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Title: Integrated High Temperature Coal-to-Hydrogen System with CO2 Separation

Abstract

A significant barrier to the commercialization of coal-to-hydrogen technologies is high capital cost. The purity requirements for H{sub 2} fuels are generally met by using a series of unit clean-up operations for residual CO removal, sulfur removal, CO{sub 2} removal and final gas polishing to achieve pure H{sub 2}. A substantial reduction in cost can be attained by reducing the number of process operations for H{sub 2} cleanup, and process efficiency can be increased by conducting syngas cleanup at higher temperatures. The objective of this program was to develop the scientific basis for a single high-temperature syngas-cleanup module to produce a pure stream of H{sub 2} from a coal-based system. The approach was to evaluate the feasibility of a 'one box' process that combines a shift reactor with a high-temperature CO{sub 2}-selective membrane to convert CO to CO{sub 2}, remove sulfur compounds, and remove CO{sub 2} in a simple, compact, fully integrated system. A system-level design was produced for a shift reactor that incorporates a high-temperature membrane. The membrane performance targets were determined. System level benefits were evaluated for a coal-to-hydrogen system that would incorporate membranes with properties that would meet the performance targets. The scientific basis for high temperaturemore » CO{sub 2}-selective membranes was evaluated by developing and validating a model for high temperature surface flow membranes. Synthesis approaches were pursued for producing membranes that integrated control of pore size with materials adsorption properties. Room temperature reverse-selectivity for CO{sub 2} was observed and performance at higher temperatures was evaluated. Implications for future membrane development are discussed.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
General Electric Company Incorporation
Sponsoring Org.:
USDOE
OSTI Identifier:
924436
DOE Contract Number:
FC26-05NT42451
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
01 COAL, LIGNITE, AND PEAT; 08 HYDROGEN; COAL GASIFICATION; HYDROGEN PRODUCTION; CARBON DIOXIDE; REMOVAL; SYNTHESIS GAS; HOT GAS CLEANUP; CARBON MONOXIDE; DESULFURIZATION; SHIFT PROCESSES; MEMBRANES; PERFORMANCE

Citation Formats

James A. Ruud, Anthony Ku, Vidya Ramaswamy, Wei Wei, and Patrick Willson. Integrated High Temperature Coal-to-Hydrogen System with CO2 Separation. United States: N. p., 2007. Web. doi:10.2172/924436.
James A. Ruud, Anthony Ku, Vidya Ramaswamy, Wei Wei, & Patrick Willson. Integrated High Temperature Coal-to-Hydrogen System with CO2 Separation. United States. doi:10.2172/924436.
James A. Ruud, Anthony Ku, Vidya Ramaswamy, Wei Wei, and Patrick Willson. Thu . "Integrated High Temperature Coal-to-Hydrogen System with CO2 Separation". United States. doi:10.2172/924436. https://www.osti.gov/servlets/purl/924436.
@article{osti_924436,
title = {Integrated High Temperature Coal-to-Hydrogen System with CO2 Separation},
author = {James A. Ruud and Anthony Ku and Vidya Ramaswamy and Wei Wei and Patrick Willson},
abstractNote = {A significant barrier to the commercialization of coal-to-hydrogen technologies is high capital cost. The purity requirements for H{sub 2} fuels are generally met by using a series of unit clean-up operations for residual CO removal, sulfur removal, CO{sub 2} removal and final gas polishing to achieve pure H{sub 2}. A substantial reduction in cost can be attained by reducing the number of process operations for H{sub 2} cleanup, and process efficiency can be increased by conducting syngas cleanup at higher temperatures. The objective of this program was to develop the scientific basis for a single high-temperature syngas-cleanup module to produce a pure stream of H{sub 2} from a coal-based system. The approach was to evaluate the feasibility of a 'one box' process that combines a shift reactor with a high-temperature CO{sub 2}-selective membrane to convert CO to CO{sub 2}, remove sulfur compounds, and remove CO{sub 2} in a simple, compact, fully integrated system. A system-level design was produced for a shift reactor that incorporates a high-temperature membrane. The membrane performance targets were determined. System level benefits were evaluated for a coal-to-hydrogen system that would incorporate membranes with properties that would meet the performance targets. The scientific basis for high temperature CO{sub 2}-selective membranes was evaluated by developing and validating a model for high temperature surface flow membranes. Synthesis approaches were pursued for producing membranes that integrated control of pore size with materials adsorption properties. Room temperature reverse-selectivity for CO{sub 2} was observed and performance at higher temperatures was evaluated. Implications for future membrane development are discussed.},
doi = {10.2172/924436},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu May 31 00:00:00 EDT 2007},
month = {Thu May 31 00:00:00 EDT 2007}
}

Technical Report:

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  • This is the first semi-annual progress report for the program "Integrated High Temperature Coal to Hydrogen System with CO2 Separation." The objective of the program is to develop a detailed design for a single high-temperature syngas-cleanup module to produce a pure stream of H2 from a coal-based system and to develop the new high-temperature membrane materials at the core of that design. The novel one-box process combines a shift reactor with a high-temperature CO2-selective membrane to convert CO to CO2, remove sulfur compounds, and remove CO2 in a simple, compact, fully integrated system. In the first six months of themore » program, a conceptual design for the one-box system was developed in Task 1 and the performance targets for the system and the membrane were evaluated. In Task 2.1 processes were developed for creating pore architectures in ceramics that are applicable to membrane structures. In Task 2.2, candidate materials were identified that have the potential for separation of CO2 and H2S at high temperatures.« less
  • The water gas shift reaction (WGSR) plays a major role in increasing the hydrogen production from fossil fuels. However, the enhanced hydrogen production is limited by thermodynamic constrains posed by equilibrium limitations of WGSR. This project aims at using a mesoporous, tailored, highly reactive calcium based sorbent system for incessantly removing the CO{sub 2} product which drives the equilibrium limited WGSR forward. In addition, a pure sequestration ready CO{sub 2} stream is produced simultaneously. A detailed project vision with the description of integration of this concept with an existing coal gasification process for hydrogen production is presented. Conceptual reactor designsmore » for investigating the simultaneous water gas shift and the CaO carbonation reactions are presented. In addition, the options for conducting in-situ sorbent regeneration under vacuum or steam are also reported. Preliminary, water gas shift reactions using high temperature shift catalyst and without any sorbent confirmed the equilibrium limitation beyond 600 C demonstrating a carbon monoxide conversion of about 80%. From detailed thermodynamic analyses performed for fuel gas streams from typical gasifiers the optimal operating temperature range to prevent CaO hydration and to effect its carbonation is between 575-830 C.« less
  • Hydrogen production cannot be maximized from fossil fuels (gas/coal) via the WGS reaction at high temperatures as the WGS-equilibrium constant K{sub WGS} (= [CO{sub 2}][H{sub 2}]/[CO][H{sub 2}O]), falls with increasing temperatures. However, CO{sub 2} removal down to ppm levels by the carbonation of CaO to CaCO{sub 3} in the temperature range 650-850 C, leads to the possibility of stoichiometric H{sub 2} production at high temperature/pressure conditions and at low steam to fuel ratios. Further, CO{sub 2} is also captured in the H{sub 2} generation process, making this coal to hydrogen process compatible with CO{sub 2} sequestration goals. While microporous CaOmore » sorbents attain <50% conversion over cyclical carbonation-calcination, the OSU-patented, mesoporous CaO sorbents are able to achieve >95% conversion. Novel calcination techniques could lead to an ever-smaller footprint, single-stage reactors that achieve maximum theoretical H{sub 2} production at high temperatures and pressures for on/off site usage. Experimental results indicate that the PCC-CaO sorbent is able to achieve complete conversion of CO for 240 seconds as compared to only a few seconds with CaO derived from natural sources.« less
  • Hydrogen production by the water gas shift reaction (WGSR) is equilibrium limited due to thermodynamic constrains. However, this can be overcome by continuously removing the product CO{sub 2}, thereby driving the WGSR in the forward direction to enhance hydrogen production. This project aims at using a high reactivity, mesoporous calcium based sorbent (PCC-CaO) for removing CO{sub 2} using reactive separation scheme. Preliminary results have shown that PCC-CaO dominates in its performance over naturally occurring limestone towards enhanced hydrogen production. However, maintenance of high reactivity of the sorbent over several reaction-regeneration cycles warrants effective regeneration methods. We have identified sub-atmospheric calcinationmore » (vacuum) as vital regeneration technique that helps preserve the sorbent morphology. Sub-atmospheric calcination studies reveal the significance of vacuum level, diluent gas flow rate, thermal properties of diluent gas, and sorbent loading on the kinetics of calcination and the morphology of the resultant CaO sorbent. Steam, which can be easily separated from CO{sub 2}, has been envisioned as a potential diluent gas due to its better thermal properties resulting in effective heat transfer. A novel multi-fixed bed reactor was designed which isolates the catalyst bed from the sorbent bed during the calcination step. This should prevent any potential catalyst deactivation due to oxidation by CO{sub 2} during the regeneration phase.« less