| 1. |
- Hildor, Fredrik, 1992, et al.
(författare)
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Effect of Weathering on Steel Converter Slag Used as an Oxygen Carrier
- 2023
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Ingår i: ACS Omega. - 2470-1343. ; 8:50, s. 47472-47481
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Tidskriftsartikel (refereegranskat)abstract
- Steel converter slag, also called LD slag, is a material that has been suggested for use as a low-cost oxygen carrier for chemical looping applications. Low-cost oxygen carriers are especially relevant for the conversion of solid fuels, which may contain large amounts of reactive ashes. Ash may limit the lifetime of the bed material, which is why a high-cost oxygen carrier will likely not be competitive. Applying LD slag on an industrial scale as an oxygen carrier makes the storage properties of the material highly interesting. LD slag has been known to be affected by weathering, thus limiting the possibilities of the material to be used in construction, e.g., as fillers in concrete. In this study, pretreated LD slag for use as an oxygen carrier was weathered outdoors for roughly 1.5 years in southwest Sweden. Afterward, the particles were characterized and used in a laboratory batch fluidized bed reactor system to evaluate the effects of storage on the oxygen carrier properties. It was found that the reactivity with the fuel of the weathered LD slag was similar to that of the original sample when used in a laboratory fluidized bed. However, the physical properties were severely degraded due to weathering. Dissolved CaO formed CaCO3, agglomerating the top layer of the sample. The particles in the bulk of the sample were found to have decreased density and increased attrition rate. This suggests that LD slag particles for use as oxygen carriers should be stored dry to avoid weathering of the particles.
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| 2. |
- Hildor, Fredrik, 1992, et al.
(författare)
-
Metal impregnation on steel converter slag as an oxygen carrier
- 2023
-
Ingår i: Greenhouse Gases: Science and Technology. - : Wiley. - 2152-3878. ; 13
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Tidskriftsartikel (refereegranskat)abstract
- Oxygen carriers used in chemical looping processes operated with biofuel are affected by the inorganic matter of the fuel. It is therefore expected that the lifetime of the oxygen carrier is limited, and preferably low-cost oxygen carriers should be used. Oxygen carriers based on iron ore or steel manufacturing waste products are available in significant quantities at low cost. However, it is common for these types of materials that their reactivity is low. This study investigates the effect of adding small amounts of more reactive elements into steel converter slag, also called LD slag. Slag particles were wet impregnated with 2 or 5 wt.% of Ni, Cu, Mn, or Ce. The new material’s morphology was evaluated using X-Ray Diffraction and SEM-EDS. Changes in reactivity towards CO, CH4 and the model tar molecule benzene were evaluated using a bench-scale laboratory fluidized bed reactor. It was observed that even small amounts of either Ni, Cu, or Mn could increase reactivity toward CO. Both Cu and Mn formed phases with LD slag that released oxygen via CLOU (chemical looping with oxygen uncoupling) and increased the conversion of methane and benzene. Ni and Ce doping also increased methane conversion but had only a minor effect on the benzene conversion.
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| 3. |
- Hildor, Fredrik, 1992, et al.
(författare)
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Steel converter slag as an oxygen carrier for chemical-looping gasification
- 2020
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Ingår i: Fuel Processing Technology. - : Elsevier BV. - 0378-3820. ; 210
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 4. |
- Hildor, Fredrik, 1992, et al.
(författare)
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Steel converter slag as an oxygen carrier in a 12 MWth CFB boiler – Ash interaction and material evolution
- 2019
-
Ingår i: International Journal of Greenhouse Gas Control. - : Elsevier BV. - 1750-5836. ; 88, s. 321-331
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Tidskriftsartikel (refereegranskat)abstract
- © 2019 Elsevier Ltd Steel converter slag or LD slag is a byproduct of the basic oxygen steel production process, where raw iron from the blast furnace is converted to steel. LD slag contains mainly calcium and iron compounds and smaller amounts of magnesium, silicon, manganese and vanadium. The iron content, about 17 wt.% of the slag, makes this material a potential oxygen carrier for combustion processes such as Oxygen Carrier Aided Combustion (OCAC) or Chemical Looping Combustion (CLC). This study will present an investigation of the use of LD slag as an oxygen carrier in OCAC at semi-industrial scale. The Chalmers 12 MWth biomass circulating fluidized bed boiler was operated using LD slag as bed material under OCAC conditions. During the operation, bed samples from the boiler were extracted and analyzed with ICP-SFMS, SEM-EDS, XRD and different mechanical tests to analyze chemical and physical changes of the bed material as a function of time. The samples were also investigated in a laboratory fluidized bed reactor to determine the change in reactivity towards common volatile fuel components, i.e. CO, H2, CH4 and C6H6. It was found that LD slag can be utilized as an oxygen carrier in a combustion process for biofuel. However, the reactivity towards syngas, CH4 and C6H6 is reduced as a function of time in the boiler, which is believed to be caused by accumulation of, and interaction with, alkali from the biofuel ash. Sulfur addition may decrease the adverse effects of alkali on combustion efficiency, but not eliminate them completely.
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| 5. |
- Keller, Martin, 1985, et al.
(författare)
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Investigation of Natural and Synthetic Bed Materials for Their Utilization in Chemical Looping Reforming for Tar Elimination in Biomass-Derived Gasification Gas
- 2014
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 1520-5029 .- 0887-0624. ; 28:6, s. 3833-3840
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Tidskriftsartikel (refereegranskat)abstract
- The removal of condensable hydrocarbons or tars from raw gas derived from biomass gasification presents an obstacle in the widespread application of biomass gasification. Hot catalytic tar cleaning as a secondary tar removal strategy is discussed as a tar cleaning technology. This can be realized in a dual-fluidized-bed reactor system, in which a catalytically active bed material is continuously regenerated. Such a process is termed chemical looping reforming (CLR). In such a process, it has been suggested that oxygen carrier particles employed for chemical looping combustion may be used, with the oxygen transfer from the particles to the gas promoting tar decomposition. Experiments were conducted in a small-scale, batch-wise fluidized-bed reactor with the aim of investigating a variety of bed materials for this process. The purpose of the present work is thus to conduct a screening study of a variety of bed materials based on the transition metals Fe, Mn, Ni, and Cu. The experiments were conducted in a batch fluidized bed, where the particles are exposed to reformer and regenerator conditions alternatingly. The conversion of ethylene from a synthetic gasification gas mixture was used as an indicator for the suitability of the materials for tar conversion. It was found that the natural material bauxite and the synthetic bed materials NiO/alpha-Al2O3, CuO/MgAl2O4, and La0.8Sr0.2FeO3/gamma-Al2O3 exhibit high ethylene conversion rates and, thus, possess promising properties for their application in CLR
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| 6. |
- Mattisson, Tobias, 1970, et al.
(författare)
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Chemical-Looping Technologies using Circulating Fluidized Bed Systems: Status of Development
- 2017
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Ingår i: 12th International Conference on Fluidized Bed Technology, CFB 2017. ; , s. 11-22
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Konferensbidrag (refereegranskat)abstract
- In chemical-looping combustion (CLC), an oxygen carrier provides lattice oxygen for complete combustion of a fuel for heat and power production. The reduced metal oxide is then oxidized in a separate reactor. The combustion products CO2 and H2O are obtained in pure form, without any nitrogen in the gas. As no gas separation work is needed, this could be a breakthrough technology for carbon capture (CCS). Normally, the fuel- and air-reactor are designed utilizing inter-connected fluidized beds. The same underlying reversible redox reactions of CLC can be used for other fuel conversion technologies. These include fluidized bed processes for gas, solid and liquid fuels for heat, power, syngas or hydrogen production. Some of these concepts were suggested as far back as the 1950’s, while others have just recently been proposed. Chalmers University of Technology has been involved in CLC research for over 18 years, and this paper will provide a review of some recent developments with respect to CLC with gaseous, liquid and solid fuels. Further, the paper will provide an overview some related technologies where Chalmers is conducting research: i) Chemical-looping gasification (CLG), ii) Chemical-looping reforming (CLR) and iii) Chemical-looping tar reforming (CLTR). In these processes, a pure syngas/hydrogen can be produced effectively, which could be utilized for chemical or fuel production.
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| 7. |
- Mattisson, Tobias, 1970, et al.
(författare)
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Chemical-looping technologies using circulating fluidized bed systems: Status of development
- 2018
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Ingår i: Fuel Processing Technology. - : Elsevier BV. - 0378-3820. ; 172, s. 1-12
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Forskningsöversikt (refereegranskat)abstract
- In chemical-looping combustion (CLC), an oxygen carrier provides lattice oxygen for complete combustion of a fuel for heat and power production. The reduced metal oxide is then oxidized in a separate reactor. The combustion products CO 2 and H 2 O are obtained in pure form, without any nitrogen in the gas. As no gas separation work is needed, this could be a breakthrough technology for carbon capture (CCS). Normally, the fuel- and air-reactor are designed utilizing inter-connected fluidized beds. The same underlying reversible redox reactions of CLC can be used for other fuel conversion technologies. These include fluidized bed processes for gas, solid and liquid fuels for heat, power, syngas or hydrogen production. Some of these concepts were suggested as far back as the 1950's, while others have just recently been proposed. This paper will provide a review of some recent developments with respect to CLC with gaseous, liquid and solid fuels, with focus on operational experience. Today, more than 35 continuous units have been used worldwide, with over 9000 h of operational time. Although most experience has been reported for methane and natural gas, significant testing has now also been performed with various solid fuels. Some recent developments include i) shift from Ni-based materials to more benign metal oxide oxygen carriers, ii) use of different types of biomass and iii) operation at semi-commercial scale. Furthermore, this paper will also provide an overview some related technologies which also utilize oxygen carriers in interconnected fluidized beds: i) Chemical-looping gasification (CLG), ii) Chemical-looping reforming (CLR) and iii) Chemical-looping tar reforming (CLTR). In these processes, a pure syngas/hydrogen can be produced effectively, which could be utilized for chemical or fuel production.
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| 8. |
- Mei, Daofeng, 1986, et al.
(författare)
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Modelling of gas conversion with an analytical reactor model for biomass chemical looping combustion (bio-CLC) of solid fuels
- 2022
-
Ingår i: Chemical Engineering Journal. - : Elsevier BV. - 1385-8947 .- 1873-3212. ; 433
-
Tidskriftsartikel (refereegranskat)abstract
- 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: 1.1·10-4 m3/(kg·s) for CH4, 6.6·10-3 m3/(kg·s) for CO and 7.5·10-3 m3/(kg·s) 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.
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| 9. |
- Mei, Daofeng, 1986, et al.
(författare)
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Oxygen Carrier and Alkali Interaction in Chemical Looping Combustion: Case Study Using a Braunite Mn Ore and Charcoal Impregnated with K 2 CO 3 or Na 2 CO 3
- 2022
-
Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 1520-5029 .- 0887-0624. ; 36:17, s. 9470-9484
-
Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 10. |
- Adanez-Rubio, Inaki, et al.
(författare)
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Investigation of Combined Supports for Cu-based Oxygen Carriers for Chemical-Looping with Oxygen Uncoupling (CLOU)
- 2013
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 1520-5029 .- 0887-0624. ; 27:7, s. 3918-3927
-
Tidskriftsartikel (refereegranskat)abstract
- The chemical-looping with oxygen uncoupling (CLOU) process is a novel solution for efficient combustion with inherent separation of carbon dioxide. The process uses a metal oxide as an oxygen carrier to transfer oxygen from an air to a fuel reactor. In the fuel reactor, the metal oxide releases gas phase oxygen which oxidizes the fuel through normal combustion. In this study, Cu-based oxygen carrier materials that combine different supports of MgAl2O4, TiO2 and SiO2 are prepared and characterized with the objective of obtaining highly reactive and attrition resistant particles. The oxygen carrier particles were produced by spray-drying and were calcined at different temperatures ranging from 950 to 1030oC for 4 h. The chemical-looping performance of the oxygen carriers was examined in a batch fluidized-bed reactor in the temperature range of 900-950oC under alternating reducing and oxidizing conditions. The mechanical stability of the oxygen carriers was tested in a jet-cup attrition rig. All of the oxygen carriers showed oxygen uncoupling behaviour with oxygen concentrations close to equilibrium. During reactivity tests with methane, oxygen carriers with lower mechanical stability showed higher reactivity, yielding almost complete fuel conversion. Oxygen carrier materials based on support mixtures of MgAl2O4/TiO2, MgAl2O4/SiO2 and TiO2/SiO2 showed a combination of high mechanical stability, low attrition rates, good reactivity with methane and oxygen uncoupling behaviour.
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| 11. |
- Andersson, Viktor, 1983, et al.
(författare)
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Alkali desorption from ilmenite oxygen carrier particles used in biomass combustion
- 2024
-
Ingår i: Fuel. - 0016-2361 .- 1873-7153. ; 359
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Tidskriftsartikel (refereegranskat)abstract
- Oxygen-carrying fluidized bed materials are increasingly used in novel technologies for carbon capture and storage, and to improve the efficiency of fuel conversion processes. Potassium- and sodium-containing compounds are released during biomass combustion and may have both negative and positive effects on conversion processes. Ilmenite is an important oxygen carrier material with the ability to capture alkali in the form of titanates. This is a desirable property since it may reduce detrimental alkali effects including fouling, corrosion, and fluidized bed agglomeration. This study investigates the interactions of alkali-containing compounds with ilmenite particles previously used in an industrial scale (115 MWth) oxygen carrier aided combustion system. The ilmenite samples were exposed to temperatures up to 1000 °C under inert and oxidizing conditions while the alkali release kinetics were characterized using online alkali monitoring. Alkali desorption occurs between 630 and 800 °C, which is attributed to loosely bound alkali at or near the surface of the particles. Extensive alkali release is observed above 900 °C and proceeds during extended time periods at 1000 °C. The release above 900 °C is more pronounced under oxidizing conditions and approximately 9.1 and 3.2 wt% of the alkali content is emitted from the ilmenite samples in high and low oxygen activity, respectively. Detailed material analyses using scanning electron microscopy with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy were conducted before and after temperature treatment, which revealed that the concentrations of potassium, sodium and chlorine decrease at the outermost surface of the ilmenite particles during temperature treatment, and Cl is depleted to a deeper level in oxidizing conditions compared to inert. The implications for ilmenite-ash interactions, oxygen carrier aided combustion and chemical looping systems are discussed.
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| 12. |
- Andersson, Viktor, 1983, et al.
(författare)
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Alkali interactions with a calcium manganite oxygen carrier used in chemical looping combustion
- 2022
-
Ingår i: Fuel Processing Technology. - : Elsevier BV. - 0378-3820 .- 1873-7188. ; 227
-
Tidskriftsartikel (refereegranskat)abstract
- 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 °C 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.
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| 13. |
- Andersson, Viktor, 1983, et al.
(författare)
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Alkali-wall interactions in a laboratory-scale reactor for chemical looping combustion studies
- 2021
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Ingår i: Fuel Processing Technology. - : Elsevier BV. - 0378-3820 .- 1873-7188. ; 217
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Tidskriftsartikel (refereegranskat)abstract
- 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 °C. 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 °C and KCl molecules rapidly diffuse to the reactor wall. Up to 92% of the alkali reaching the wall below 700 °C 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.
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| 14. |
- Andersson, Viktor, 1983, et al.
(författare)
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Design and first application of a novel laboratory reactor for alkali studies in chemical looping applications
- 2023
-
Ingår i: Fuel Processing Technology. - 0378-3820. ; 252
-
Tidskriftsartikel (refereegranskat)abstract
- Alkali compounds are readily released during biomass conversion and their complex interactions with reactor walls and sampling equipment makes detailed investigations challenging. This study evaluates a novel laboratory-scale fluidized bed reactor for chemical looping combustion (CLC) studies. The reactor design is based on detailed consideration of the behavior of alkali-containing molecules and aerosol particles and is guided by computational fluid dynamic simulations. The design allows for interactions between gaseous alkali and a fluidized bed, while minimizing alkali interactions with walls before and after the fluidized bed. The function of the laboratory reactor is demonstrated in experiments using online gas and alkali analysis. Alkali is continuously fed to the reactor as KOH or KCl aerosol with and without a fluidized bed of the oxygen carrier CaMn0.775Ti0.125Mg0.1O3-δ present in inert, reducing and oxidizing conditions at temperatures up to 900 °C. Alkali uptake by the OC is characterized in all conditions, and observed to sensitively depend on gas composition, reactor temperature and type of alkali compound. The experimental setup is concluded to have a significantly improved functionality compared to a previously used reactor, which opens up for detailed studies of interactions between alkali compounds and oxygen carriers used in CLC.
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| 15. |
- Andersson, Viktor, 1983, et al.
(författare)
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Gaseous alkali interactions with ilmenite, manganese oxide and calcium manganite under chemical looping combustion conditions
- 2024
-
Ingår i: Fuel Processing Technology. - 0378-3820 .- 1873-7188. ; 254
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Tidskriftsartikel (refereegranskat)abstract
- Alkali species present in biomass pose significant challenges in chemical looping combustion (CLC) processes and other thermal conversion applications. The interactions between different alkali species and three common oxygen carrier (OC) materials that are considered to be state of the art in CLC applications have been investigated. A dedicated fluidized bed laboratory reactor was used to study interactions of KCl, NaCl, KOH, NaOH, K2SO4 and Na2SO4 with manganese oxide, calcium manganite and ilmenite. Alkali vapor was generated by injecting alkali salts under reducing, oxidizing and inert conditions at 900 °C. Gaseous species were measured online downstream of the reactor, and the efficiency of alkali uptake was determined under different conditions. The result show significant alkali uptake by all OCs under the studied conditions. Ilmenite shows near complete alkali uptake in reducing conditions, while manganese oxide and calcium manganite exhibited less effective alkali uptake, but have advantages in terms of fuel conversion and oxidizing efficiency. Alkali chlorides, sulfates and hydroxides show distinctly different behavior, with alkali hydroxides being efficiently captured all three investigate OC materials. The findings contribute to a deeper understanding of alkali behavior and offer valuable guidance for the design and optimization of CLC with biomass.
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| 16. |
- Arjmand, Mehdi, 1986, et al.
(författare)
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CaxLa1−xMn1−yMyO3−δ (M = Mg, Ti, Fe or Cu) as Oxygen Carriers for Chemical-Looping with Oxygen Uncoupling (CLOU)
- 2013
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 1520-5029 .- 0887-0624. ; 27:8, s. 4097-4107
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Tidskriftsartikel (refereegranskat)abstract
- Perovskite materials of the type CaxLa1−xMn1−yMyO3−δ (M = Mg, Ti, Fe or Cu) have been investigated as oxygen carriers for the chemical-looping with oxygen uncoupling (CLOU) process. The oxygen carrier particles were produced by mechanical homogenization of primary solids in a rotary evaporator followed by extrusion and calcination at 1300°C for 6 h. The chemical-looping characteristics of the substituted perovskites developed in this work were evaluated in a laboratory-scale fluidized-bed reactor in the temperature range of 900−1000°C during alternating reducing and oxidizing conditions. The oxygen carriers showed oxygen releasing behaviour (CLOU) in inert atmosphere between 900−1000°C. In addition, their reactivity with methane was high, approaching complete gas yield for all of the materials at 950°C, the exception being the Cu-doped perovskite which defluidized during reduction. The rates of oxygen release were also investigated using devolatilized wood char as solid fuel, and were found to be similar. The required solids inventory in the fuel reactor for the perovskite oxygen carriers is estimated to be 325 kg/MWth. All of the formulations exhibited high rates of oxidation and high degree of stability with no particle fragmentation or agglomeration. The high reactivity and favourable oxygen uncoupling properties make these oxygen carriers promising candidates for the CLOU process.
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| 17. |
- Arjmand, Mehdi, 1986, et al.
(författare)
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CaZrO3 and SrZrO3-based CuO Oxygen Carriers for Chemical-Looping with Oxygen Uncoupling (CLOU)
- 2014
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Ingår i: Energy Procedia. - : Elsevier BV. - 1876-6102. ; 51, s. 75-84
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Konferensbidrag (refereegranskat)abstract
- The chemical-looping combustion (CLC) and chemical-looping with oxygen uncoupling (CLOU) processes are novel solutions for efficient combustion with inherent separation of carbon dioxide. In this work, oxygen carriers based on CuO supported by zirconates of SrZrO3 and CaZrO3 are investigated. The oxygen carriers were produced by mechanical homogenization of primary solids in a rotary evaporator followed by extrusion, drying and calcination at 950 and 1030 degrees C for 6 h. Their chemical-looping performance was evaluated in a laboratory-scale fluidized-bed reactor at 900 and 925 degrees C under cyclic oxidizing, inert (N-2) and reducing (CH4) conditions. All oxygen carriers exhibited rapid release of oxygen in the inert environment (CLOU) with high conversion of methane. The carrier calcined at 1030 degrees C with SrZrO3 as support showed no agglomeration or deactivation and exhibited the highest reactivity. Thus, the use of this oxygen carrier could be of interest for the CLOU process.
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| 18. |
- Arjmand, Mehdi, 1986, et al.
(författare)
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Evaluation of CuAl2O4 as an Oxygen Carrier in Chemical-Looping Combustion
- 2012
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Ingår i: Industrial & Engineering Chemistry Research. - : American Chemical Society (ACS). - 1520-5045 .- 0888-5885. ; 51:43, s. 13924-13934
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Tidskriftsartikel (refereegranskat)abstract
- The chemical-looping combustion (CLC) process is a novel solution for efficient combustion with intrinsic separation of carbon dioxide. The process uses a metal oxide as an oxygen carrier to transfer oxygen from an air to a fuel reactor where the fuel, or gasification products of the fuel, reacts with the solid oxygen carrier. In this work, copper(II) aluminate (CuAl2O4) was assessed as a potential oxygen carrier using methane as fuel. The carrier particles were produced by freeze–granulation and calcined at 1050 °C for a duration of 6 h. The chemical-looping characteristics were evaluated in a laboratory-scale fluidized-bed reactor in the temperature range of 900–950 °C during 45 alternating redox cycles. The oxygen carrier exhibited reproducible and stable reactivity behavior in this temperature range. Neither agglomeration nor defluidization was noticed in any of the cycles carried out at 900–925 °C. However, after reactivity tests at 950 °C, soft agglomeration and particle fragmentation were observed. Systematic phase analysis of the Cu–Al–O system during the redox cycle was carried out as a function of duration of reduction and oxygen concentration during the oxidation period. It was found that the CuAl2O4 is reduced to copper(I) aluminate (CuAlO2; delafossite), Cu2O, and elemental Cu. The CuAlO2 phase is characterized by slow kinetics for oxidation into CuO and CuAl2O4. Despite this kinetic limitation, complete conversion of methane with reproducible reactivity of the oxygen carrier is achieved. Thus, CuAl2O4 could be a potential oxygen carrier for chemical-looping combustion.
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| 19. |
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| 20. |
- Arjmand, Mehdi, 1986, et al.
(författare)
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Investigation of Different Manganese Ores as Oxygen Carriers in Chemical-Looping Combustion (CLC) for Solid Fuels
- 2014
-
Ingår i: Applied Energy. - : Elsevier BV. - 1872-9118 .- 0306-2619. ; 113, s. 1883-1894
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Tidskriftsartikel (refereegranskat)abstract
- The chemical-looping combustion (CLC) process is a novel solution for efficient combustion with direct capture of carbon dioxide. The process uses a metal oxide as an oxygen carrier to transfer oxygen from an air to a fuel reactor, where the fuel reacts with the solid oxygen carrier. In this work, six different manganese ores are investigated as oxygen carriers for CLC application. The chemical-looping characteristics of the oxygen carriers were evaluated in a laboratory-scale fluidized-bed reactor in the temperature range of 900-970oC during alternating reducing and oxidizing conditions. Three of the manganese ores showed a small oxygen release in inert environment between 850 and 950oC. During reactivity tests, the gas yield with methane increased with the temperature and complete conversion of 50% CO in H2 was obtained for all of the ores. The rates of char gasification of two fuels, namely Mexican petroleum coke and Swedish wood char, were compared for the different manganese ores at 970oC and with 50% H2O in N2 as fluidizing gas. Ilmenite and a manufactured Mn-oxide oxygen carrier consisting of Mn3O4 and MgO-stabilized ZrO2 as support were also included for comparison. The char gasification rate and the gas conversion were higher with the manganese ores and the Mn-oxide oxygen carrier compared to ilmenite. However, the higher reactivity of the manganese ores with H2 and the ensuing decrease in H2 inhibition for manganese ores is not sufficient to explain their higher rate of char gasification. Surface analysis of partially gasified petcoke particles in the presence of manganese ores showed formation of cavities and channels as well as a uniform distribution of potassium and sodium elements. The rate of char gasification also increased with the concentration of potassium and sodium impurities in the manganese ores. Thus the results suggest that the increased rate of char conversion for manganese ores is due to alkali-catalyzed steam gasification. The increase in rate of char gasification, in combination with potentially low costs of these materials suggests that manganese ores could be interesting materials for CLC with solid fuels.
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| 21. |
- Arjmand, Mehdi, 1986, et al.
(författare)
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Oxygen Release and Oxidation Rates of MgAl2O4-Supported CuO Oxygen Carrier for Chemical-Looping Combustion with Oxygen Uncoupling (CLOU)
- 2012
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 1520-5029 .- 0887-0624. ; 26:11, s. 6528-6539
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Tidskriftsartikel (refereegranskat)abstract
- The chemical-looping combustion (CLC) and chemical-looping with oxygen uncoupling (CLOU) processes are novel solutions for efficient combustion with inherent separation of carbon dioxide. These processes use a metal oxide as an oxygen carrier to transfer oxygen from an air reactor to a fuel reactor, where the fuel reacts with the solid oxygen carrier. When solid fuel is used in CLC, the char must be gasified by, e.g., steam to form H2 and CO, that can be subsequently oxidized to H2O and CO2 by the oxygen carrier. In the case of CLOU, the oxygen carrier releases oxygen gas in the fuel reactor. This enables a high rate of conversion of char from solid fuels, because it eliminates the need for the gasification step needed in normal CLC with solid fuels. In this work, the rate of oxygen release and oxidation of an oxygen carrier consisting of CuO supported by MgAl2O4 (40/60 wt %) for the CLOU process is investigated. The oxygen carrier was produced by freeze-granulation, calcined at 950 °C, and sieved to a size range of 125–180 μm. The reaction rates were obtained in a laboratory-scale fluidized-bed reactor in the temperature range of 850–900 °C, under alternating reducing and oxidizing conditions. The rate of oxygen release was obtained using devolatilized wood char as the fuel in N2 fluidization. Care was taken to obtain reliable measurements not affected by the availability of the fuel and temperature increase in the bed during combustion of the fuel with the released oxygen from the carrier. The Avrami–Erofeev mechanism was used to model the rates of oxygen release and the values of ko and Eapp were estimated to be 2.5 × 105 s–1 and 139.3 kJ mol–1, respectively. The rates of Cu2O oxidation were investigated in a flow of 5% O2 at the inlet of the reactor. However, it was observed that the oxidation rate is limited by the oxygen supply, indicating rapid conversion of the oxygen carrier. From the obtained reaction rates, the minimum total amount of the investigated oxygen carrier needed in the air and the fuel reactor is estimated to be between 69–139 kg MWth–1.
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| 22. |
- Arjmand, Mehdi, 1986, et al.
(författare)
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Prospects of Al2O3 and MgAl2O4-Supported CuO Oxygen Carriers in Chemical-Looping Combustion (CLC) and Chemical-Looping with Oxygen Uncoupling (CLOU)
- 2011
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 1520-5029 .- 0887-0624. ; 25:11, s. 5493-5502
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Tidskriftsartikel (refereegranskat)abstract
- The chemical-looping combustion (CLC) and chemical-looping with oxygen uncoupling (CLOU) processes are attractive solutions for efficient combustion with direct separation of carbon dioxide. In this work, the feasibility of CuO supported on Al2O3 and MgAl2O4 for CLC and CLOU processes is investigated. The oxygen carriers were produced by freeze-granulation and calcined at 950 and 1050 degrees C. The chemical-looping characteristics were evaluated in a laboratory-scale fluidized bed at 900 and 925 degrees C under alternating reducing and oxidizing conditions. Tendencies toward agglomeration, defluidization, and loss of active phase were analyzed by changing the experimental process variables, such as reaction time, temperature, and reducing and inert environments. Complete conversion of methane was obtained for all oxygen carriers investigated in this work Three out of four oxygen carriers also featured the rapid release of oxygen in an inert environment (CLOU). In the case of Al2O3) as support, a CLC and a CLOU oxygen carrier were obtained depending on the calcination temperature. In addition, analyses of the CuO-Al2O3 phase equilibria system under oxidizing and reducing conditions have been carried out. At the investigated temperatures, it is inferred for the case of Al2O3 as support that part of the active phase (either CuO or CuAl2O4 is bound as CuAlO2 during incomplete reduction with slow kinetics for reoxidation. However, when complete reduction is attained, the original active phase composition is rejuvenated upon oxidation. As a result, the use of CuAl2O4 is suggested for CLC processes from the point of agglomeration and attrition-free functioning of the oxygen carrier. In the case of MgAl2O4 as support, the oxygen carrier exhibited a stable oxygen-releasing behavior due to the existence of relatively intact CuO. Together with the absence of agglomeration and major morphological changes, the use of MgAl2O4-supported CuO is suggested as a suitable oxygen carrier for CLOU processes.
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| 23. |
- Arjmand, Mehdi, 1986, et al.
(författare)
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Screening of Combined Mn-Fe-Si Oxygen Carriers for Chemical Looping with Oxygen Uncoupling (CLOU)
- 2015
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 1520-5029 .- 0887-0624. ; 29:3, s. 1868-1880
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Tidskriftsartikel (refereegranskat)abstract
- Combined oxygen carriers of Mn, Fe, and Si were screened for the chemical looping with oxygen uncoupling process with the objective of identifying materials with high reactivity and sufficient attrition resistance. Eleven oxygen carrier materials were produced by spray-drying and then calcined for 4 h at 1100 and 1200 degrees C. The ability of the oxygen carriers to release oxygen and to convert gaseous fuels was investigated in a batch fluidized-bed reactor under alternating reducing and oxidizing conditions for temperatures ranging from 850 degrees C to 1050 degrees C. The attrition behavior of the different materials was evaluated in a jet-cup attrition rig. All investigated oxygen carriers proved to release oxygen and showed high reactivity toward synthesis gas (50% CO in H-2). Oxygen carrier materials with comparably lower mechanical stability were found to have a higher reactivity toward methane. One of the investigated formulations showed to have both high mechanical stability and resistance toward attrition, as well as good methane conversion and oxygen release.
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| 24. |
- Arjmand, Mehdi, 1986, et al.
(författare)
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Standard Enthalpy of Formation of CuAl2O4 Revisited
- 2015
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Ingår i: Chemical Engineering Communications. - : Informa UK Limited. - 0098-6445 .- 1563-5201. ; 202:5, s. 694-697
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Tidskriftsartikel (refereegranskat)abstract
- Due to discrepancy in the standard enthalpy of formation, ΔH_f^0, of copper(II) aluminate (CuAl2O4) reported in thermodynamic databases, the calculated reaction enthalpy, ΔH_r, of CuAl2O4 with reducing gases varies considerably. In this work, the standard enthalpy of formation, ΔH_f^0, of copper(II) aluminate (CuAl2O4) is reassessed using the reaction enthalpy, ΔH_r, of CuAl2O4 with CO measured by differential scanning calorimetry (DSC). A value of –1824.4±4.1 kJ/mol was found for the standard enthalpy of formation, ΔH_f^0, of CuAl2O4.
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| 25. |
- Arjmand, Mehdi, 1986, et al.
(författare)
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Sulfur Tolerance and Rate of Oxygen Release of Combined Mn-Si Oxygen Carriers in Chemical-Looping with Oxygen Uncoupling (CLOU)
- 2014
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Ingår i: Industrial & Engineering Chemistry Research. - : American Chemical Society (ACS). - 1520-5045 .- 0888-5885. ; 53:50, s. 19488-19497
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Tidskriftsartikel (refereegranskat)abstract
- Sulfur tolerance and rate of oxygen release of combined Mn-Si oxygen carriers for chemical-looping with oxygen uncoupling (CLOU) is investigated. The oxygen carriers were produced by spray-drying and calcined at 1150 degrees C. The resistance toward sulfur and the rates of oxygen release were evaluated in a laboratory-scale fluidized-bed reactor. It was found that the combined Mn-Si oxygen carrier is tolerant to SO2, at least up to a partial pressure of 5000 vppm. The rates of oxygen release were determined in the temperature range of 975 to 1100 degrees C using devolatilized wood char as fuel while fluidizing with N-2, to maintain a low oxygen partial pressure surrounding the particles. The Arrhenius parameters k(o) and E-app for the release of oxygen were estimated for the investigated materials assuming a zero-order reaction with respect to oxygen. The rates of oxygen release were relatively high, particularly at above 1050 degrees C. From the obtained reaction rates, the solids inventory required for combustion of coal was determined to be as low as 40 kg/MWth in the fuel reactor at 1100 degrees C. The results indicated that combined Mn-Si oxygen carriers could be interesting materials for the CLOU process by virtue of their resistance to sulfur deactivation and high rate of oxygen release.
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