Removal of Elemental Mercury from Dry Methane Gas with Manganese Oxides

Abstract

In this study, we sought to investigate the mercury removal efficiency of manganese oxides from natural gas. The fundamental studies on mercury removal with manganese oxides sorbents were carried out in a laboratory scale fixed bed reactor at 30 °C with a mixture of methane (20%) and nitrogen gas laden with 4.8 ppb of elemental mercury. Manganese oxides with varying surface area and crystalline phase were prepared by conventional precipitation method in this study. The effects of surface area, crystallinity and other metal oxides on mercury removal efficiency were investigated. Effect of Ag impregnation on mercury removal efficiency was also investigated. Ag supported on metal oxide such titania and zirconia as reference materials were also used in this study for comparison. The characteristics of mercury removal reaction with manganese oxide was investigated using a temperature programmed desorption (TPD) technique. Manganese oxides showed very high Hg removal activity (about 73-93% Hg removal) for first time use. Surface area of the manganese oxide samples decreased after heat-treatment and resulted in complete loss of Hg removal ability for repeated use after Hg desorption in the case of amorphous MnO2, and 75% loss of the initial Hg removal activity for the crystalline MnO2. Mercury desorption efficiency of crystalline MnO2 was very low (37%) for first time use and high (98%) after second time use. Residual potassium content in MnO2 may have some effect on the thermal stability of the adsorbed Hg species. Desorption of Hg from manganese oxides occurs at much higher temperatures (with a peak at 400 °C) than Ag/TiO2 or Ag/ZrO2. Mercury may be captured on manganese oxides in the form of mercury manganese oxide. Keywords—Mercury removal, Metal and metal oxide sorbents, Methane, Natural gas.