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Title: Single Membrane Reactor Configuration for Separation of Hydrogen, Carbon Dioxide and Hydrogen Sulfide

Abstract

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, hydrogen 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-temperaturemore » 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

Authors:
; ; ;
Publication Date:
Research Org.:
Gas Technology Institute, Des Plaines, IL (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
958104
DOE Contract Number:  
FC26-05NT42450
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 01 COAL, LIGNITE, AND PEAT; CAPITALIZED COST; CARBON DIOXIDE; CARBON MONOXIDE; CARBONATES; COAL GASIFICATION; CONFIGURATION; HEAT TREATMENTS; HYDROGEN; HYDROGEN PRODUCTION; HYDROGEN SULFIDES; MEMBRANE TRANSPORT; MEMBRANES; POWER GENERATION; REACTOR TECHNOLOGY; REMOVAL; SULFIDES; SULFUR; WATER GAS

Citation Formats

Roberts, Micheal, Zabransky, Robert, Doong, Shain, and Lin, Jerry. Single Membrane Reactor Configuration for Separation of Hydrogen, Carbon Dioxide and Hydrogen Sulfide. United States: N. p., 2008. Web. doi:10.2172/958104.
Roberts, Micheal, Zabransky, Robert, Doong, Shain, & Lin, Jerry. Single Membrane Reactor Configuration for Separation of Hydrogen, Carbon Dioxide and Hydrogen Sulfide. United States. https://doi.org/10.2172/958104
Roberts, Micheal, Zabransky, Robert, Doong, Shain, and Lin, Jerry. 2008. "Single Membrane Reactor Configuration for Separation of Hydrogen, Carbon Dioxide and Hydrogen Sulfide". United States. https://doi.org/10.2172/958104. https://www.osti.gov/servlets/purl/958104.
@article{osti_958104,
title = {Single Membrane Reactor Configuration for Separation of Hydrogen, Carbon Dioxide and Hydrogen Sulfide},
author = {Roberts, Micheal and Zabransky, Robert and Doong, Shain and Lin, Jerry},
abstractNote = {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, hydrogen 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.},
doi = {10.2172/958104},
url = {https://www.osti.gov/biblio/958104}, journal = {},
number = ,
volume = ,
place = {United States},
year = {2008},
month = {5}
}