Conversion of Hydrogen Sulfide in Coal Gases to Liquid Elemental Sulfur with Monolithic Catalysts

Abstract

Removal of hydrogen sulfide (H{sub 2}S) from coal gasifier gas and sulfur recovery are key steps in the development of Department of Energy's (DOE's) advanced power plants that produce electric power and clean transportation fuels with coal and natural gas. These plants will require highly clean coal gas with H{sub 2}S below 1 ppmv and negligible amounts of trace contaminants such as hydrogen chloride, ammonia, alkali, heavy metals, and particulate. The conventional method of sulfur removal and recovery employing amine, Claus, and tail-gas treatment is very expensive. A second generation approach developed under DOE's sponsorship employs hot-gas desulfurization (HGD) using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process (DSRP). However, this process sequence does not remove trace contaminants and is targeted primarily towards the development of advanced integrated gasification combined cycle (IGCC) plants that produce electricity (not both electricity and transportation fuels). There is an immediate as well as long-term need for the development of cleanup processes that produce highly clean coal gas for next generation power plants. To this end, a novel process is now under development at several research organizations in which the H{sub 2} in coal gas is directly oxidized to elemental sulfur over a selective catalyst. Such a process is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S In the Single-Step Sulfur Recovery Process (SSRP), the direct oxidation of H{sub 2}S to elemental sulfur in the presence of SO{sub 2} is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H{sub 2}S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and HGD/DSRP. The H{sub 2} and CO components of syngas appear to behave as inert with respect to sulfur formed at the SSRP conditions. One problem in the SSRP process that needs to be eliminated or minimized is COS formation that may occur due to reaction of CO with sulfur formed from the Claus reaction. The objectives of this research are to formulate monolithic catalysts for removal of H{sub 2}S from coal gases and minimum formation of COS with monolithic catalyst supports, {gamma}-alumina wash or carbon coats, and catalytic metals, to develop a catalytic regeneration method for a deactivated monolithic catalyst, to measure kinetics of both direct oxidation of H{sub 2}S to elemental sulfur with SO{sub 2} as an oxidizer and formation of COS in the presence of a simulated coal gas mixture containing H{sub 2}, CO, CO{sub 2}, and moisture, using a monolithic catalyst reactor, and to develop kinetic rate equations and model the direct oxidation process to assist in the design of large-scale plants. This heterogeneous catalytic reaction has gaseous reactants such as H{sub 2}S and SO{sub 2}. However, this heterogeneous catalytic reaction has heterogeneous products such as liquid elemental sulfur and steam. To achieve the above-mentioned objectives using a monolithic catalyst reactor, experiments on conversion of hydrogen sulfide into elemental sulfur and formation of COS were carried out for the space time range of 40-560 seconds at 120-150 C to evaluate effects of reaction temperatures, total pressure, space time, and catalyst regeneration on conversion of hydrogen sulfide into elemental sulfur and formation of COS. Simulated coal gas mixtures consist of 3,600-4,000-ppmv hydrogen sulfide, 1,800-2,000 ppmv sulfur dioxide, 23-27 v% hydrogen, 36-41 v% CO, 10-12 v% CO{sub 2}, 0-10 vol % moisture, and nitrogen as remainder. Volumetric feed rates of a simulated coal gas mixture to the reactor are 30-180 SCCM. The temperature of the reactor is controlled in an oven at 120-150 C. The pressure of the reactor is maintained at 40-210 psia. The molar ratio of H{sub 2}S to SO{sub 2} in the monolithic catalyst reactor is maintained approximately at 2 for all the reaction experiment runs.