Enhancing properties of iron and manganese ores as oxygen carriers for chemical looping processes by dry impregnation

The use of naturally occurring ores as oxygen carriers in CLC processes is attractive because of their relative abundance and low cost. Unfortunately, they typically exhibit lower reactivity and lack the mechanical robustness required, when compared to synthetically produced carriers. Impregnation is a suitable method for enhancing both the reactivity and durability of natural ores when used as oxygen carriers for CLC systems. This investigation uses impregnation to improve the chemical and mechanical properties of a Brazilian manganese ore and a Canadian iron ore. The manganese ore was impregnated with Fe2O3 and the iron ore was impregnated with Mn2O3 with the goal of forming a combined Fe/Mn oxygen carrier. The impregnated ore’s physical characteristics were assessed by SEM, BET and XRD analysis. Measurements of the attrition resistance and crushing strength were used to investigate the mechanical robustness of the oxygen carriers. The impregnated ore’s mechanical and physical properties were clearly enhanced by the impregnation method, with boosts in crushing strength of 11–26% and attrition resistance of 37–31% for the impregnated iron and manganese ores, respectively. Both the unmodified and impregnated ore’s reactivity, for the conversion of gaseous fuel (CH4 and syngas) and gaseous oxygen release (CLOU potential) were investigated using a bench-scale quartz fluidised-bed reactor. The impregnated iron ore exhibited a greater degree of syngas conversion compared to the other samples examined. Iron ore based oxygen carrier’s syngas conversion increases with the number of oxidation and reduction cycles performed. The impregnated iron ore exhibited gaseous oxygen release over extended periods in an inert atmosphere and remained at a constant 0.2% O2 concentration by volume at the end of this inert period. This oxygen release would help ensure the efficient use of solid fuels. The impregnated iron ore’s reactivity for CH4 conversion was similar to the reactivity of its unmodified counterpart. The unmodified manganese ore converted CH4 to the greatest extent of all the samples tested here, while the impregnated manganese ore exhibited a decrease in reactivity with respect to syngas and CH4 conversion.EPSR

Tar characteristics generated from a 10 kWth chemical-looping biomass gasifier using steel converter slag as an oxygen carrier

Tar management is one of the key components to achieve high energy efficiency and low operational costs connected to thermal gasification of biomass. Tars contain a significant amount of energy, and unconverted tars result in energy efficiency losses. Also, heavy tars can condense downstream processes, resulting in increased maintenance. Dual fluidized beds for indirect gasification operated with active bed material can be a way to better convert and control the tar generated in the process. Using an active material to transport oxygen in an indirect dual reactor gasification setup is referred to as chemical-looping gasification (CLG). A higher oxidative environment in the gas phase, in addition to possible catalytic sites, could mean lower yields in comparison to normal indirect gasification. This paper investigates the effect of using Steel converter slag (LD slag), a byproduct of steel manufacturing, as an oxygen-carrying bed material on tar species generated in a 10 kWth dual fluidized bed biomass gasifier. The results are compared to the benchmark oxygen carrier ilmenite and conventional silica sand. Three different solid biofuels were used in the reactor system: steam exploded pellets, pine forest residue and straw. Tar was absorbed from the raw syngas using a Solid Phase Adsorption (SPA) column and was analyzed using GC-FID. Bench-scale experiments were also performed to investigate benzene conversion of LD slag and ilmenite at different oxidation levels. The findings of this study suggest that oxygen carriers can be used to decrease the tars generated in a dual fluidized bed system during gasification. Phases in LD slag possess catalytic properties, resulting in a decreased ratio of heavy tar components compared to both ilmenite and sand. Temperature and fuel load showed a significant effect on the tar generation compared to the circulation and steam ratio in this reactor system. Increased temperature generated lower tar yields and lower ratios of heavy tar components for LD slag in contrast to sand

Effect of the Mass Conversion Degree of an Oxygen Carrier on Char Conversion and Its Implication for Chemical Looping Gasification

Chemical looping gasification (CLG) is an emerging process that aims to produce valuable chemical feedstocks. The key operational requirement of CLG is to limit the oxygen transfer from the air reactor (AR) to the fuel reactor (FR). This can be accomplished by partially oxidizing the oxygen carrier in the AR, which may lead to a higher reduction degree of the oxygen carrier under the fuel conversion. A highly reduced oxygen carrier may experience multiple issues, such as agglomeration and defluidization. Given such an interest, this study examined how the variation of the mass conversion degree of ilmenite may affect the conversion of pine forest residue char in a fluidized bed batch reactor. Ilmenite was pre-reduced using diluted CO and then underwent the char conversion at 850, 900, 950, and 975 degrees C. Our investigations showed that the activation energy of the char conversion was between 194 and 256 kJ/mol, depending upon the mass conversion degree of ilmenite. Furthermore, the hydrogen partial pressure in the particle bed increased as the oxygen carrier mass conversion degree decreased, which was accompanied by a lower reaction rate and a higher reduction potential. Such a hydrogen inhibition effect was confirmed in the experiments; therefore, the change in the mass conversion degree indirectly affected the char conversion. Langmuir-Hinshelwood mechanism models used to evaluate the char conversion were validated. On the basis of the physical observation and characterizations, the use of ilmenite in CLG with biomass char as fuel will likely not suffer from major agglomeration or fluidization issues

Modelling of gas conversion with an analytical reactor model for biomass chemical looping combustion (bio-CLC) of solid fuels

Manganese ores are promising oxygen carriers for chemical looping combustion (CLC), due to their high reactivity with combustible gases. In this work, a manganese ore called EB (Elwaleed B, originating from Egypt) is studied for its reaction rate with CH4, CO and H2 and the data are used in an analytically solved reactor model. The reactivity of fresh and three used EB samples from previous operation in a 10 kWth pilot was examined in a batch fluidized bed reactor with CH4 and syngas (50%CO + 50%H2). In comparison with other manganese ores, the EB ore has a lower rate of reaction with CH4, while showing a significantly higher reactivity with syngas. Nevertheless, this manganese ore always presents a better conversion of CH4 and syngas than the benchmark ilmenite. Mass-based reaction rate constants were obtained using a pseudo first-order reaction mechanism: 1.1\ub710-4 m3/(kg\ub7s) for CH4, 6.6\ub710-3 m3/(kg\ub7s) for CO and 7.5\ub710-3 m3/(kg\ub7s) for H2. These rate constants were used in an analytical reactor model to further investigate results from previous operation in the 10 kWth unit. According to the analytical model, in the 10 kWth operation, 98% of the char in the biomass fuels was gasified before leaving the fuel reactor, while the char gasification products (CO and H2) have a 90% contact efficiency with the bed material. On the contrary, the volatiles have a much lower contact efficiency with the oxygen carrier bed, i.e. 20%, leading to low conversion of volatiles released. Thus, the results emphasize the importance of improving the contact between volatiles and bed material in order to promote combustion performance in the CLC process

Alkali interactions with a calcium manganite oxygen carrier used in chemical looping combustion

Chemical-Looping Combustion (CLC) of biofuels is a promising technology for cost-efficient CO2 separation and can lead to negative CO2 emissions when combined with carbon capture and storage. A potential challenge in developing CLC technology is the effects of alkali metal-containing compounds released during fuel conversion. This study investigates the interactions between alkali and an oxygen carrier (OC), CaMn0.775Ti0.125Mg0.1O3-δ, to better understand the fate of alkali in CLC. A laboratory-scale fluidized bed reactor is operated at 800–900 \ub0C in oxidizing, reducing and inert atmospheres to mimic CLC conditions. Alkali is fed to the reactor as aerosol KCl particles, and alkali in the exhaust is measured online with a surface ionization detector. The alkali concentration changes with gas environment, temperature, and alkali loading, and the concentration profile has excellent reproducibility over repeated redox cycles. Alkali-OC interactions are dominated by alkali uptake under most conditions, except for a release during OC reduction. Uptake is significant during stable reducing conditions, and is limited under oxidizing conditions. The total uptake during a redox cycle is favored by a high alkali loading, while the influence of temperature is weak. The implications for the understanding of alkali behavior in CLC and further development are discussed

Alkali-wall interactions in a laboratory-scale reactor for chemical looping combustion studies

Alkali metal-containing compounds are readily released during thermal conversion of solid fuels, and may have both detrimental and beneficial effects on chemical looping combustion. Here, we characterize alkali interactions with the inner walls of a laboratory-scale reactor under oxidizing, reducing and inert conditions at temperatures up to 900 \ub0C. KCl aerosol particles are continuously introduced to the stainless steel reactor and the alkali concentration is measured on-line with a surface ionization detector. Aerosol particles evaporate at temperatures above 500 \ub0C and KCl molecules rapidly diffuse to the reactor wall. Up to 92% of the alkali reaching the wall below 700 \ub0C remains adsorbed, while re-evaporation is important at higher temperatures, where up to 74% remains adsorbed. Transient changes in alkali concentration are observed during repeated redox cycles, which are associated with changes in chemical composition of the wall material. Metal oxides on the reactor wall are partially depleted under reducing conditions, which allow for the formation of a new potassium-rich phase that is stable in a reducing atmosphere, but not under inert conditions. The observed wall effects are concluded to be extensive and include major transient effects depending on gas composition, and the implications for laboratory studies and improved experimental methodology are discussed

Performance of iron sand as an oxygen carrier at high reduction degrees and its potential use for chemical looping gasification

Iron sand as an industrial by-product has a reasonable iron content (35 wt% Fe) and low economical cost. The reactivity of iron sand as an oxygen carrier was examined in a bubbling fluidized bed reactor using both gaseous and solid fuels at 850–975 \ub0C. Pre-reductions of iron sand were performed prior to fuel conversion to adapt the less-oxygen-requiring environment in chemical looping gasification (CLG). Based on the investigations using CO and CH4, iron sand has an oxygen transfer capacity of around 1 wt%, which is lower than that of ilmenite. The conversion of pine forest residue char to CO and H2 was higher when using iron sand compared to ilmenite. Depending on the mass conversion degree of iron sand, the activation energy of pine forest residue char conversion using iron sand was between 187 and 234 kJ/mol, which is slightly lower than that of ilmenite. Neither agglomeration nor defluidization of an iron sand bed occurred even at high reduction degrees. These suggests that iron sand can be utilized as an oxygen carrier in CLG. Furthermore, this study presents novel findings in the crystalline phase transformation of iron sand at various degrees of oxidation, altogether with relevant thermodynamic stable phases

Characteristics of Copper-based Oxygen Carriers Supported on Calcium Aluminates for Chemical-Looping Combustion with Oxygen Uncoupling (CLOU)

Eight different oxygen carriers (OC) containing CuO (60 wt %) and different mass ratios of CaO to Al2O3 as the support were synthesized by wet-mixing followed by calcination at 1000 °C. The method of synthesis used involved the formation of calcium aluminum hydrate phases and ensured homogeneous mixing of the Ca2+ and Al3+ ions in the support at the molecular level. The performance of the OCs for up to 100 cycles of reduction and oxidation was evaluated in both a thermogravimetric analyzer (TGA) and a fluidized bed reactor, covering a temperature range of 800 to 950 °C. In these cycling experiments, complete conversion of the OC, from CuO to Cu and vice versa, was always achieved for all OCs. The reactivity of the materials was so high that no deactivation could be observed in the TGA, owing to mass transfer limitations. It was found that OCs prepared with a mass ratio of CaO to Al2O3 in the support >0.55 agglomerated in the fluidized bed, resulting in an apparent deactivation over 25 cycles for all temperatures investigated. High ratios of mass of CaO to Al2O3 in the support resulted in CuO interacting with CaO, forming mixed oxides that have low melting temperatures, and this explains the tendency of these materials to agglomerate. This behavior was not observed when the mass ratio of CaO to Al2O3 in the support was ≤0.55 and such materials showed excellent cyclic stability operating under redox conditions at temperatures as high as 950 °C.The authors thank Mohammad Ismail and Matthew Dunstan for helping with the XRD analysis and Alex Casabuena-Rodriguez and for helping with the SEM. This work was supported by the Engineering and Physical Sciences Research Council (EPSRC grant EP/I010912/1).This is the final version of the article. It first appeared from ACS via http://dx.doi.org/10.1021/acs.iecr.5b0117

Mercury release and speciation in chemical looping combustion of coal

In the in situ Gasification Chemical Looping Combustion of coal (iG-CLC), the fuel is gasified in situ in the fuel reactor and gasification products are converted to CO2 and H2O by reaction with the oxygen carrier. This work is the first study on mercury release in Chemical Looping Combustion of coal. The fraction of the mercury in coal vaporized in the fuel reactor depended mainly on the fuel reactor temperature and the coal type. In the fuel reactor, mercury was mainly emitted as Hg0 in the gas phase and the amount increased with the temperature. In the air reactor, mercury was mostly emitted as Hg2+. In a real CLC system, mercury emissions to the atmosphere will decrease compared to conventional combustion as only mercury released in the air reactor will reach the atmosphere. However, measures should be taken to reduce Hg0 in the CO2 stream before the purification and compression steps in order to avoid operational problems.The authors thank the Government of Aragón and La Caixa (2012-GA-LC-076 project) and the Spanish Ministry for Science and Innovation (ENE2010-19550 project) for the financial support. P. Gayán thanks CSIC for the financial support of the project 201180E102. The authors also thank to Alcoa Europe-Alúmina Española S.A. for providing the Fe-enriched sand fraction used in this work. G. Galo is acknowledged for his contribution to the experimental results.Peer reviewe

Oxygen-Carrier-Aided Combustion in a Bench-Scale Fluidized Bed

In a circulating fluidized bed (CFB) boiler, one of the basic functions of the bed materials is to transport heat between different parts of the boiler to clecrease heat gradients and, thereby, smoothen the operation. A novel concept, oxygen Carrier-aided combustion (OCAC), replaces some or all of the bed materials with an oxygen carrier, which is a metal oxide that, through chemical redox reaction, not only transports heat but also transports oxygen between oxygen-lean and oxygen-rich areas of the boiler. The oxygen carrier also acts as internal oxygen storage, which increases the total amount of available oxygen in the boiler. The concept of OCAC was demonstrated by Thunman et al. at Chalmers University of Technology, where the bed material (sand) in a 12 MW boiler was replaced with iron titanium mineral (ilmenite). In this work, a small fluidized bed reactor is used to mimic the condition in OCAC with regard to fuel conversion as well as NO formation and to test other oxygen carrier, materials. Four oxygen carriers were tested, two ores (ilmenite and manganese ore), and two Oxide scales (denoted as AQS and LDst), which were byproducts from the steel production of the Swedish company SSAB. Sand was also used as a reference. Wood char was used as the fuel, and concentrations of CO2, CO, CH4, O-2, and NO in the exhaust gases were monitored. The effect of oxygen carriers on combustion efficiency and NO emission was investigated at different air/fuel ratios. The results Show that, utilization of an oxygen carrier reduces the level of CO emission, thereby increasing the efficiency of combustion. It is also Shown that the increase In combustion efficiency can be largely attributed to the reactivity of the oxygen carriers with CO. With OCAC, it was possible to reduce the level of excess air and, thereby, lower the level of NO emissions while maintaining the same level of CO emission