skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Dense ceramic membranes for methane conversion

Abstract

This report focuses on a mechanism for oxygen transport through mixed- oxide conductors as used in dense ceramic membrane reactors for the partial oxidation of methane to syngas (CO and H{sub 2}). The in-situ separation of O{sub 2} from air by the membrane reactor saves the costly cryogenic separation step that is required in conventional syngas production. The mixed oxide of choice is SrCo{sub 0.5}FeO{sub x}, which exhibits high oxygen permeability and has been shown in previous studies to possess high stability in both oxidizing and reducing conditions; in addition, it can be readily formed into reactor configurations such as tubes. An understanding of the electrical properties and the defect dynamics in this material is essential and will help us to find the optimal operating conditions for the conversion reactor. In this paper, we discuss the conductivities of the SrFeCo{sub 0.5}O{sub x} system that are dependent on temperature and partial pressure of oxygen. Based on the experimental results, a defect model is proposed to explain the electrical properties of this system. The oxygen permeability of SrFeCo{sub 0.5}O{sub x} is estimated by using conductivity data and is compared with that obtained from methane conversion reaction.

Authors:
; ;  [1];  [2]
+ Show Author Affiliations
  1. Argonne National Lab., IL (United States)
  2. Amoco Oil Co., Naperville, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab., IL (United States)
Sponsoring Org.:
USDOE, Washington, DC (United States)
OSTI Identifier:
267578
Report Number(s):
ANL/ET/CP-90022; CONF-9607126-5
ON: DE96012714
DOE Contract Number:
W-31109-ENG-38
Resource Type:
Technical Report
Resource Relation:
Conference: 1. joint power and fuel systems contractors conference, Pittsburgh, PA (United States), 9-11 Jul 1996; Other Information: PBD: May 1996
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; 03 NATURAL GAS; 36 MATERIALS SCIENCE; SYNTHESIS GAS; PRODUCTION; METHANE; CONVERSION; PARTIAL OXIDATION PROCESSES; MEMBRANES; MATERIALS TESTING; CERAMICS; IONIC CONDUCTIVITY; OXYGEN; MEMBRANE TRANSPORT; SEPARATION PROCESSES; AIR; STRONTIUM OXIDES; COBALT OXIDES; IRON OXIDES; EXPERIMENTAL DATA; CHEMICAL REACTORS

Citation Formats

Balachandran, U., Mieville, R.L., Ma, B., and Udovich, C.A. Dense ceramic membranes for methane conversion. United States: N. p., 1996. Web. doi:10.2172/267578.
Copy to clipboard
Balachandran, U., Mieville, R.L., Ma, B., & Udovich, C.A. Dense ceramic membranes for methane conversion. United States. doi:10.2172/267578.
Copy to clipboard
Balachandran, U., Mieville, R.L., Ma, B., and Udovich, C.A. Wed . "Dense ceramic membranes for methane conversion". United States. doi:10.2172/267578. https://www.osti.gov/servlets/purl/267578.
Copy to clipboard
@article{osti_267578,
title = {Dense ceramic membranes for methane conversion},
author = {Balachandran, U. and Mieville, R.L. and Ma, B. and Udovich, C.A.},
abstractNote = {This report focuses on a mechanism for oxygen transport through mixed- oxide conductors as used in dense ceramic membrane reactors for the partial oxidation of methane to syngas (CO and H{sub 2}). The in-situ separation of O{sub 2} from air by the membrane reactor saves the costly cryogenic separation step that is required in conventional syngas production. The mixed oxide of choice is SrCo{sub 0.5}FeO{sub x}, which exhibits high oxygen permeability and has been shown in previous studies to possess high stability in both oxidizing and reducing conditions; in addition, it can be readily formed into reactor configurations such as tubes. An understanding of the electrical properties and the defect dynamics in this material is essential and will help us to find the optimal operating conditions for the conversion reactor. In this paper, we discuss the conductivities of the SrFeCo{sub 0.5}O{sub x} system that are dependent on temperature and partial pressure of oxygen. Based on the experimental results, a defect model is proposed to explain the electrical properties of this system. The oxygen permeability of SrFeCo{sub 0.5}O{sub x} is estimated by using conductivity data and is compared with that obtained from methane conversion reaction.},
doi = {10.2172/267578},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed May 01 00:00:00 EDT 1996},
month = {Wed May 01 00:00:00 EDT 1996}
}
Copy to clipboard
Technical Report:
View Technical Report (0.48 MB)
DOI:  10.2172/267578
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

  • ; ; ; ...
    The most significant cost associated with partial oxidation of methane to syngas is that of the oxygen plant. In this paper, the authors offer a technology that is based on dense ceramic membranes and that uses air as the oxidant for methane-conversion reactions, thus eliminating the need for the oxygen plant. Certain ceramic materials exhibit both electronic and ionic conductivities (of particular interest is oxygen-ion conductivity). These materials transport not only oxygen ions (functioning as selective oxygen separators) but also electrons back from the reactor side to the oxygen/reduction interface. No external electrodes are required and if the driving potentialmore » of transport is sufficient, the partial oxidation reactions should be spontaneous. Such a system will operate without an externally applied potential. Oxygen is transported across the ceramic material in the form of oxygen anions, not oxygen molecules. In principle, the dense ceramic materials can be shaped into a hollow-tube reactor, with air passed over the outside of the membrane and methane through the inside. The membrane is permeable to oxygen at high temperatures, but not to nitrogen or any other gas. Long tubes of La-Sr-Fe-Co-O (SFC) membrane were fabricated by plastic extrusion, and thermal stability of the tubes was studied as a function of oxygen partial pressure by high-temperature XRD. Mechanical properties were measured and found to be acceptable for a reactor material. Fracture of certain SFC tubes was the consequence of an oxygen gradient that introduced a volumetric lattice difference between the inner and outer walls. However, tubes made with a particular stoichiometry (SFC-2) provided methane conversion efficiencies of >99% in a reactor. Some of the reactor tubes have operated for up to {approx} 1,000 h.« less

  • ; ; ; ...
    In conventional conversion of methane to syngas, a significant cost of the partial oxidation process is that of the oxygen plant. In this report, the authors offer a technology that is based on dense ceramic membranes and that uses air as the oxidant for methane-conversion reactions, thus eliminating the need for the oxygen plant. Certain ceramic materials exhibit both electronic and ionic conductivities (of particular interest is oxygen-ion conductivity). These materials transport not only oxygen ions (functioning as selective oxygen separators) but also electrons back from the reactor side to the oxygen/reduction interface. No external electrodes are required and ifmore » the driving potential of transport is sufficient, the partial-oxidation reactions should be spontaneous. Such a system will operate without an externally applied potential. Oxygen is transported across the ceramic material in the form of oxygen anions, not oxygen molecules. Long tubes of Sr-Fe-Co-O (SFC) membrane were fabricated by plastic extrusion, and thermal stability of the tubes was studied as a function of oxygen partial pressure and high-temperature XRD. Mechanical properties were measured and found to be acceptable for a reactor material. Fracture of certain SFC tubes was the consequence of an oxygen gradient that introduced a volumetric lattice difference between the inner and outer walls. However, tubes made with a particular stoichiometry (SFC-2) provided methane conversion efficiencies of >99% in a reactor and some of these tubes have operated for up to {approx}1,000 h.« less

  • ; ; ; ...
    The most significant cost associated with partial oxidation of methane to syngas is that of the oxygen plant. In this paper, the authors offer a technology, based on dense ceramic membranes, that uses air as the oxidant for methane conversion reactions, thus eliminating the need for the oxygen plant. Certain ceramic materials exhibit both electronic and ionic conductivities (of particular interest is oxygen-ion conductivity). These materials transport not only oxygen ions (functioning as selective oxygen separators) but also electrons back from the reactor side to the oxygen/reduction interface. No external electrodes are required, and, if the driving potential of transportmore » is adequate, the partial oxidation reactions should be spontaneous. Such a system will operate without an externally applied potential. Oxygen is transported across the ceramic material in the form of oxygen ions, not oxygen molecules. Recent reports in the literature suggest that dense ceramic membranes made of these mixed conductors can successfully separate oxygen from air at flux rates that could be considered commercially feasible. Thus, these membranes have the potential to improve the economics of methane conversion processes. In principle, the dense ceramic materials can be shaped into hollow-tube reactors, in which air passes over the outside of the membrane and methane flows through the inside. The surfaces can also be reversed. The membrane is permeable to oxygen at high temperatures, but not to nitrogen or other gases. Thus, only oxygen from air can be transported through the membrane to the inside of the reactor surface, where it reacts with methane. Other geometric forms, such as honeycombs or corrugations, of the reactor are possible and can provide substantially greater surface areas for reaction.« less

  • ; ; ; ...
    Numerous studies have been conducted in recent years on the partial oxidation of methane to synthesis gas (syngas: CO + H{sub 2}) with air as the oxidant. In partial oxidation, a mixed-oxide ceramic membrane selectively transports oxygen from the air; this transport is driven by the oxygen potential gradient. Of the several ceramic materials the authors have tested, a mixed oxide based on the Sr-Fe-Co-O system has been found to be very attractive. Extensive oxygen permeability data have been obtained for this material in methane conversion experiments carried out in a reactor. The data have been analyzed by a transportmore » equation based on the phenomenological theory of diffusion under oxygen potential gradients. Thermodynamic calculations were used to estimate the driving force for the transport of oxygen ions. The results show that the transport equation deduced from the literature describes the permeability data reasonably well and can be used to determine the diffusion coefficients and the associated activation energy of oxygen ions in the ceramic membrane material.« less

  • Mixed-conducting membranes have the ability to conduct oxygen with perfect selectivity at elevated temperatures, which makes them an extremely attractive alternative for oxygen separation and membrane reactor applications. The ability to reliably fabricate these membranes in thin or thick films would enable solid-state divisional limitations to be minimized, thus providing higher oxygen flux. Based on that motivation, the overall objective for this project is to develop and demonstrate a strategy for the fabrication of supported Wick film ceramic mixed conducting membranes, and improve the understanding of the fundamental issues associated with reliable fabrication of these membranes. The project has focusedmore » on the mixed-conducting ceramic composition SrCo{sub 0.5}FeO{sub x} because of its superior permeability and stability in reducing atmospheres. The fabrication strategy employed involves the deposition of SrCo{sub 0.5}FeO{sub x} thick films onto porous supports of the same composition. In the second year of this project, we completed characterization of the sintering and phase behavior of the porous SrCo{sub 0.5}FeO{sub x} supports, leading to a standard support fabrication methodology. Using a doctor blade method, pastes made from aerosol-derived SrCo{sub 0.5}FeO{sub x} powder dispersed with polyethylene glycol were applied to the supports, and the sintering behavior of the thick film membranes was examined in air and nitrogen atmospheres. It has been demonstrated that the desired crystalline phase content can be produced in the membranes, and that the material in the membrane layer can be highly densified without densifying the underlying support. However, considerable cracking and opening of the film occurred when films densified to a high extent. The addition of MgO into the SrCo{sub 0.5}FeO{sub x} supports was shown to inhibit support sintering so that temperatures up to 1300 C, where significant liquid formation occurs, could be used for film sintering. This successfully reduced cracking, however the films retained open porosity. The investigation of this concept will be continued in the final year of the project. Investigation of a metal organic chemical vapor deposition (MOCVD) method for defect mending in dense membranes was also initiated. An appropriate metal organic precursor (iron tetramethylheptanedionate) was identified whose deposition can be controlled by access to oxygen at temperatures in the 280-300 C range. Initial experiments have deposited iron oxide, but only on the membrane surface; thus refinement of this method will continue.« less