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Title: SEPARATION OF HYDROGEN AND CARBON DIOXIDE USING A NOVEL MEMBRANE REACTOR IN ADVANCED FOSSIL ENERGY CONVERSION PROCESS

Abstract

Inorganic membrane reactors offer the possibility of combining reaction and separation in a single operation at high temperatures to overcome the equilibrium limitations experienced in conventional reactor configurations. Such attractive features can be advantageously utilized in a number of potential commercial opportunities, which include dehydrogenation, hydrogenation, oxidative dehydrogenation, oxidation and catalytic decomposition reactions. However, to be cost effective, significant technological advances and improvements will be required to solve several key issues which include: (a) permselective thin solid film, (b) thermal, chemical and mechanical stability of the film at high temperatures, and (c) reactor engineering and module development in relation to the development of effective seals at high temperature and high pressure. In this project, we are working on the development and application of palladium and palladium-silver alloy thin-film composite membranes in membrane reactor-separator configuration for simultaneous production and separation of hydrogen and carbon dioxide at high temperature. From our research on Pd-composite membrane, we have demonstrated that the new membrane has significantly higher hydrogen flux with very high perm-selectivity than any of the membranes commercially available. The steam reforming of methane by equilibrium shift in Pd-composite membrane reactor is being studied to demonstrate the potential application of this new development.more » A two-dimensional, pseudo-homogeneous membrane-reactor model was developed to investigate the steam-methane reforming (SMR) reactions in a Pd-based membrane reactor. Radial diffusion was taken into consideration to account for the concentration gradient in the radial direction due to hydrogen permeation through the membrane. With appropriate reaction rate expressions, a set of partial differential equations was derived using the continuity equation for the reaction system. The equations were solved by finite difference method. The solution of the model equations is complicated by the coupled reactions. At the inlet, if there is no hydrogen, rate expressions become singular. To overcome this problem, the first element of the reactor was treated as a continuous stirred tank reactor (CSTR). Several alternative numerical schemes were implemented in the solution algorithm to get a converged, stable solution. The model was also capable of handling steam-methane reforming reactions under non-membrane condition and equilibrium reaction conversions. Some of the numerical results were presented in the previous report. To test the membrane reactor model, we fabricated Pd-stainless steel membranes in tubular configuration using electroless plating method coupled with osmotic pressure. Scanning Electron Microscopy (SEM) and Energy Dispersive Xray (EDX) were used to characterize the fabricated Pd-film composite membranes. Gas-permeation tests were performed to measure the permeability of hydrogen, nitrogen and helium using pure gas. Some of these results are discussed in this progress report.« less

Authors:
Publication Date:
Research Org.:
North Carolina A& T State University (US)
Sponsoring Org.:
(US)
OSTI Identifier:
822761
DOE Contract Number:
FG26-99FT40620
Resource Type:
Technical Report
Resource Relation:
Other Information: PBD: 17 Feb 2004
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; ALGORITHMS; ALLOYS; CARBON DIOXIDE; CONTINUITY EQUATIONS; ENERGY CONVERSION; FINITE DIFFERENCE METHOD; HYDROGEN; MEMBRANES; NITROGEN; OXIDATION; PALLADIUM; PARTIAL DIFFERENTIAL EQUATIONS; PROGRESS REPORT; REACTION KINETICS; SCANNING ELECTRON MICROSCOPY

Citation Formats

Shamsuddin Ilias. SEPARATION OF HYDROGEN AND CARBON DIOXIDE USING A NOVEL MEMBRANE REACTOR IN ADVANCED FOSSIL ENERGY CONVERSION PROCESS. United States: N. p., 2004. Web. doi:10.2172/822761.
Shamsuddin Ilias. SEPARATION OF HYDROGEN AND CARBON DIOXIDE USING A NOVEL MEMBRANE REACTOR IN ADVANCED FOSSIL ENERGY CONVERSION PROCESS. United States. doi:10.2172/822761.
Shamsuddin Ilias. 2004. "SEPARATION OF HYDROGEN AND CARBON DIOXIDE USING A NOVEL MEMBRANE REACTOR IN ADVANCED FOSSIL ENERGY CONVERSION PROCESS". United States. doi:10.2172/822761. https://www.osti.gov/servlets/purl/822761.
@article{osti_822761,
title = {SEPARATION OF HYDROGEN AND CARBON DIOXIDE USING A NOVEL MEMBRANE REACTOR IN ADVANCED FOSSIL ENERGY CONVERSION PROCESS},
author = {Shamsuddin Ilias},
abstractNote = {Inorganic membrane reactors offer the possibility of combining reaction and separation in a single operation at high temperatures to overcome the equilibrium limitations experienced in conventional reactor configurations. Such attractive features can be advantageously utilized in a number of potential commercial opportunities, which include dehydrogenation, hydrogenation, oxidative dehydrogenation, oxidation and catalytic decomposition reactions. However, to be cost effective, significant technological advances and improvements will be required to solve several key issues which include: (a) permselective thin solid film, (b) thermal, chemical and mechanical stability of the film at high temperatures, and (c) reactor engineering and module development in relation to the development of effective seals at high temperature and high pressure. In this project, we are working on the development and application of palladium and palladium-silver alloy thin-film composite membranes in membrane reactor-separator configuration for simultaneous production and separation of hydrogen and carbon dioxide at high temperature. From our research on Pd-composite membrane, we have demonstrated that the new membrane has significantly higher hydrogen flux with very high perm-selectivity than any of the membranes commercially available. The steam reforming of methane by equilibrium shift in Pd-composite membrane reactor is being studied to demonstrate the potential application of this new development. A two-dimensional, pseudo-homogeneous membrane-reactor model was developed to investigate the steam-methane reforming (SMR) reactions in a Pd-based membrane reactor. Radial diffusion was taken into consideration to account for the concentration gradient in the radial direction due to hydrogen permeation through the membrane. With appropriate reaction rate expressions, a set of partial differential equations was derived using the continuity equation for the reaction system. The equations were solved by finite difference method. The solution of the model equations is complicated by the coupled reactions. At the inlet, if there is no hydrogen, rate expressions become singular. To overcome this problem, the first element of the reactor was treated as a continuous stirred tank reactor (CSTR). Several alternative numerical schemes were implemented in the solution algorithm to get a converged, stable solution. The model was also capable of handling steam-methane reforming reactions under non-membrane condition and equilibrium reaction conversions. Some of the numerical results were presented in the previous report. To test the membrane reactor model, we fabricated Pd-stainless steel membranes in tubular configuration using electroless plating method coupled with osmotic pressure. Scanning Electron Microscopy (SEM) and Energy Dispersive Xray (EDX) were used to characterize the fabricated Pd-film composite membranes. Gas-permeation tests were performed to measure the permeability of hydrogen, nitrogen and helium using pure gas. Some of these results are discussed in this progress report.},
doi = {10.2172/822761},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2004,
month = 2
}

Technical Report:

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  • Inorganic membrane reactors offer the possibility of combining reaction and separation in a single operation at high temperatures to overcome the equilibrium limitations experienced in conventional reactor configurations. Such attractive features can be advantageously utilized in a number of potential commercial opportunities, which include dehydrogenation, hydrogenation, oxidative dehydrogenation, oxidation and catalytic decomposition reactions. However, to be cost effective, significant technological advances and improvements will be required to solve several key issues which include: (a) permselective thin solid film, (b) thermal, chemical and mechanical stability of the film at high temperatures, and (c) reactor engineering and module development in relation tomore » the development of effective seals at high temperature and high pressure. In this project, we are working on the development and application of palladium and palladium-silver alloy thin-film composite membranes in membrane reactor-separator configuration for simultaneous production and separation of hydrogen and carbon dioxide at high temperature. From our research on Pd-composite membrane, we have demonstrated that the new membrane has significantly higher hydrogen flux with very high perm-selectivity than any of the membranes commercially available. The steam reforming of methane by equilibrium shift in Pd-composite membrane reactor is being studied to demonstrate the potential application this new development. To have better understanding of the membrane reactor, during this reporting period, we developed a two-dimensional pseudo-homogeneous reactor model for steam reforming of methane by equilibrium shift in a tubular membrane reactor. In numerical solution of the reactor model equations, numerical difficulties were encountered and we seeking alternative solution techniques to overcome the problem.« less
  • Inorganic membrane reactors offer the possibility of combining reaction and separation in a single operation at high temperatures to overcome the equilibrium limitations experienced in conventional reactor configurations. Such attractive features can be advantageously utilized in a number of potential commercial opportunities, which include dehydrogenation, hydrogenation, oxidative dehydrogenation, oxidation and catalytic decomposition reactions. However, to be cost effective, significant technological advances and improvements will be required to solve several key issues which include: (a) permselective thin solid film, (b) thermal, chemical and mechanical stability of the film at high temperatures, and (c) reactor engineering and module development in relation tomore » the development of effective seals at high temperature and high pressure. In this project, we are working on the development and application of palladium and palladium-silver alloy thin-film composite membranes in membrane reactor-separator configuration for simultaneous production and separation of hydrogen and carbon dioxide at high temperature. From our research on Pd-composite membrane, we have demonstrated that the new membrane has significantly higher hydrogen flux with very high perm-selectivity than any of the membranes commercially available. The steam reforming of methane by equilibrium shift in Pd-composite membrane reactor is being studied to demonstrate the potential application this new development. We designed and built a membrane reactor to study the reforming reaction. A two-dimensional pseudo-homogeneous reactor model was developed to study the performance of the membrane reactor parametrically. The important results are presented in this report.« less
  • Inorganic membrane reactors offer the possibility of combining reaction and separation in a single operation at high temperatures to overcome the equilibrium limitations experienced in conventional reactor configurations. Such attractive features can be advantageously utilized in a number of potential commercial opportunities, which include dehydrogenation, hydrogenation, oxidative dehydrogenation, oxidation and catalytic decomposition reactions. However, to be cost effective, significant technological advances and improvements will be required to solve several key issues which include: (a) permselective thin solid film, (b) thermal, chemical and mechanical stability of the film at high temperatures, and (c) reactor engineering and module development in relation tomore » the development of effective seals at high temperature and high pressure. In this project, we are working on the development and application of palladium and palladium-silver alloy thin-film composite membranes in membrane reactor-separator configuration for simultaneous production and separation of hydrogen and carbon dioxide at high temperature. From our research on Pd-composite membrane, we have demonstrated that the new membrane has significantly higher hydrogen flux with very high perm-selectivity than any of the membranes commercially available. The steam reforming of methane by equilibrium shift in Pd-composite membrane reactor is being studied to demonstrate the potential application of this new development. A two-dimensional, pseudo-homogeneous membrane-reactor model was developed to investigate the steam-methane reforming (SMR) reactions in a Pd-based membrane reactor. Radial diffusion was taken into consideration to account for the concentration gradient in the radial direction due to hydrogen permeation through the membrane. With appropriate reaction rate expressions, a set of partial differential equations was derived using the continuity equation for the reaction system. The equations were solved by finite difference method. The solution of the model equations is complicated by the coupled reactions. At the inlet, if there is no hydrogen, rate expressions become singular. To overcome this problem, the first element of the reactor was treated as a continuous stirred tank reactor (CSTR). Several alternative numerical schemes were implemented in the solution algorithm to get a converged, stable solution. The model was also capable of handling steam-methane reforming reactions under non-membrane condition and equilibrium reaction conversions. Some of the numerical results were presented in the previous report. To test the membrane reactor model, we fabricated Pd-stainless steel membranes in tubular configuration using electroless plating method coupled with osmotic pressure. Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) were used to characterize the fabricated Pd-film composite membranes. Gas-permeation tests were performed to measure the permeability of hydrogen, nitrogen and helium using pure gas. The membranes showed excellent perm-selectivity for hydrogen. This makes the Pd-composite membrane attractive for selective separation and recovery of H{sub 2} from mixed gases at elevated temperature.« less
  • The objective of the project was to develop a novel complementary membrane reactor process that can consolidate two or more downstream unit operations of a coal gasification system into a single module for production of a pure stream of hydrogen and a pure stream of carbon dioxide. The overall goals were to achieve higher hydrogen production efficiencies, lower capital costs and a smaller overall footprint than what could be achieved by utilizing separate components for each required unit process/operation in conventional coal-to-hydrogen systems. Specifically, this project was to develop a novel membrane reactor process that combines hydrogen sulfide removal, hydrogenmore » separation, carbon dioxide separation and water-gas shift reaction into a single membrane configuration. The carbon monoxide conversion of the water-gas-shift reaction from the coal-derived syngas stream is enhanced by the complementary use of two membranes within a single reactor to separate hydrogen and carbon dioxide. Consequently, hydrogen production efficiency is increased. The single membrane reactor configuration produces a pure H{sub 2} product and a pure CO{sub 2} permeate stream that is ready for sequestration. This project focused on developing a new class of CO{sub 2}-selective membranes for this new process concept. Several approaches to make CO{sub 2}-selective membranes for high-temperature applications have been tested. Membrane disks using the technique of powder pressing and high temperature sintering were successfully fabricated. The powders were either metal oxide or metal carbonate materials. Experiments on CO{sub 2} permeation testing were also performed in the temperature range of 790 to 940 C for the metal carbonate membrane disks. However, no CO{sub 2} permeation rate could be measured, probably due to very slow CO{sub 2} diffusion in the solid state carbonates. To improve the permeation of CO{sub 2}, one approach is to make membranes containing liquid or molten carbonates. Several different types of dual-phase membranes were fabricated and tested for their CO{sub 2} permeation in reducing conditions without the presence of oxygen. Although the flux was quite low, on the order of 0.01-0.001 cc STP/cm{sup 2}/min, the selectivity of CO{sub 2}/He was almost infinite at temperatures of about 800 C. A different type of dual-phase membrane prepared by Arizona State University (ASU) was also tested at GTI for CO{sub 2} permeation. The measured CO{sub 2} fluxes were 0.015 and 0.02 cc STP/cm{sup 2}/min at 750 and 830 C, respectively. These fluxes were higher than the previous flux obtained ({approx}0.01 cc STP/cm{sup 2}/min) using the dual-phase membranes prepared by GTI. Further development in membrane development should be conducted to improve the CO{sub 2} flux. ASU has also focused on high temperature permeation/separation experiments to confirm the carbon dioxide separation capabilities of the dual-phase membranes with La{sup 0.6}Sr{sub 0.4}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} (LSCF6482) supports infiltrated with a Li/Na/K molten carbonate mixture (42.5/32.5/25.0 mole %). The permeation experiments indicated that the addition of O{sub 2} does improve the permeance of CO{sub 2} through the membrane. A simplified membrane reactor model was developed to evaluate the performance of the process. However, the simplified model did not allow the estimation of membrane transport area, an important parameter for evaluating the feasibility of the proposed membrane reactor technology. As a result, an improved model was developed. Results of the improved membrane reactor model show that the membrane shift reaction has promise as a means to simplify the production of a clean stream of hydrogen and a clean stream of carbon dioxide. The focus of additional development work should address the large area required for the CO{sub 2} membrane as identified in the modeling calculations. Also, a more detailed process flow diagram should be developed that includes integration of cooling and preheating feed streams as well as particulate removal so that steam and power generation could be optimized. For the tubular membranes that were fabricated by solution impregnation with metal carbonates, difficulties were encountered in removing the impurity salts that were trapped inside the porous support tube. The membrane tube would continue losing weight even after being heated up to 500 C in air and could not maintain its nonporous characteristics. This approach was therefore abandoned. Dual-phase membranes with molten carbonates were subsequently shown to have CO{sub 2} permeability in reducing conditions without the presence of oxygen; they were also tested for H{sub 2}S permeation. Permeation tests were conducted with a gas feed composition consisting of 33.6% CO{sub 2}, 8.4% He, 57.6% H{sub 2} and 0.4% H{sub 2}S at temperatures between 820 and 850 C and a pressure of 1 bar.« less
  • CO{sub 2} captured from coal-fired power plants represents three-quarters of the total cost of an entire carbon sequestration process. Conventional amine absorption or cryogenic separation requires high capital investment and is very energy intensive. Our novel membrane process is energy efficient with great potential for economical CO{sub 2} capture. Three classes of microporous sol-gel derived silica-based membranes were developed for selective CO{sub 2} removal under simulated flue gas conditions (SFG), e.g. feed of 10% vol. CO{sub 22} in N{sub 2}, 1 atm total pressure, T = 50-60 C, RH>50%, SO2>10 ppm. A novel class of amine-functional microporous silica membranes wasmore » prepared using an amine-derivatized alkoxysilane precursor, exhibiting enhanced (>70) CO{sub 2}:N{sub 2} selectivity in the presence of H{sub 2}O vapor, but its CO{sub 2} permeance was lagging (<1 MPU). Pure siliceous membranes showed higher CO{sub 2} permeance (1.5-2 MPU) but subsequent densification occurred under prolonged SFG conditions. We incorporated NiO in the microporous network up to a loading of Ni:Si = 0.2 to retard densification and achieved CO2 permeance of 0.5 MPU and CO{sub 2}:N{sub 2} selectivity of 50 after 163 h exposure to SFG conditions. However, CO{sub 2} permeance should reach greater than 2.0 MPU in order to achieve the cost of electricity (COE) goal set by DOE. We introduced the atomic layer deposition (ALD), a molecular deposition technique that substantially reduces membrane thickness with intent to improve permeance and selectivity. The deposition technique also allows the incorporation of Ni or Ag cations by proper selection of metallorganic precursors. In addition, preliminary economic analysis provides a sensitivity study on the performance and cost of the proposed membranes for CO{sub 2} capture. Significant progress has been made toward the practical applications for CO{sub 2} capture. (1 MPU = 1.0 cm{sup 3}(STP){center_dot}cm-2{center_dot}min-1{center_dot}atm-1)« less