Removal of NH3 and H2S from Biomass Gasification Producer Gas
Thesis DisciplineChemical Engineering
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
Biomass gasification is a promising technology for conversion of various biomass feedstocks to producer gas for subsequent production of fuels and chemicals. A dual fluidised bed (DFB) steam gasifier is used in the present research to produce the producer gas for Fischer-Tropsch (FT) liquid fuel synthesis. However, NH3 and H2S gases in the producer gas remain an issue to be resolved because they are poisonous to the catalysts employed in the FT reactor. To remove NH3 and H2S, two methods were investigated in this research: (1) primary measures which were employed in the DFB steam gasifier including process optimisation and application of bed materials for catalytic NH3 decomposition and H2S adsorption; and (2) secondary measures or downstream cleaning methods after the gasifier. The combination of the primary measures and the secondary measures is an effective way to remove the NH3 and H2S in the producer gas from gasification process.
Studies on the primary measures were divided into two parts. In the first part, in situ reduction of NH3 and H2S in biomass producer gas from the DFB steam gasifier was performed. The primary measures consisted of optimisation of operation conditions and application of bed materials. The main operation conditions in the DFB steam gasifier studied were gasification temperature, steam to fuel (S/F) ratio, and mean gas residence time (f). The bed materials tested include silica sand, iron sand (ilmenite), and calcined olivine sand. For the second part of the primary measures, an influence of the lignite to fuel (L/F) ratio on NH3 and H2S concentrations and conversions in co-gasification of blended lignite and wood pellets in the DFB steam gasifier was investigated. Experiments were performed in the DFB steam gasifier at 800C with blended lignite and radiata pine wood with the L/F ratio ranging from 0% to 100%. It was found that all of the studied parameters including gasification temperature, S/F ratio, f, bed material, and L/F ratio significantly influenced the NH3 and H2S concentrations and conversions in the producer gas.
For the secondary measures, a novel hot catalytic reactor and adsorber was developed in the present research for the simultaneous removal of NH3 and H2S. In a hot gas reactor operated at 500-800C and under atmospheric pressure, titanomagnetite was tested for NH3 and H2S removal by hot catalytic NH3 decomposition and H2S adsorption reactions. Titanomagnetite was tested with three different gas streams including 2,000 ppmv NH3 in Ar, 2,000 ppmv NH3 and 230 ppmv H2S in Ar, and 2,000 ppmv NH3 and 230 ppmv H2S in simulated biomass producer gas. From the experimental results, it was discovered that ferrite (α-Fe) readily formed by the H2 reduction of titanomagnetite has shown almost complete NH3 decomposition (100%) in Ar gas at 700 and 800C. The presence of H2S in the gas mixture of NH3 and Ar slightly reduced the catalytic activity for NH3 decomposition at 700 and 800C (>96%) and H2S adsorption of more than 98% could be achieved at the same temperature range. However, in the test with simulated biomass producer gas, 60% NH3 decomposition and 9% H2S adsorption were obtained at 800C, whereas 40% NH3 decomposition and 80% H2S adsorption were obtained at 500C. The decrease of NH3 decomposition and H2S adsorption at 800C in simulated biomass producer gas could be due to the high content of H2 (45 vol%) in the feed gas that favours the reverse reactions of NH3 decomposition and H2S adsorption, the increased surface coverage of the active α-Fe phase by adsorbed hydrogen, and the competition of α-Fe for the reverse water-gas shift reaction. Besides, it was discovered that the temperature significantly affected the removal of NH3 and H2S in simulated biomass producer gas and thus it needs to be optimised.