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Title: Fabrication and processing of next-generation oxygen carrier materials for chemical looping combustion

Abstract

Among numerous methods of controlling the global warming effect, Chemical Looping Combustion is known to be the most viable option currently. A key factor to a successful chemical looping process is the presence of highly effective oxygen carriers that enable fuel combustion by going through oxidation and reduction in the presence of air and fuel respectively. In this study, CaMnO 3-δ was used as the base material and doped on the A-site (Sr or La) and B-site (Fe, Ti, Zn and Al) by 10 mol % of dopants. Solid state reaction followed by mechanical extrusion (optimized paste formula) was used as the preparation method A series of novel doped perovskite-type oxygen carrier particles (Ca xLa (Or Sa) 1-x Mn 1-yByO 3-δ (B-site = Fe, Ti, Al, or Zr)) were synthesized by the proposed extrusion formula. The produced samples were characterized with XRD, SEM, BET and TGA techniques. According to the results obtained from TGA analysis, the oxygen capacity of the samples ranged between 1.2 for CLMZ and 1.75 for CSMF. Reactivity and oxygen uncoupling behaviors of the prepared samples were also evaluated using a fluidized bed chemical looping reactor using methane as the fuel at four different temperatures (800, 850,more » 900, 950 °C). All of the oxygen carriers showed oxygen uncoupling behavior and they were able to capture and release oxygen. Mass-based conversion of the perovskites was calculated and temperature increase proved to increase the mass-based conversion rate in all of the samples under study. Gas yield was calculated at 950 °C as well, and results showed that CLMZ, CM and CSMF showed 100% gas yields and CLMF and CSMZ showed approximately 85% yield in fluidized bed reactor, which is a high and acceptable quantity. Based on extended reactor tests the modified calcium manganese perovskite structures (CSMF) can be a good candidate for future pilot tests.« less

Authors:
 [1]
  1. Univ. of Toledo, OH (United States)
Publication Date:
Research Org.:
Univ. of Toledo, OH (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE), Clean Coal and Carbon (FE-20)
OSTI Identifier:
1353031
Report Number(s):
DE-FE0008774
DOE Contract Number:
FE0008774
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION; Porous perovskite; Chemical looping combustion and Calcium manganese

Citation Formats

Nadarajah, Arunan. Fabrication and processing of next-generation oxygen carrier materials for chemical looping combustion. United States: N. p., 2017. Web. doi:10.2172/1353031.
Nadarajah, Arunan. Fabrication and processing of next-generation oxygen carrier materials for chemical looping combustion. United States. doi:10.2172/1353031.
Nadarajah, Arunan. Wed . "Fabrication and processing of next-generation oxygen carrier materials for chemical looping combustion". United States. doi:10.2172/1353031. https://www.osti.gov/servlets/purl/1353031.
@article{osti_1353031,
title = {Fabrication and processing of next-generation oxygen carrier materials for chemical looping combustion},
author = {Nadarajah, Arunan},
abstractNote = {Among numerous methods of controlling the global warming effect, Chemical Looping Combustion is known to be the most viable option currently. A key factor to a successful chemical looping process is the presence of highly effective oxygen carriers that enable fuel combustion by going through oxidation and reduction in the presence of air and fuel respectively. In this study, CaMnO3-δ was used as the base material and doped on the A-site (Sr or La) and B-site (Fe, Ti, Zn and Al) by 10 mol % of dopants. Solid state reaction followed by mechanical extrusion (optimized paste formula) was used as the preparation method A series of novel doped perovskite-type oxygen carrier particles (CaxLa (Or Sa)1-x Mn1-yByO3-δ (B-site = Fe, Ti, Al, or Zr)) were synthesized by the proposed extrusion formula. The produced samples were characterized with XRD, SEM, BET and TGA techniques. According to the results obtained from TGA analysis, the oxygen capacity of the samples ranged between 1.2 for CLMZ and 1.75 for CSMF. Reactivity and oxygen uncoupling behaviors of the prepared samples were also evaluated using a fluidized bed chemical looping reactor using methane as the fuel at four different temperatures (800, 850, 900, 950 °C). All of the oxygen carriers showed oxygen uncoupling behavior and they were able to capture and release oxygen. Mass-based conversion of the perovskites was calculated and temperature increase proved to increase the mass-based conversion rate in all of the samples under study. Gas yield was calculated at 950 °C as well, and results showed that CLMZ, CM and CSMF showed 100% gas yields and CLMF and CSMZ showed approximately 85% yield in fluidized bed reactor, which is a high and acceptable quantity. Based on extended reactor tests the modified calcium manganese perovskite structures (CSMF) can be a good candidate for future pilot tests.},
doi = {10.2172/1353031},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Apr 26 00:00:00 EDT 2017},
month = {Wed Apr 26 00:00:00 EDT 2017}
}

Technical Report:

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  • Chemical-looping combustion (CLC) is a combustion technology for clean and efficient utilization of fossil fuels for energy production. This process which produces sequestration ready CO2 systems is a promising technology to be utilized with coal gasification systems. In the present work, chemical-looping combustion has been studied with an oxygen carrier, NiO/bentonite (60 wt % NiO) for the gasification systems utilizing simulated synthesis gas. Global reaction rates of reduction and oxidation as a function of conversion were calculated for oxidation-reduction cycles utilizing the thermogravimetric analysis (TGA) data on multicycle tests conducted with NiO/bentonite at atmospheric pressure between 700 and 900 °C.more » The rate of reduction increased slightly with an increase in temperature, while the rate of oxidation decreased at 900 °C. The effect of particle size of the oxygen carrier on CLC was studied for the particle size between 20 and 200 mesh. The rates of reactions depended on the particle size of the oxygen carrier. The smaller the particle size, the higher the reaction rates. The multicycle CLC tests conducted in a high-pressure flow reactor showed stable reactivity for the production of CO2 from fuel gas at 800 and 900 °C and full consumption of hydrogen during the reaction. The data from a one cycle test on the effect of the pressure on the performance with NiO/bentonite utilizing the tapered element oscillating microbalance (TEOM) showed a positive effect of the pressure on the global rates of reduction-oxidation reactions at higher fractional conversions. The X-ray diffraction (XRD) analysis confirmed the presence of the NiO phase in NiO/bentonite with the oxidized sample in the highpressure reactor and Ni phase with the reduced sample. The presence of a small amount of NiO in the reduced sample detected by X-ray photoelectron spectroscopy (XPS) may be due to its exposure to air during sample transfer from the reactor to XPS. Scanning electron microscopy (SEM) analysis showed no significant changes in morphology of NiO/bentonite reacted in the temperature range 700-800 °C in an atmospheric TGA for 10 oxidation-reduction cycles, but some loss of surface area and porosity was observed at 900 °C. This effect was found to be greater with increase in the particle size of the oxygen carrier.« less
  • In the present work, NETL researchers have studied chemical looping combustion (CLC) with an oxygen carrier NiO/bentonite (60 wt.% NiO) for the IGCC systems utilizing simulated synthesis gas. Multi cycle CLC was conducted with NiO/Bentonite in TGA at atmospheric pressure and in a high pressure reactor in a temperature range between 700-900°C. Global reaction rates of reduction and oxidation as a function of conversion were calculated for all oxidation-reduction cycles utilizing the TGA data. The effect of particle size of the oxygen carrier on CLC was studied for the size between 20-200 mesh. The multi cycle CLC tests conducted inmore » a high pressure packed bed flow reactor indicated constant total production of CO2 from fuel gas at 800°C and 900°C and full consumption of hydrogen during the reaction.« less
  • This paper is the second in a series of two on the investigation of the chemical looping combustion (CLC) of solid fuels. The first paper put forward the concept of the CLC of solid fuels using a circulating fluidized bed as a reactor and Cu-CuO as the oxygen carrier, which was based on an analysis of oxygen transfer capability, reaction enthalpy, and chemical equilibrium. In this second paper, we report the results of the evaluation of the reduction of CuO reduced by solid fuels such as coal and some other 'opportunity' solid fuels. Tests on the reduction of CuO bymore » the selected solid fuels were conducted using simultaneous differential scanning calorimetry and thermogravimetric analysis, which simulates a microreactor. An attached mass spectrometer (MS) was used for the characterization of evolved gaseous products. The X-ray diffractometer (XRD) and scanning electron microscope (SEM) were used for the characterization of the solid residues. Results strongly supported the feasibility of CuO reduction by selected solid fuels. CuO can be fully converted into Cu in a reduction process, either in a direct path by solid fuels, which was verified by MS analysis under a N{sub 2} atmosphere, or in an indirect path by pyrolysis and gasification products of solid fuels in the reducer. No Cu{sub 2}O exists in reducing atmospheres, which was characterized by an XRD analysis and mass balance calculations. No carbon deposit was found on the surface of the reduced Cu, which was characterized by SEM analysis. CuO reduction by solid fuels can start at temperatures as low as approximately 500 C. Tests indicated that the solid fuels with higher reactivity (higher volatile matter) would be desirable for the development of the chemical looping combustion process of solid fuels, such as sub-bituminous Powder River Basin coal and solid waste and biomass. 4 refs., 12 figs., 3 tabs.« less
  • Chemical looping combustion (CLC) has been suggested as an energy-efficient method for the capture of carbon dioxide from combustion. It is indirect combustion by the use of an oxygen carrier, which can be used for CO{sub 2} capture in power-generating processes. The possibility of CLC using a calcium-based oxygen carrier is investigated in this paper. In the air reactor air is supplied to oxidize CaS to CaSO{sub 4}, where oxygen is transferred from air to the oxygen carrier; the reduction of CaSO{sub 4} to CaS takes place in the fuel reactor. The exit gas from the fuel reactor is CO{submore » 2} and H{sub 2}O. After condensation of water, almost pure CO{sub 2} could be obtained. The thermodynamic and kinetic problem of the reduction reactions of CaSO{sub 4} with CO and H{sub 2} and the oxidization reactions of CaS with O{sub 2} is discussed in the paper to investigate the technique possibility. To prevent SO{sub 2} release from the process of chemical looping combustion using a calcium-based oxygen carrier, thermochemical CaSO{sub 4} reduction and CaS oxidation are discussed. Thermal simulation experiments are carried out using a thermogravimetric analyzer (TGA). The properties of the products are characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray diffractometry (XRD), and the optimal reaction parameters are evaluated. The effects of reaction temperature, reductive gas mixture, and oxygen partial pressure on the composition of flue gas are discussed. The suitable temperature of the air reactor is between 1050 and 1150 C and the optimal temperature of the fuel reactor between 900 and 950 C. (author)« less