Spray drying and attrition behavior of iron catalysts for slurry phase Fischer-Tropsch synthesis

This thesis describes results of a study aimed at developing and evaluating attrition resistant iron catalysts prepared by spray drying technique. These catalysts are intended for Fischer-Tropsch (F-T) synthesis in a slurry bubble column reactor (SBCR). One of the major challenges associated with the use of SBCR for this purpose is the problem of catalyst/wax separation. If the catalyst particles break up into smaller ones during the F-T synthesis, these small particles (>5-10 m in diameter) will cause problems with the catalyst/wax separation. Several research groups have worked on development of attrition resistant spray-dried iron catalysts, and methodology to measure and predict their attrition behavior. However, these attrition tests were not conducted under conditions representative of those encountered in a SBCR.

In this work, the attrition behavior of six spray-dried catalysts and two precipitated catalysts was evaluated under slurry reaction conditions in a stirred tank slurry reactor (STSR). Spray-dried catalysts used in this study were prepared at Texas A&M University (TAMU) and at Hampton University (HU), employing different preparation procedures and silica sources (potassium silicate, tetraethyl orthosilicate or colloidal silica). The attrition properties of F-T catalysts were determined by measuring particle size distribution (PSD) of catalysts before and after F-T synthesis in the STSR. This provides a direct measure of changes in particle size distribution in the STSR, and accounts for both physical and chemical attrition effects. Also, scanning electron microscopy (SEM) was used to investigate the mechanism of attrition - erosion vs. fracture, and to obtain morphological characteristics of catalysts. Spray dried 100Fe/3Cu/5K/16SiO2 catalyst (WCS3516-1), prepared from wet precursors using colloidal silica as the silica source, was the best in terms of its attrition strength. After 337 hours of F-T synthesis in the STSR, the reduction in the average particle size and generation of particles less than 10 m in diameter were found to be very small. This indicates that both particle fracture and erosion were insignificant during testing in the STSR. All other catalysts, except one of the spray dried catalysts synthesized at Hampton University, also had a good attrition resistance and would be suitable for use in slurry reactors for F-T synthesis.