Internal Tar/CH4 Reforming in Biomass Dual Fluidised Bed Gasifiers towards Fuel Synthesis
Sammanfattning: Production of high-quality syngas from biomass gasification in a dual fluidised bed gasifier (DFBG) has made a significant progress in R&D and Technology demonstration. An S&M scale bio-automotive fuel plant close to the feedstock resources is preferable as biomass feedstock is widely sparse and has relatively low density, low heating value and high moisture content. This requires simple, reliable and cost-effective production of clean and good syngas. Indirect DFBGs, with steam as the gasification agent, produce a syngas of high content H2 and CO with 12-20 MJ/mn3 heating value. The Mid Sweden University (MIUN) gasifier, built for research on synthetic fuel production, is a dual fluidised bed gasifier. Reforming of tars and CH4 (except for methanation application) in the syngas is a major challenge for commercialization of biomass fluidised-bed gasification technology towards automotive fuel production. A good syngas from DFBGs can be obtained by optimised design and operation of the gasifier, by the use of active catalytic bed material and internal reforming. This thesis presents a series of experimental tests with different operation parameters, reforming of tar and CH4 with catalytic bed material and reforming of tar and CH4 with catalytic internal reformer. The first test was carried out to evaluate the optimal operation and performance of the MIUN gasifier. The test provides basic information for temperature control in the combustor and the gasifier by the bed material circulation rate. After proven operation and performance of the MIUN gasifier, an experimental study on in-bed material catalytic reforming of tar/CH4 is performed to evaluate the catalytic effects of the olivine and Fe-impregnated olivine (10%wtFe/olivine Catalyst) bed materials, with reference to non-catalytic silica sand operated in the mode of dual fluidised beds (DFB). A comparative experimental test is then carried out with the same operation condition and bed-materials but when the gasifier was operated in the mode of single bubbling fluidised bed (BFB). The behaviour of catalytic and non-catalytic bed materials differs when they are used in the DFB and the BFB. Fe/olivine and olivine in the BFB mode give lower tar and CH4 content together with higher H2+CO concentration, and higher H2/CO ratio, compared to DFB mode. It is hard to show a clear advantage of Fe/olivine over olivine regarding tar/CH4 catalytic reforming. In order to significantly reduce the tar/CH4 contents, an internal reformer, referred to as the FreeRef reformer, is developed for in-situ catalytic reforming of tar and CH4 using Ni-catalyst in an environment of good gas-solids contact at high temperature. A study on the internal reformer filled with and without Ni-catalytic pellets was carried out by evaluation of the syngas composition and tar/CH4 content. It can be concluded that the reformer with Ni-catalytic pellets clearly gives a higher H2 content together with lower CH4 and tar contents in the syngas than the reformer without Ni-catalytic pellets. The gravimetric tar content decreases from 25 g/m3 down to 5 g/m3 and the CH4 content from 11% down below 6% in the syngas. The MIUN gasifier has a unique design suitable for in-bed tar/CH4 catalytic reforming and continuously internal regeneration of the reactive bed material. The novel design in the MIUN gasifier increases the gasification efficiency, suppresses the tar generation and upgrades the syngas composition.
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