Performance of an oxy-polishing step in the 100 kWth chemical looping combustion prototype

Unconverted fuel gases are normally present in the gas leaving the fuel reactor of a Chemical Looping Combustion (CLC) process. Depending on several factors, including oxygen carrier and fuel volatiles content, the unconverted gases represent 5–30% of the oxygen needed for full combustion. Further conversion of these fuel components is imperative to achieve adequate combustion and to fulfill the requirements for CO2\ua0storage. An oxy-polishing step using highly concentrated O2\ua0to fully oxidize the fuel components offers a straightforward one-step way to reach complete combustion. However, systematic and detailed investigation is lacking while it is essential for design, scale up and optimization. In this work, the oxy-polishing is studied in a post-oxidation chamber (POC) of a 100 kWth\ua0unit using different solid fuels and manganese ores in the CLC process. With various flows of air as oxidation agent, the POC performance was evaluated under stable operations in a wide range of operating conditions. An overall oxygen ratio was defined to analyze the effect of O2\ua0excess in the POC. Experimental results show that the oxidation of fuel gas from the fuel reactor can be greatly enhanced by air entering the POC, with the gas conversion being improved from 87 to 90% before the POC to as high as 99–100% after the POC. Full oxidation in POC can be accomplished with excess of O2. For the cases of incomplete oxidation, CO was normally found in higher concentrations than CH4. In a few cases close to optimum, CO and O2\ua0simultaneously have normalized concentrations below 0.5–1% with a low overall oxygen ratio of around 1.01. The POC performance was further compared to the results from a simple reactor model

Negative emissions of carbon dioxide through chemical-looping combustion (CLC) and gasification (CLG) using oxygen carriers based on manganese and iron

Carbon capture and storage (CCS) is an economically attractive strategy for avoiding carbon dioxide (CO 2 ) emissions from, e.g., power plants to the atmosphere. The combination of CCS and biomass combustion would result in a reduction of atmospheric CO 2 , or net negative emissions, as plant growth is a form of sequestration of atmospheric carbon. Carbon capture can be achieved in a variety of ways, one of which is chemical looping. Chemical-looping combustion (CLC) and chemical looping gasification (CLG) are two promising technologies for conversion of biomass to heat and power or syngas/methane with carbon capture. There have been significant advances made with respect to CLC in the last two decades for all types of fuel, with much less research on the gasification technology. CLG offers some interesting opportunities for production of biofuels together with carbon capture and may have several advantages with respect to the bench mark indirect gasification process or dual-bed fluidized bed (DFBG) in this respect. In CLG, an oxygen carrier is used as a bed material instead of sand, which is common in indirect gasification, and this could have several advantages: (i) all generated CO 2 is present together with the syngas or methane in the fuel reactor outlet stream, thus in a concentrated stream, viable for separation and capture; (ii) the air reactor (or combustion chamber) should largely be free from trace impurities, thus preventing corrosion and fouling in this reactor; and (iii) the highly oxidizing conditions in the fuel reactor together with solid oxide surfaces should be advantageous with respect to limiting formation of tar species. In this study, two manganese ores and an iron-based waste material, LD slag, were investigated with respect to performance in these chemical-looping technologies. The materials were also impregnated with alkali (K) in order to gauge possible catalytic effects and also to establish a better understanding of the general behavior of oxygen carriers with alkali, an important component in biomass and biomass waste streams and often a precursor for high-temperature corrosion. The viability of the oxygen carriers was investigated using a synthetic biogas in a batch fluidized bed reactor. The conversion of CO, H 2 , CH 4 , and C 2 H 4 was investigated in the temperature interval 800–950\ua0\ub0C. The reactivity, or oxygen transfer rate, was highest for the manganese ores, followed by the LD slag. The conversion of C 2 H 4 was generally high but could largely be attributed to thermal decomposition. The K-impregnated samples showed enhanced reactivity during combustion conditions, and the Mangagran-K sample was able to achieve full conversion of benzene. The interaction of the solid material with alkali showed widely different behavior. The two manganese ores retained almost all alkali after redox testing, albeit exhibiting different migration patterns inside the particles. LD slag lost most alkali to the gas phase during testing, although some remained, possibly explaining a small difference in reactivity. In summary, the CLC and CLG processes could clearly be interesting for production of heat, power, or biofuel with negative CO 2 emissions. Manganese ores are most promising from this study, as they could absorb alkali, giving a better conversion and perhaps also inhibiting or limiting corrosion mechanisms in a combustor or gasifier

Chemical-looping combustion of synthetic biomass-volatiles with manganese-ore oxygen carriers

Carbon capture and storage of CO2 from combustion of biomass, i.e., bio-energy carbon capture and storage (BECCS), makes it possible to obtain so-called negative emissions – the atmosphere is cleansed from carbon dioxide. The purpose of the present study was to investigate the suitability of different manganese ores as oxygen carriers in chemical-looping combustion of biomass fuels. For this screening study, a laboratory-scale, circulating fluidized-bed CLC system with a nominal fuel input of 300 Wth was used. The primary focus was to investigate the reactivity of these oxygen carriers towards biomass fuels, and find a reactive oxygen carrier with sufficient mechanical stability that could be suitable for large-scale chemical-looping combustion of biomass. A synthetic “biomass volatiles” gas was used to study how the different gas components react with the oxygen-carrier particles. Additional experiments were conducted with methane and a syngas. Parameter studies concerning temperature and specific fuel-reactor bed mass (bed mass per fuel thermal power in kg/MWth) were carried out. With the synthetic biomass volatiles, conversion of fuel carbon to CO2 as high as 97.6% was achieved. For a majority of the investigated ores, essentially all C2 and C3 hydrocarbons were converted, as well as a very high fraction of the CO. Reactivity towards CH4 was generally lower, but improved at higher temperatures. The resistance of the oxygen carriers towards mechanical degradation was measured in a jet-cup attrition test rig. The measured attrition was estimated as “intermediate” for four of the five tested materials, while one of the ores displayed high attrition

Steel converter slag as an oxygen carrier for chemical-looping gasification

Chemical Looping Gasification (CLG) is a dual fluidized bed gasification technique where an oxygen carrier is used as bed material instead of sand. An optimized process could have several advantages, including i) one concentrated CO2 stream, amiable for carbon capture, ii) less tar formation, iii) additional reaction pathways for syngas production, iv) less corrosion and v) CO2 is generated in one stream from the fuel reactor that could be captured. Steel converter slag, also called LD slag, is a by-product from the steel industry which, besides iron, contains significant fractions of Ca, Mg, Al and Mn in a complex matrix of phases. The low cost and presence of known catalytic solid phases in the slag makes it interesting as an oxygen carrier in CLG. In this work, LD slag was investigated using a batch reactor with gaseous and solid fuel as well as with TGA. It was found that during gasification with LD slag, the material can i) transfer oxygen to the fuel, ii) catalyze the water-gas-shift reaction, iii) react with CO2 forming carbonates and iv) split water to hydrogen. The overall result was a raw gas with a higher H2/CO ratio for LD slag than the other tested materials

Oxygen Carrier and Alkali Interaction in Chemical Looping Combustion: Case Study Using a Braunite Mn Ore and Charcoal Impregnated with K2CO3or Na2CO3

Alkali is a problematic component in biomass and may create various operation issues in normal combustion as well as chemical looping combustion using biomass fuels (bio-CLC). To investigate the interaction of alkali with an oxygen carrier, a methodology has been developed where alkali salts are added with impregnated charcoal particles. This work studies the effect of K2CO3 and Na2CO3 on the fluidization/agglomeration behavior and reactivity as well as the interaction of a braunite manganese ore oxygen carrier with K and Na in a batch fluidized bed reactor. Charcoal impregnated with K2CO3 (K-charcoal) and charcoal impregnated with Na2CO3 (Na-charcoal) were used as solid fuels in the reduction step of the simulated CLC cycles. CH4 and syngas (50% CO + 50% H2) were periodically used to evaluate the reactivity of braunite before and after solid fuel experiments. In total, more than 50 cycles were performed for both K-charcoal series and Na-charcoal series tests, while some additional cycles with non-impregnated charcoal were conducted and considered as a reference. Partial agglomeration and partial defluidization were found after cycles with K-charcoal and Na-charcoal, and the use of K-charcoal tends to lead to the partial agglomeration/defluidization faster than the use of Na-charcoal. K, Na, Si, and Ca were found at a higher concentration on the surface of the agglomerated particles and can be assumed to be responsible for the partial agglomeration. The partial agglomeration with K-charcoal happened likely as a result of surface melting of the braunite particles, whereas the formation of the low-melting-point Na-Si-Ca system could be responsible for agglomeration in the Na-charcoal experiments. The concentration of K and Na in the braunite bed was found to increase during cycles with the alkali charcoals. In total, the added masses of K and Na were 0.8 and 1.2% of the bed, and around 40 and 80% of added K and Na were found, respectively, in the used oxygen carrier particles. Although partial agglomeration and accumulation were observed in the presence of these alkalis, the reactivity of used braunite was scarcely changed in comparison to the fresh sample

Commissioning, performance benchmarking, and investigation of alkali emissions in a 10 kWth solid fuel chemical looping combustion pilot

Chemical looping combustion of biomass-sourced fuels (bio-CLC) is a novel bio-energy with carbon capture and storage (BECCS) technology for power and heat generation with net negative CO2 emissions. In this study, a new 10 kWth CLC pilot designed for high-volatiles biomass fuels was commissioned with ilmenite oxygen carrier and five different biomass fuels of varying volatile and alkali content fractions. The system was tested for its ability to convert high and low volatile content biomass, while achieving high carbon capture efficiency. The new pilot achieved carbon capture close to 100% for high-volatiles biomass, and >94% for low-volatiles biomass char fuels. Furthermore, due to the implementation of a volatiles distributor, the new pilot demonstrated an improvement of up to 10 percentage points of gas conversion efficiency for high-volatiles biomass vs. the previous generation reactor. Gaseous alkali emissions were measured with a surface ionization detection system. Flue gas alkali release levels were found to rise with higher fuel alkali content. Alkali emissions were found to be approximately similar in the AR and the FR for all but the straw pellet mixture fuel (highest alkali content fuel). For the straw pellet mixture, gaseous alkali release levels in the AR were up to seven times higher than those of the FR. In all cases, over 96% of the fuel\u27s alkalis were absorbed by the ilmenite bed material. Ilmenite\u27s strong alkali absorption characteristics were concluded to be the key determinant of gas-phase release of biomass alkali in the conducted experiments

Investigation on the Performance of Volatile Distributors with Different Configurations under Different Fluidization Regimes

The uniform horizontal distribution of volatiles over the cross section of a fluidized bed with the purpose to obtain good contact between volatiles and bed materials is a key issue to improve the gas conversion in the fuel reactor of chemical looping combustion of solid fuels. The effectiveness of the volatile distributor (VD) concept on the lateral distribution of volatiles in a fluidized bed has been investigated under different operational conditions using a cold-flow model. Furthermore, the performance of the VD has been examined using different configurations of the holes used to distribute the volatiles. The fluidization regimes, i.e., single bubble regime, with only one large bubble formed at a time at the bottom bed, exploding bubble regime, with irregular bubbles containing more particles, and multiple bubble regime, with many small bubbles formed and distributed in the bed, are determined by visual observation of the bottom riser and analysis of the pressure fluctuations, including frequency analysis. The VDs with uneven hole arrangements, which have less distribution holes at the simulated volatile inlet side and a larger open area far from the inlet, provide a more even horizontal distribution of volatiles compared to the VD with equally distributed holes. A larger simulated volatile flow and less open area of the VD increase the pressure drop over the distribution holes and improve the horizontal distribution. In general, the VD gives a more uniform distribution of the volatiles under the exploding bubble regime and better distribution in the single bubble regime compared to the multiple bubble regime. However, the bottom leakage, i.e., the volatile leakage from the bottom of the VD, should be considered, especially in the single bubble regime

Performance of a volatiles distributor equipped with internal baffles under different fluidization regimes

Chemical looping combustion of biomass is a promising carbon capture technology due to its inherent CO2 separation advantage. However, complete fuel conversion, particularly volatiles conversion for biomass, is usually not achieved in the fuel reactor. A novel concept named volatiles distributor (VD) has been proposed and tested in a cold-flow fluidized-bed, which shows good potential to achieve a more uniform horizontal distribution of the volatiles and improve the gas-solid contact. In this work, the VD has been further developed by introducing an array of internal baffles inside the VD. The objective is to improve the horizontal gas distribution and reduce the volatiles slip from the bottom of the VD. The results show that the uniformity of the horizontal distribution is improved significantly by the VD equipped with the internal baffles, especially in the single and multiple bubble regimes. The volatiles slip from the bottom of the VD is reduced by the installation of internal baffles according to the visual observation, even though there is a higher CO2 concentration detected above the bottom edge of the VD near the wall. A pronounced back-mixing of gas near the wall in the main riser may be the principal reason for the higher measured CO2 concentration

Reactivity and lifetime assessment of an oxygen releasable manganese ore with biomass fuels in a 10 kWth pilot rig for chemical looping combustion

Finding a suitable oxygen carrier is crucial for the development of Chemical Looping Combustion (CLC). A new manganese ore was tested with different biomass fuels in a recently commissioned 10 kWth unit. The ore maintains the capability of generating O2 gas in N2 after continuous operations with the fuels, however, the concentration was relatively low within 0.45–1.0 vol% at 820 to 975 \ub0C. Influence of temperature, solids circulation and fuel power was examined for different fuels. Temperature increase enhances the carbon capture and reduces the oxygen demand, while the solids circulation and fuel power should be carefully controlled. Using biomass char the oxygen demand can be lowered to 2.6% while the carbon capture was close to 99%. The manganese ore showed a higher reactivity than the often-used ilmenite. Thus, a decrease of 8–10% in oxygen demand was achieved by using the manganese ore in comparison to ilmenite. During the 42 h of hot operation, defluidisation was not observed. Based on the analysis of the 35 fine samples collected, the initial attrition after first hours of operation was high, but gradually decreased to a relatively stable value of 0.27 and 0.12 wt%/h for hot and fuel operations, respectively, corresponding a lifetime of 370–830 h

Experimental evaluation of manganese ores for chemical looping conversion of synthetic biomass volatiles in a 300 W reactor system

Two manganese ores with different iron content were investigated as oxygen carriers for chemical looping conversion of simulated biomass volatiles. The aim was to study the performance of the oxygen carriers with regards to combustion and potential use for chemical-looping gasification of wood-based biomass. The oxygen carriers were studied in a 300 W chemical-looping reactor system with circulation of oxygen carriers between the fluidized air and fuel reactors. The temperature was 850-900 \ub0C and the fuel flow rates were 0.6-3 Lmin-1. The Mn ore with higher iron content showed significant oxygen release at 900 \ub0C under inert conditions, as well as full conversion of CO, H2 and methane at low fuel flow. The other Mn ore showed little methane conversion and poorer conversion of the other gases when compared at similar fuel flows. However, the gas composition attained was rather similar if compared for a similar overall gas conversion. Nonetheless, a slightly higher syngas fraction and H2 to CO ratio in the product stream was obtained with the Mn ore with lower iron content. In all cases the syngas fraction in the product gas increased with temperature and fuel flow. The formation of fines (attrition rate), particle size distribution, and the bulk density of the oxygen carriers were measured to evaluate their mechanical properties during chemical looping of biomass volatiles