Kinetics Of Mn Based Sorbents For Hot Coal Gas Desulfurization Quarterly Report December 15 1993 March 15 1997

Manganese-based sorbents have been investigated for the removal of hydrogen sulfide (the primary sulfur bearing compound) from hot coal gases prior to its use in combined cycle turbines. Four formulations of Mn-based sorbents were tested in an ambient-pressure fixed-bed reactor to determine steady state H2S concentrations, breakthrough times and effectiveness of the sorbent when subjected to cyclic sulfidation and regeneration testing. In previous reports, the sulfidation and regeneration results from cyclic testing done at 600°C were presented. Manganese-based sorbents, with molar ratios> 1:1 Mn:Substrate were effective in reducing the H2S concentration in simulated coal gases to less than 100 ppmv over five cycles. Actual breakthrough time for formulation C6-2-1100 was as high as 73% of breakthrough time based on wt% Mn in sorbent. Regeneration tests determined that loaded pellets can be fully regenerated in air/steam mixture at 750°C with minimal sulfate formation. In this report, the results from cyclic crush strength tests, Sulfur profile tests and cyclic testing at 550°C and lower flowrate cyclic testing are presented. Crush strength testing done after 5 cycles showed decreases in strength from 12.6% to 57.9%. Cyclic testing at 550°C showed pre breakthrough concentrations as low as 10 ppmv. Cyclic testing done at 2 L/min and 3 L/min did not show any significant difference in pre breakthrough concentrations or capacity.

Manganese-based sorbents have been investigated for the removal of hydrogen sulfide (the primary sulfur bearing compound) from hot coal gases prior to its use in combined cycle turbines. Four formulations of Mn-based sorbents were tested in an ambient-pressure fixed-bed reactor to determine steady state H2S concentrations, breakthrough times and effectiveness of the sorbent when subjected to cyclic sulfidation and regeneration testing. In previous reports, the sulfidation and regeneration results from cyclic testing done at 600°C were presented. Manganese-based sorbents with molar ratios>1:1 Mn:substrate were effective in reducing the H2S concentration in simulated coal gases to less than 100 ppmv over five cycles. Actual breakthrough time for formulation C6-2-1100 was as high as 73% of breakthrough time based on wt% Mn in sorbent. Regeneration tests determined that loaded pellets can be fully regenerated in air/steam mixture at 750°C with minimal sulfate formation. In this report, the results from the cyclic crush strength tests, sulfur profile test, and cyclic testing done after 5 cycles showed decreases in strength from 12.6% to 57.9%. Cyclic testing at 550°C showed pre-breakthrough concentrations as low as 10 ppmv. Cyclic testing done at 2 L/min and 3 L/min did not show any significant difference in pre-breakthrough concentrations or capacity.

Currently, the Morgantown Energy Technology Center, is actively investigating alternative hot fuel gas desulfurization sorbents for application to the Integrated Gasification Combined Cycle (IGCC). A sorbent must be highly active towards sulfur at high temperatures and pressure's, and under varying degrees of reducing atmospheres. Thus, high conversion of the metal oxide and low hydrogen sulfide exit partial pressures. Also, it must regenerate nearly ideally to maintain activity over numerous cycles. Furthermore, regeneration must yield a sulfur product which is economically recoverable directly or indirectly. This cyclic process requires a holistic approach as any one criteria may eliminate a candidate sorbent from further consideration. Over fifty induration campaigns have been conducted among the fifteens Mn-based sorbent formulations. All indurated sorbents has been tested for crush strength and chemical analysis. Also, fifteen sorbent formulations have been tested in a TGA for at least on e induration condition. Subsequently described are the three main groups of formulations tested. They are the MnCO3 supported with TiO2 (with or without bentonite), MnCO3 supported with Al2O3 (with or without porosity enhancers), and MnO2 ore supported with alundum (with and without bentonite).

Manganese-based sorbents have been investigated for the removal of hydrogen sulfide (the primary sulfur bearing compound) from hot coal gases prior to its use in combined cycle turbines. Four formulations of Mn-based sorbents were tested in an ambient-pressure fixed-bed reactor to determine steady state H2S concentrations, breakthrough times and effectiveness of the sorbent when subjected to cyclic sulfidation and regeneration testing. In a previous report, the sulfidation results were presented. Manganese-based sorbents with molar ratios> 1:1 Mn:Substrate were effective in reducing the H2S concentration in simulated coal gases to less than 100 ppmv over five cycles. Actual breakthrough time for formulation C6-2-1100 was as high as 73% of breakthrough time based on wt% Mn in sorbent. In this report, the regeneration results will be presented. Regeneration tests determined that loaded pellets can be fully regenerated in air/steam mixture at 750°C with minimal sulfate formation. 16 refs., 9 figs., 5 tabs.

Hot gas desulfurization may be accomplished by using solid sorbents such as oxides of those metals that form stable sulfides. The effectiveness of a desulfurizing agent in treating such gases is related to the predicted equilibrium partial pressure of hydrogen sulfide which will be present in a phase combination of the reduced form of sulfide and oxide phases. The focus of much current work being performed by the Department of Energy on sorbent development is in the use of zinc ferrite, zinc titanate, and Z-Sorb. The latter sorbent is a commercial product consisting of ZnO, a promoter, and a proprietary supporting matrix designed to provide stability and prolong sorbent life. Although these Zn-based sorbents have been the subject of extensive pilot-scale and process development work, all sorbents produced to date still experience structural and reactive degradation over multi-cycle use at relatively moderate temperatures. An effective alternative to zinc-based sorbents could be manganese sorbents which withstand high temperature operation and also maintain structural and reactive integrity over many cycles, as investigations by Ben-Slimane and Hepworth have indicated. Thermodynamic limits may prevent MnO from achieving the low sulfur specifications of the product gas for use in a molten carbonate fuel cell, but under the correct conditions the guideline for IGCC systems can easily be achieved. Furthermore, manganese sorbents could possibly be used in conjunction with a polishing sorbent (such as zinc oxide) possessing more favorable thermodynamic properties to reach levels acceptable for fuel cell applications (

The Morgantown Energy Technology Center (METC) of the U.S. Department of Energy (DOE) is actively pursuing the development of reliable and cost-effective processes to clean coal gasifier gases for application to integrated gasification combined cycle (IGCC) and molten carbonate fuel cell (MCFC) power plants. A large portion of gas cleanup research has been directed towards hot gas desulfurization using Zn-based sorbents. However, zinc titanate sorbents undergo reduction to the metal at temperatures approaching 700°C and lose reactivity because of volatilization. In addition, sulfate formation during regeneration leads to spalling of reactive surfaces. Because of these problems with zinc-based sorbents, METC has shown interest in formulating and testing manganese-based sorbents. Currently, many proposed IGCC processes include a water quench prior to desulfurization. This quench is required for two reasons; limitations in the process hardware (1000°C), and excessive Zn-based sorbent loss (about 700°C). With manganese, the water quench is not necessary to avoid sorbent loss, since Mn-based sorbents have been shown to retain reactivity under cyclic testing at 900°C. This advantage of manganese over zinc has potential to increase thermal efficiency as the trade-off of increasing the equilibrium H2S over-pressure obtainable with a manganese sorbent. In the work which is reported here, lower loading temperatures (as low as 400°C) are studied. Also formulations containing titania rather then alumina are studied to attempt to improve performance.