either oxygen uncoupling or reactivity of the oxygen carrier. In general, particles with greater extent of oxygen release have superior methane combustion properties.     

Using continuous and pulse experiments to compare two promising nickel-based oxygen carriers for use in chemical-looping technologies

Chemical-looping technologies have obtained widespread recognition as power or hydrogen production units with inherent carbon capture in a future scenario where CO₂ capture and storage (CCS) is reality. In this paper three different techniques are described; chemical-looping combustion and two categories of chemical-looping reforming. The three techniques are all based on oxygen carriers that are circulating between an air- and a fuel reactor, providing the fuel with undiluted oxygen. Two different oxygen carriers; NiO/NiAl₂O₄ (40/60 wt/wt) and NiO/MgAl₂O₄ (60/40 wt/wt) are compared. Both continuous and pulse experiments were performed in a batch laboratory fluidized bed working at 950 °C using methane as fuel. It was found that pulse experiments offer advantages in comparison to continuous experiments, particularly when evaluating suitable particles for autothermal chemical-looping reforming. Firstly, smaller conversion ranges can be investigated in more detail, and secondly, the onset and extent of carbon formation can be determined more accurately. Of the two oxygen carriers, NiO/MgAl₂O₄ offers several advantages at elevated temperatures, i.e. higher methane conversion, higher selectivity to reforming and lesser tendency for carbon formation.     

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.     

Ilmenite with addition of NiO as oxygen carrier for chemical-looping combustion

The naturally occurring mineral ilmenite, FeTiO₃, has been examined as oxygen carrier for chemical-looping combustion. NiO-based particles have been used as an additive, in order to examine if it is possible to utilize the catalytic properties of metallic Ni to facilitate decomposition of hydrocarbons into more reactive combustion intermediates such as CO and H₂. Firstly, ilmenite was examined by oxidation and reduction experiments in a batch fluidized-bed reactor. These experiments indicated moderate reactivity between ilmenite and CH₄, which was used as reducing gas. However, adding 5 wt.% of NiO-based particles to the ilmenite improved the conversion of CH₄ greatly, resulting in an increase in combustion efficiency with a factor of 3. Secondly, 83 h of chemical-looping combustion experiments were conducted in a small circulating fluidized-bed reactor, using ilmenite as oxygen carrier and natural gas as fuel. A wide range of process parameters and different levels of NiO addition were examined. Occasionally, there were problems with the circulation of solids between the air reactor and fuel reactor, but most of the time the experiments worked well. The products were mostly CO₂, H₂O and unconverted CH₄. Adding small amounts of NiO-based particles to the reactor increased the conversion of the fuel considerably. For the base case conducted at 900°, the combustion efficiency was 76% for pure ilmenite and 90% for the corresponding experiments with 1 wt.% NiO-based particles added to the reactor. The properties of ilmenite were found to change considerably during operation. Used particles had lower density, were more reactive and more porous than fresh particles. These changes appear to have been physical, and no unexpected chemical phases could be identified.     

Syngas and a separate nitrogen/argon stream via chemical looping reforming - A 140 kW pilot plant study

A dual circulating fluidized bed pilot plant was operated in chemical looping reforming conditions at a scale of 140 kW fuel power with natural gas as fuel. A nickel-based oxygen carrier was used as bed material. The pilot plant is equipped with an adjustable cooling system. Three experimental campaigns have been carried out at 747 °C (1020 K), 798 °C (1071 K) and 903 °C (1176 K), respectively. In each campaign, the global stoichiometric air/fuel ratio was varied step-wise between 1.1 and the minimum value possible to keep the desired operating temperature when the cooling is finally switched off. The results show that the fuel reactor exhaust gas approaches thermodynamic equilibrium. The residual amount of methane left decreases with increasing fuel reactor temperature. Further, the oxygen in the air reactor can be completely absorbed by the solids as soon as the air reactor operating temperature is higher than 900 °C (1173 K). Even though no steam was added to the natural gas feed no carbon formation was found for global excess air ratios larger than 0.4.     

Long-term integrity testing of spray-dried particles in a 10-kW chemical-looping combustor using natural gas as fuel

Chemical-looping combustion, CLC, is a combustion concept with inherent separation of CO₂. The fuel and combustion air are kept apart by using an oxygen carrier consisting of metal oxide. The oxygen carriers used in this study were prepared from commercially available raw materials by spray-drying. The aim of the study was to subject the particles to long-term operation (>1000 h) with fuel and study changes in particles, with respect to reactivity and physical characteristics. The experiments were carried out in a 10-kW chemical-looping combustor operating with natural gas as fuel. 1016 h of fuel operation were achieved. The first 405 h were accomplished using a single batch of NiO/NiAl₂O₄-particles. The last 611 h were achieved using a 50/50_mass-mixture of (i) particles used for 405 h, and (ii) a second batch of particles similar in composition to the first batch, but with an MgO additive. Thus, at the conclusion of the test series, approximately half of the particles in the reactor system had been subjected to >1000 h of chemical-looping combustion. The reason for mixing the two batches was to improve the fuel conversion. Fuel conversion was better with the mixture of the two oxygen carriers than it was using only the batch of NiO/NiAl₂O₄-particles. The CO fraction was slightly above the equilibrium fraction at all temperatures. Using the oxygen carrier mixture, the methane fraction was typically 0.4-1% and the combustion efficiency was around 98%. The loss of fines decreased slowly throughout the test period, although the largest decrease was seen during the first 100 h. An estimated particle lifetime of 33 000 h was calculated from the loss of fines. No decrease in reactivity was seen during the test period.     

Solid fuels in chemical-looping combustion using a NiO-based oxygen carrier

The feasibility of using three different solid fuels in chemical-looping combustion (CLC) has been investigated using NiO as oxygen carrier. A laboratory fluidized-bed reactor system for solid fuel was used, simulating a chemical-looping combustion system by exposing the sample to alternating reducing and oxidizing conditions. In each reducing phase 0.2 g of fuel was added to the reactor containing 20 g oxygen carrier. The experiments were performed at 970 °C. Compared to previously published results with other oxygen carriers the reactivity of the used Ni-particles was considerably lower for the high-sulphur fuel and higher for the low-sulphur fuel. Much more unconverted CO was released and the fuel conversion was much slower for high-sulphur fuel such as petroleum coke, suggesting that the nickel-based oxygen carrier was deactivated by the presence of sulphur. The NiO particles also showed good reactivity with methane and a syngas mixture of 50% H₂ and 50% CO. For all experiments the oxygen carrier showed good fluidizing properties without any signs of agglomeration.     

Reactivity of a CaSO<Subscript>4</Subscript>-oxygen carrier in chemical-looping combustion of methane in a fixed bed reactor

Chemical-looping combustion (CLC) is a promising technology for the combustion of gas or solid fuel with efficient use of energy and inherent separation of CO₂. A reactivity study of CaSO₄ oxygen carrier in CLC of methane was conducted in a laboratory scale fixed bed reactor. The oxygen carrier particles were exposed in six cycles of alternating reduction methane and oxidation air. A majority of CH₄ reacted with CaSO₄ to form CO₂ and H₂O. The oxidation was incomplete, possibly due to the CaSO₄ product layer. The reactivity of CaSO₄ oxygen carrier increased for the initial cycles but slightly decreased after four cycles. The product gas yields of CO₂, CH₄, and CO with cycles were analyzed. Carbon deposition during the reduction period was confirmed with the combustible gas (CO+H₂) in the product gas and slight CO₂ formed during the early stage of oxidation. The mechanism of carbon deposition and effect was also discussed. SO₂ release behavior during reduction and oxidation was investigated, and the possible formation mechanism and mitigation method was discussed. The oxygen carrier conversion after the reduction decreased gradually in the cyclic test while it could not restore its oxygen capacity after the oxidation. The mass-based reaction rates during the reduction and oxidation also demonstrated the variation of reactivity of CaSO₄ oxygen carrier. XRD analysis illustrated the phase change of CaSO₄ oxygen carrier. CaS was the main reduction product, while a slight amount of CaO also formed in the cyclic test. ESEM analysis demonstrated the surface change of particles during the cyclic test. The reacted particles tested in the fixed bed reactor were not uniform in porosity. EDS analysis demonstrated the transfer of oxygen from CaSO₄ to fuel gas while leaving CaS as the dominant reduced product. The results show that CaSO₄ oxygen carrier may be an interesting candidate for oxygen carrier in CLC. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, China, June 26–28, 2008.     

Gas leakage measurements in a cold model of an interconnected fluidized bed for chemical-looping combustion

In chemical-looping combustion (CLC) a gaseous fuel is burnt with inherent separation of the greenhouse gas carbon dioxide. The oxygen is transported from the combustion air to the fuel by means of metal oxide particles acting as oxygen carriers. A CLC system can be designed similar to a circulating fluidized bed, but with the addition of a bubbling fluidized bed on the return side. Thus, the system consists of a riser (fast fluidized bed) acting as the air reactor. This is connected to a cyclone, where the particles and the gas from the air reactor are separated. The particles fall down into a second fluidized bed, the fuel reactor, and are via a fluidized pot-seal transported back into the riser. The gas leaving the air reactor consists of nitrogen and unreacted oxygen, while the reaction products, carbon dioxide and water, come out from the fuel reactor. The water can easily be condensed and removed, and the remaining carbon dioxide can be liquefied for subsequent sequestration.The gas leakage between the reactors must be minimized to prevent the carbon dioxide from being diluted with nitrogen, or to prevent carbon dioxide from leaking to the air reactor decreasing the efficiency of carbon dioxide capture. In this system, the possible gas leakages are: (i) from the fuel reactor to the cyclone and to the pot-seal, (ii) from the cyclone down to the fuel reactor, (iii) from the pot-seal to the fuel reactor. These gas leakages were investigated in a scaled cold model. A typical leakage from the fuel reactor was 2%, i.e. a CO₂ capture efficiency of 98%. No leakage was detected from the cyclone to the fuel reactor. Thus, all product gas from the air reactor leaves the system from the cyclone. A typical leakage from the pot-seal into the fuel reactor was 6%, which corresponds to 0.3% of the total air added to the system, and would give a dilution of the CO₂ produced by approximately 6% air. However, this gas leakage can be avoided by using steam, instead of air, to fluidize the whole, or part of, the pot-seal. The disadvantages of diluting the CO₂ are likely to motivate the use of steam.     

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。     

Hydrogen production through chemical looping using NiO/NiAl2O4 as oxygen carrier

A new autothermal route to produce hydrogen from natural gas via chemical looping technology was investigated. Tests were conducted in a micro-fixed bed reactor loaded with 200 mg of NiO/NiAl₂O₄ as oxygen carrier. Methane reacts with a nickel oxide in the absence of molecular oxygen at 800 °C for a period of time as high as 10 min. The NiO is subsequently contacted with a synthetic air stream (21% O₂ in argon) to reconstitute the surface and combust carbon deposited on the surface. Methane conversion nears completion but to minimize combustion of the hydrogen produced, the oxidation state of the carrier was maintained below 30% (where 100% represents a fully oxidized surface). Co-feeding water together with methane resulted in stable hydrogen production. Although the carbon deposition increased with time during the reduction cycle, the production rate of hydrogen remained virtually constant. A new concept is also presented where hydrogen is obtained from methane with inherent CO₂ capture in an energy neutral 3-reactors CFB process. This process combines a methane combustion step where oxygen is provided via an oxygen carrier, a steam methane reforming step catalyzed by the reduced oxygen carrier and an oxidizing step where the O-carrier is reconstituted to its original state.