Shape-selective catalysts for Fischer-Tropsch chemistry : iron-containing particulate catalysts. Activity report : January 1, 2001 - December 31, 2004.

Cronauer, D. ; Engineering, Chemical

Argonne National Laboratory

关键词: Research Programs;    Hydrocarbons;    Aging;    Precursor;    Membranes;   

DOI  :  10.2172/928626
RP-ID  :  ANL-05/63
RP-ID  :  DE-AC02-06CH11357
RP-ID  :  928626

美国|其它

来源: UNT Digital Library

【 摘 要 】

Argonne National Laboratory is carrying out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry--specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it is desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. It is desired that selectivity be directed toward producing diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. The goal is to produce shape-selective catalysts that have the potential to limit the formation of longchain products and yet retain the active metal sites in a protected 'cage'. This cage also restricts their loss by attrition during use in slurry-bed reactors. The first stage of this program was to prepare and evaluate iron-containing particulate catalysts. This activity report centers upon this first stage of experimentation with particulate FT catalysts. (For reference, a second experimental stage is under way to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes.) To date, experimentation has centered upon the evaluation of a sample of iron-based, spray-dried catalyst prepared by B.H. Davis of the Center of Applied Energy Research (CAER) and samples of his catalyst onto which inorganic 'shells' were deposited. The reference CAER catalyst contained a high level of dispersed fine particles, a portion of which was removed by differential settling. Reaction conditions have been established using a FT laboratory unit such that reasonable levels of CO conversion can be achieved, where therefore a valid catalyst comparison can be made. A wide range of catalytic activities was observed with SiO{sub 2}-coated FT catalysts. Two techniques were used for SiO{sub 2}coating. The first involved a caustic precipitation of SiO{sub 2} from an organo-silicate onto the CAER catalyst. The second was the acidic precipitation of an organo-silicate with aging to form fractal particles that were then deposited onto the CAER catalyst. Several resulting FT catalysts were as active as the coarse catalyst on which they were prepared. The most active ones were those with the least amount of coating, namely about 2.2 wt% SiO{sub 2}. In the case of the latter acid technique, the use of HCl and HNO{sub 3} was much more effective than that of H{sub 2}SO{sub 4}. Scanning electron microscopy (SEM) was used to observe and analyze as-received and treated FT catalysts. It was observed that (1) spherical particles of CAER FT catalyst were made up of agglomerates of particles that were, in turn, also agglomerates; (2) the spray drying process of CAER apparently concentrated the Si precursor at the surface during drying; (3) while SEM pointed out broad differences in the appearance of the prepared catalyst particles, there was little indication that the catalysts were being uniformly coated with a cage-like protective surface, with perhaps the exception of HNO{sub 3}-precipitated catalyst; and (4) there was only a limited penetration of carbon (i.e., CO) into the FT catalyst during the conditioning and FT reaction steps.