Hot-Gas Desulfurization with Sulfur Recovery

The objective of this study is to develop a second generation HGD process that regenerates the sulfided sorbent directly to elemental sulfur using SO{sub 2}, with minimal consumption of coal gas. The goal is to have better overall economics than DSRP when integrated with the overall IGCC system

ADVANCED SULFUR CONTROL CONCEPTS

Conventional sulfur removal in integrated gasification combined cycle (IGCC) power plants involves numerous steps: COS (carbonyl sulfide) hydrolysis, amine scrubbing/regeneration, Claus process, and tail-gas treatment. Advanced sulfur removal in IGCC systems involves typically the use of zinc oxide-based sorbents. The sulfides sorbent is regenerated using dilute air to produce a dilute SO{sub 2} (sulfur dioxide) tail gas. Under previous contracts the highly effective first generation Direct Sulfur Recovery Process (DSRP) for catalytic reduction of this SO{sub 2} tail gas to elemental sulfur was developed. This process is currently undergoing field-testing. In this project, advanced concepts were evaluated to reduce the number of unit operations in sulfur removal and recovery. Substantial effort was directed towards developing sorbents that could be directly regenerated to elemental sulfur in an Advanced Hot Gas Process (AHGP). Development of this process has been described in detail in Appendices A-F. RTI began the development of the Single-step Sulfur Recovery Process (SSRP) to eliminate the use of sorbents and multiple reactors in sulfur removal and recovery. This process showed promising preliminary results and thus further process development of AHGP was abandoned in favor of SSRP. The SSRP is a direct Claus process that consists of injecting SO{sub 2} directly into the quenched coal gas from a coal gasifier, and reacting the H{sub 2}S-SO{sub 2} mixture over a selective catalyst to both remove and recover sulfur in a single step. The process is conducted at gasifier pressure and 125 to 160 C. The proposed commercial embodiment of the SSRP involves a liquid phase of molten sulfur with dispersed catalyst in a slurry bubble-column reactor (SBCR)

Carbon Dioxide Capture from Flue Gas Using Dry Regenerable Sorbents

Laboratory studies were conducted to investigate dry, regenerable, alkali carbonate-based sorbents for the capture of CO{sub 2} from power plant flue gas. Electrobalance, fixed-bed and fluid-bed reactors were used to examine both the CO{sub 2} capture and sorbent regeneration phases of the process. Sodium carbonate-based sorbents (calcined sodium bicarbonate and calcined trona) were the primary focus of the testing. Supported sodium carbonate and potassium carbonate sorbents were also tested. Sodium carbonate reacts with CO{sub 2} and water vapor contained in flue gas at temperatures between 60 and 80 C to form sodium bicarbonate, or an intermediate salt (Wegscheider's salt). Thermal regeneration of this sorbent produces an off-gas containing equal molar quantities of CO{sub 2} and H{sub 2}O. The low temperature range in which the carbonation reaction takes place is suited to treatment of coal-derived flue gases following wet flue gas desulfurization processes, but limits the concentration of water vapor which is an essential reactant in the carbonation reaction. Sorbent regeneration in an atmosphere of CO{sub 2} and water vapor can be carried out at a temperature of 160 C or higher. Pure CO{sub 2} suitable for use or sequestration is available after condensation of the H{sub 2}O. Flue gas contaminants such as SO{sub 2} react irreversibly with the sorbent so that upstream desulfurization will be required when sulfur-containing fossil fuels are used. Approximately 90% CO{sub 2} capture from a simulated flue gas was achieved during the early stages of fixed-bed reactor tests using a nominal carbonation temperature of 60 C. Effectively complete sorbent carbonation is possible when the fixed-bed test is carried out to completion. No decrease in sorbent activity was noted in a 15-cycle test using the above carbonation conditions coupled with regeneration in pure CO{sub 2} at 160 C. Fluidized-bed reactor tests of up to five cycles were conducted. Carbonation of sodium carbonate in these tests is initially very rapid and high degrees of removal are possible. The exothermic nature of the carbonation reaction resulted in a rise in bed temperature and subsequent decline in removal rate. Good temperature control, possibly through addition of supplemental water and evaporative cooling, appears to be the key to getting consistent carbon dioxide removal in a full-scale reactor system. The tendency of the alkali carbonate sorbents to cake on contact with liquid water complicates laboratory investigations as well as the design of larger scale systems. Also their low attrition resistance appears unsuitable for their use in dilute-phase transport reactor systems. Sodium and potassium carbonate have been incorporated in ceramic supports to obtain greater surface area and attrition resistance, using a laboratory spray dryer. The caking tendency is reduced and attrition resistance increased by supporting the sorbent. Supported sorbents with loading of up to 40 wt% sodium and potassium carbonate have been prepared and tested. These materials may improve the feasibility of large-scale CO{sub 2} capture systems based on short residence time dilute-phase transport reactor systems

Demonstration of a Piston Plug feed System for Feeding Coal/Biomass Mixtures across a Pressure Gradient for Application to a Commercial CBTL System

Producing liquid transportation fuels and power via coal and biomass to liquids (CBTL) and integrated gasification combined cycle (IGCC) processes can significantly improve the nation's energy security. The Energy Independence and Security Act of 2007 mandates increasing renewable fuels nearly 10-fold to >2.3 million barrels per day by 2022. Coal is abundantly available and coal to liquids (CTL) plants can be deployed today, but they will not become sustainable without large scale CO{sub 2} capture and storage. Co-processing of coal and biomass in CBTL processes in a 60 to 40 ratio is an attractive option that has the potential to produce 4 million barrels of transportation fuels per day by 2020 at the same level of CO{sub 2} emission as petroleum. In this work, Southern Research Institute (Southern) has made an attempt to address one of the major barriers to the development of large scale CBTL processes - cost effective/reliable dry-feeding of coal-biomass mixtures into a high pressure vessel representative of commercial entrained-flow gasifiers. Present method for dry coal feeding involves the use of pressurized lock-hopper arrangements that are not only very expensive with large space requirements but also have not been proven for reliably feeding coal-biomass mixtures without the potential problems of segregation and bridging. The project involved the development of a pilot-scale 250 lb/h high pressure dry coal-biomass mixture feeder provided by TKEnergi and proven for feeding biomass at a scale up to 6 ton/day. The aim of this project is to demonstrate cost effective feeding of coal-biomass mixtures (50:50 to 70:30) made from a variety of coals (bituminous, lignite) and biomass (wood, corn stover, switch grass). The feeder uses a hydraulic piston-based approach to produce a series of plugs of the mixture that act as a seal against high back-pressure of the gasification vessel in to which the mixture is being fed. The plugs are then fed one by one via a plug breaker into the high pressure gasification vessel. A number of runs involving the feeding of coal and biomass mixtures containing 50 to 70 weight % coal into a high pressure gasification vessel simulator have shown that plugs of sufficient density can be formed to provide a seal against pressures up to 450 psig if homogeneity of the mixture can be maintained. However, the in-homogeneity of coal-biomass mixtures can occur during the mixing process because of density, particle size and moisture differences. Also, the much lower compressibility of coal as opposed to biomass can contribute to non-uniform plug formation which can result in weak plugs. Based on present information, the piston plug feeder offered marginal economic advantages over lock-hoppers. The results suggest a modification to the piston feeder that can potentially seal against pressure without the need for forming plugs. This modified design could result in lower power requirements and potentially better economics

Scale-Up of Advanced Hot-Gas Desulfurization Sorbents

The overall objective of this project is to develop regenerable sorbents for hot gas desulfurization in IGCC systems. The specific objective of the project is to develop durable advanced sorbents that demonstrate a strong resistance to attrition and chemical deactivation, and high activity at temperatures as low as 343 C (650 F). A number of formulations will be prepared and screened in a 1/2-inch fixed bed reactor at high pressure (1 to 20 atm) and high temperatures using simulated coal-derived fuel-gases. Screening criteria will include, chemical reactivity, stability, and regenerability over the temperature range of 343 C to 650 C. After initial screening, at least 3 promising formulations will be tested for 25-30 cycles of absorption and regeneration. One of the superior formulations with the best cyclic performance will be selected for investigating scale up parameters. The scaled-up formulation will be tested for long term durability and chemical reactivity

DEVELOPMENT OF ADVANCED HOT-GAS DESULFURIZATION PROCESSES

The techniques employed in this project have successfully demonstrated the feasibility of preparing sorbents that achieve greater than 99% H{sub 2}S removal at temperatures 480 C and that retain their activity over 50 cycles. Fundamental understanding of phenomena leading to chemical deactivation and high regeneration light-off temperature has enabled us to successfully prepare and scale up a FHR-32 sorbent that showed no loss in reactivity and capacity over 50 cycles. This sorbent removed H{sub 2}S below 80 ppmv and lighted-off nicely at 480 C during regeneration. Overall the test is a success with potential for an optimized FHR-32 to be a candidate for Sierra-Pacific. An advanced attrition resistant hot-gas desulfurization sorbent that can eliminate the problematic SO{sub 2} tail gas and yield elemental sulfur directly has been developed. Attrition resistant Zn-Fe sorbent (AHI-2) formulations have been prepared that can remove H{sub 2}S to below 20 ppmv from coal gas and can be regenerated using SO{sub 2} to produce elemental sulfur

Bench-Scale Demonstration of Hot-Gas Desulfurization Technology

Prior to the current project, development of the DSRP was done in a laboratory setting, using synthetic gas mixtures to simulate the regeneration off-gas and coal gas feeds. The objective of the current work is to further the development of zinc titanate fluidized-bed desulfurization (ZTFBD) and the DSRP for hot-gas cleanup by testing with actual coal gas. The objectives of this project are to: (1) Develop and test an integrated, skid-mounted, bench-scale ZTFBD/DSRP reactor system with a slipstream of actual coal gas; (2) Test the bench-scale DSRP over an extended period with a slipstream of actual coal gas to quantify the degradation in performance, if any, caused by the trace contaminants present in coal gas (including heavy metals, chlorides, fluorides, and ammonia); (3) Expose the DSRP catalyst to actual coal gas for extended periods and then test its activity in a laboratory reactor to quantify the degradation in performance, if any, caused by static exposure to the trace contaminants in coal gas; (4) Design and fabricate a six-fold larger-scale DSRP reactor system for future slipstream testing; (5) Further develop the fluidized-bed DSRP to handle high concentrations (up to 14 percent) of SO{sub 2} that are likely to be encountered when pure air is used for regeneration of desulfurization sorbents; and (6) Conduct extended field testing of the 6X DSRP reactor with actual coal gas and high concentrations of SO{sub 2}. The accomplishment of the first three objectives--testing the DSRP with actual coal gas, integration with hot-gas desulfurization, and catalyst exposure testing--was described previously (Portzer and Gangwal, 1994, 1995; Portzer et al., 1996). This paper summarizes the results of previous work and describes the current activities and plans to accomplish the remaining objectives

Bench-Scale Demonstration of Hot-Gas Desulfurization Technology

The U.S. Department of Energy (DOE), Federal Energy Technology Center (FETC), is sponsoring research in advanced methods for controlling contaminants in hot coal gasifier gas (coal-derived fuel-gas) streams of integrated gasification combined-cycle (IGCC) power systems. The hot gas cleanup work seeks to eliminate the need for expensive heat recovery equipment, reduce efficiency losses due to quenching, and minimize wastewater treatment costs

CHAIN-LIMITING OPERATION OF FISCHER-TROPSCH REACTOR

The use of pulsing in Fischer-Tropsch (FT) synthesis to limit the hydrocarbon chain growth and maximize the yield of diesel-range (C{sub 10}-C{sub 20}) products was examined on high-chain-growth-probability ({alpha} {ge} 0.9) FT catalysts. Pulsing experiments were conducted using a stainless-steel fixed-bed micro-reactor, equipped with both on-line (for the permanent gases and light hydrocarbons, C{sub 1}-C{sub 15}) and off-line (for the heavier hydrocarbons, C{sub 10}-C{sub 65}) gas chromatography analysis. Additional experiments were performed using a highly active attrition-resistant iron-based FT synthesis catalyst in a 1-liter continuous stirred-tank rector (CSTR). On both a Co-ZrO{sub 2}/SiO{sub 2} and a Co/Al{sub 2}O{sub 3} FT synthesis catalyst application of H{sub 2} pulsing causes significant increase in CO conversion, and only an instantaneous increase in undesirable selectivity to CH{sub 4}. Increasing the frequency of H{sub 2} pulsing enhances the selectivity to C{sub 10}-C{sub 20} compounds but the chain-growth probability {alpha} remains essentially unaffected. Increasing the duration of H{sub 2} pulsing results in enhancing the maximum obtained CO conversion and an instantaneous selectivity to CH{sub 4}. An optimum set of H{sub 2} pulse parameters (pulse frequency, pulse duration) is required for maximizing the yield of desirable diesel-range C{sub 10}-C{sub 20} products. Application of a suitable H{sub 2} pulse in the presence of added steam in the feed is a simple method to overcome the loss in activity and the shift in paraffin vs. olefin selectivity (increase in the olefin/paraffin ratio) caused by the excess steam. A decrease in syngas concentration has a strong suppressing effect on the olefin/paraffin ratio of the light hydrocarbon products. Higher syngas concentration can increase the chain growth probability {alpha} and thus allow for better evaluation of the effect of pulsing on FT synthesis. On a high-{alpha} Fe/K/Cu/SiO{sub 2} FT synthesis catalyst H{sub 2} pulsing enhances the yield of C{sub 10}-C{sub 20} but at the same time decreases the catalyst activity (CO conversion) and increases the selectivity to CH{sub 4}. On the other hand, pulsing with CO also increases the yield of C{sub 10}-C{sub 20} but has no impact on the selectivity to CH{sub 4} or CO{sub 2} and decreases catalytic activity only moderately. FT reaction experiments using the Fe/K/Cu/SiO{sub 2} FT synthesis catalyst in a 1-liter CSTR indicate that both the catalyst activity and yield of all products (both favorable and unfavorable) are enhanced by increasing reaction pressure and H{sub 2}:CO feed ratio, as well as with decreasing reaction temperature. The selectivity to the desirable C{sub 5+} product fraction is favored by lower reaction temperatures and H{sub 2}:CO feed ratios. Based on the results of this study, the following recommendations should be considered: Pulsing experiments on FT synthesis catalysts (either cobalt-based or iron-based) should be performed under conditions that maximize the yield of the heavy hydrocarbon products (high chain-growth probability {alpha}), such as high synthesis gas partial pressure and low space velocity. More aggressive pulsing conditions (higher pulse frequency) should be examined, so as to establish the long-term impact of pulsing on product formation beyond experimental uncertainty. Also, more emphasis should be given to pulsing experiments in the CSTR which, due to its superior control of the catalyst temperature, would allow the evaluation of a more extensive range of pulsing parameters (pulse frequency and duration)