Chemical-looping combustion of solid fuels - Status of development

Chemical-looping combustion (CLC) of solid fuels is a technology with the potential of reducing the costs and energy penalty dramatically for CO2 capture. The potential for low costs is based on the similarity to coal combustion in fluidized beds. However, this assumes reaching high performance with respect to fuel and gas conversion, or that inadequate performance can be readily mitigated by downstream options. There are uncertainties with respect to the performance that can be reached in large-scale units, as well as with the extra costs needed to compensate for inadequate performance. Performance will be dependent on both reactor design and oxygen carrier properties. The status of chemical-looping combustion of solid fuels is discussed with respect to performance and experiences from pilot operation. (C) 2013 Elsevier Ltd. All rights reserved

Using steam reforming to produce hydrogen with carbon dioxide capture by chemical-looping combustion

In this paper, a novel process for hydrogen production by steam reforming of natural gas with inherent capture of carbon dioxide by chemical-looping combustion is proposed. The process resembles a conventional circulating fluidized bed combustor with reforming taking place in reactor tubes located inside a bubbling fluidized bed. Energy for the endothermic reforming reactions is provided by indirect combustion that takes place in two separate reactors: one for air and one for fuel. Oxygen is transferred between the reactors by a metal oxide. There is no mixing of fuel and air so carbon dioxide for sequestration is easily obtained. Process layout and expected performance are evaluated and a preliminary reactor design is proposed. It is found that the process should be feasible. It is also found that it has potential to achieve better selectivity towards hydrogen than conventional steam reforming plants due to low reactor temperatures and favorable heat-transfer conditions

A 1000 MWth boiler for chemical-looping combustion of solid fuels - Discussion of design and costs

More than 2000 h of solid-fuel CLC operation in a number of smaller pilot units clearly indicate that the concept works. A scale-up of the technology to 1000 MWth is investigated in terms of mass and heat balances, flows, solids inventories, boiler dimensions and the major differences between a full-scale Circulating Fluidized-Bed (CFB) boiler and a Chemical-Looping Combustion CFB (CLC-CFB). Furthermore, the additional cost of CLC-CFB relative to CFB technology is analysed and found to be 20 (sic)/tonne CO2. The largest cost is made up of compression of CO2, which is common to all capture technologies. Although the need for oxygen to manage incomplete conversion is estimated to be only a tenth of that of oxy-fuel combustion, oxygen production is nonetheless the second largest cost. Other significant costs include oxygen-carrier material, increased boiler cost and steam for fluidization of the fuel reactor

Steam methane reforming with chemical-looping combustion: Scaling of fluidized-bed-heated reformer tubes

The combination of chemical-looping combustion (CLC) and steam methane reforming (SMR) bears the potential for quantitative and energy-efficient CO2 capture along with hydrogen production from natural gas. A 2-dimensional axisymmetric model of a SMR tube was used to estimate the possibility to adapt the tube dimensions to better fit into fluidized-bed heat exchangers. A constant surrounding fluidized-bed temperature was set as the boundary condition. There are two phenomena that affect the reactor performance: the effective heat-transfer rate from the fluidized bed to and through the tube wall and onward to and into the catalyst bed on the one hand and the effective reaction rates of the governing chemical reactions on the other hand. Literature models were used for the heat-transfer description assuming a state-of-the-art reforming catalyst and classical SMR kinetics were formulated. The simulation results show a temperature decrease toward the tube center in steady state operation. The gas phase composition at the tube outlet reflects the radial temperature distribution as the chemical equilibrium is approached well. Simulations with smaller tube diameters indicate that the necessary tube length for equivalent gas conversion is significantly reduced. In a 1/2-scale setting with 63 mm inner diameter (ID) of the tube instead of 126 mm ID in full scale, the necessary tube length is only 6.0 m instead of 12.5 m, and in a 1/4-scale setting with 31.5 mm ID, the necessary tube length is only 3.3 m. A temperature increase of the fluidized bed from 900 to 950 and 1000 \ub0C may reduce the necessary tube length in the 1/4 scale from 3.3 to 2.6 and 2.2 m, respectively. These indications are promising with respect to the possibilities for fluidized-bed immersed reformer tube dimensioning and arrangement. More detailed reactor design studies will be necessary to judge the industrial feasibility of the CLC-SMR combination

An experimental study of a volatiles distributor for solid fuels chemical-looping combustion process

A novel concept called volatiles distributor (VD), with the purpose to achieve an even distribution of volatiles over the cross-section of a fluidized-bed and better contact between volatiles and bed materials, has been investigated. The concept could be useful for chemical- looping combustion, as well as other solid fuel conversion processes in fluidized-beds. An experimental study of the VD in a circulating fluidized-bed (CFB) cold-flow model was conducted under different fluidization velocities and flows of simulated volatiles. In the reference case without VD, a local plume of volatiles is formed and the maldistribution becomes more pronounced at higher fluidization velocity in the range from 1 m/s to 4 m/s. Conversely, higher fluidization velocity gives a more even volatiles distribution in the presence of VD. The relative standard deviation of volatiles horizontal distribution decreases from 131% in absence of VD to 22% in presence of VD at the fluidization velocity of 4 m/s. There is no significant effect of volatiles flow rate on VD performance at a fluidization velocity 1 m/s. As the fluidization velocity and volatiles flow rate increase, the bed level inside VD is lowered and the volatiles inside the VD become less diluted, because less air from the main fluidization passes through the VD

Synthesis gas generation by chemical-looping reforming in a continuously operating laboratory reactor

Chemical-looping reforming is a technology that can be used for partial oxidation and steam reforming of hydrocarbon fuels. This paper describes continuous chemical-looping reforming of natural gas in a laboratory reactor consisting of two interconnected fluidized beds. Particles composed of 60 wt% NiO and 40 wt% MgAl2O4 are used as bed material, oxygen carrier and reformer catalyst. There is a continuous circulation of particles between the reactors. In the fuel reactor, the particles are reduced by the fuel, which in turn is partially oxidized to H-2, CO, CO2 and H2O. In the air reactor the reduced oxygen h of reforming were recorded. Formation of solid carbon was noticed for some cases. Adding 25 vol% steam to the natural gas reduced or eliminated the carbon formation

Fate of NO and Ammonia in Chemical Looping Combustion-Investigation in a 300 W Chemical Looping Combustion Reactor System

Chemical looping combustion (CLC) is a novel combustion concept that transfers oxygen from air to fuel using an oxygen carrier that circulates between an air reactor and a fuel reactor. Thus, the combustion products, H2O and CO2, are obtained in a separate flow, and ideally, a pure CO2 gas stream is obtained after condensation of H2O. Consequently, CLC has a unique potential for avoiding the high costs and energy penalties of CO2 capture. Further, NO emissions can potentially be avoided. CLC is flameless, and the temperature is too low for the formation of thermal NOx. Moreover, fuel NOx and prompt NOx do not form in the air reactor in the absence of fuel. In the fuel reactor, the absence of oxygen prevents normal NOx formation. However, when using fuels containing nitrogen, NO may form in the fuel reactor because the oxygen carrier can oxidize fuel nitrogen compounds. To achieve a CO2 stream suited for storage, NO must be removed. Dependent upon how NO is removed, the process could be free from any NO emissions. NO formation and NO reduction were investigated in a 300 W CLC reactor by adding either NH3 or NO. The work involved two different oxygen carriers, Linz-Donawitz (LD) slag and ilmenite, two temperatures, 850 and 900 degrees C, two circulation rates, and different flows of syngas fuel. Further, operation without fuel with a fully and partially oxidized oxygen carrier was studied. For LD slag, lower fuel flow promoted the formation of NO and decreased the reduction of NO. Likewise, higher temperatures raised NO formation and lowered NO reduction. Ilmenite, however, was by far more superior with respect to NO. Thus, NO formation only occurred in the absence of fuel and with a fully oxidized oxygen carrier. Likewise, NO was fully reduced to N-2 for all conditions, except in the absence of fuel and with fully oxidized ilmenite

Negative CO 2 emissions - An analysis of the retention times required with respect to possible carbon leakage

With present emissions the global CO 2 budget associated with a maximum temperature increase of about 1.5–2 \ub0C will likely be spent within a few decades, Thus, it will be very difficult or perhaps even impossible to meet the climate targets agreed upon in Paris only by decreasing emissions of greenhouse gases. Scenarios presented in the IPCC reports accommodate for this by introducing so-called negative CO 2 emissions. The idea is that the cumulative CO 2 emission budget will be exceeded, but that massive negative emissions, especially during the latter part of the century, will remove the surplus of CO 2 in the atmosphere. A number of different Negative Emissions Technologies (NETs) have been proposed, including Biomass Energy with Carbon Capture and Storage (BECCS), afforestation/reforestation, altered agricultural practices, biochar production, enhanced weathering and direct air captured. However, many of the options proposed could be associated with carbon leakage which could compromise the purpose of negative emissions, e.g. storage in of carbon in growing/dead biomass that leaks to the atmosphere. Furthermore, it may be difficult to safely assess the long-term leakage rates. To reach the large negative emissions needed it is expected to require a mix of approaches having different expected retention times, and different safety in terms of leakage rates. Could the risk of leakage mean that we are just delaying the problem and transferring the problem to coming generations? The short answer to this is that it all depends on the leakage rates. Different leakage rates and mixes of leakage rates are investigated in the paper. For the case of a mixture of leakage time scales of 300, 1000 and 10,000 years and assuming that 80% or more was permanently stored, the contribution to the atmospheric stock was small, peaking at about 3 ppm CO 2 . It was concluded that leakage would not significantly compromise the benefits of negative emissions unless leakage is substantial and rapid. To quantify what could be meant by substantial and rapid, an example would be if 100% of the CO 2 stored would leak out at a rate of the order of 1%/year

Testing of minerals and industrial by-products as oxygen carriers for chemical-looping combustion in a circulating fluidized-bed 300W laboratory reactor

Chemical-looping combustion (CLC) is a promising technology for future energy production with inherent CO2 separation. One approach is to use minerals or industrial by-products as oxygen carriers to reduce the costs of the process. This study focuses on the investigation of two iron-based oxygen carriers, which were examined under continuous operation in a 300 W laboratory reactor. Ilmenite is an iron–titanium oxide mineral, whereas iron oxide scale (IOS) is obtained as a by-product from the rolling of sheet steel. Syngas was used as a fuel – pure and with steam addition to suppress the formation of solid carbon. During the experiments the variables reactor temperature, fuel flow and air flow were changed. Furthermore the effect of steam addition to the fuel was investigated. Particle properties were compared over the span of 85 h of continuous operation for ilmenite and 37 h for IOS. The analysis is based on gas measurements from the actual CLC operation, but also on scanning electron microscopy, X-ray powder diffractometry and measurements of BET surface area and density. With ilmenite oxygen carrier it was possible to achieve full conversion of syngas up to about 190 Wth fuel equivalent at 900 °C. With design fuel flow of about 300 Wth at 900 °C the combustion efficiency was above 98%. There was almost no visible difference in reactivity of fresh activated particles and those used for 85 h. Combustion efficiency up to 99% was achieved with IOS oxygen carrier at 900 °C and about 100 Wth fuel equivalent. At 300 Wth fuel equivalent and 900 °C a combustion efficiency of only 90% could be reached. Both oxygen carriers were operated for tens of hours, which allowed for a better understanding of lifetime behavior and other basic characteristics. Whereas ilmenite oxygen-carrier particles were mostly stable over the course of 85 h of experiments, a large fraction of IOS oxygen-carrier particles had disintegrated to fines after only 37 h of experiments. The gathered data indicates that both oxygen carriers could be an alternative to synthesized particles, though with more drawbacks for IOS than for ilmenite

Chemical-Looping Combustion and Chemical-Looping Reforming in a Circulating Fluidized-Bed Reactor Using Ni-Based Oxygen Carriers

Three oxygen carriers for chemical-looping combustion and chemical-looping reforming have been investigated in a small circulating fluidized-bed reactor. N2AM1400 was produced by freeze granulation with MgAl2O4 as a support material and had a NiO content of 20%. Ni18-αAl was produced by impregnation onto α-Al2O3 and had a NiO content of 18%. Ni21-γAl was produced by impregnation onto γ-Al2O3 and had a NiO content of 21%. Over 160 h of operation has been recorded. The conversion of natural gas into products was 96−100% depending on oxygen carrier and experimental conditions. For chemical-looping combustion, N2AM1400 and Ni21-γAl provided poor selectivity toward CO2 and H2O while Ni18-αAl initially showed very high selectivity, which declined as a function of time. For chemical-looping reforming, operating the reactor at the desired process parameters, which was a fuel reactor temperature of 950 °C and an air factor of 0.30, was possible with all of the tested oxygen-carrier materials. When only natural gas was used as fuel, there was significant formation of solid carbon in the fuel reactor for Ni18-αAl and Ni21-γAl. Adding 30% steam or CO2 to the fuel removed or decreased the carbon formation. During the course of the experiments, N2AM1400 and Ni18-αAl retained their physical and chemical structure, while Ni21-γAl displayed a significant reduction in porosity but remained highly reactive