Iron-based catalysts catalyst preparation, activation

F-T Catalysts The patent literature is replete with recipes for the production of F-T catalysts, with most formulations being based on iron, cobalt, or ruthenium, typically with the addition of some pro-moter(s). Nickel is sometimes listed as a F-T catalyst, but nickel has too much hydrogenation activity and produces mainly methane. In practice, because of the cost of ruthenium, commercial plants use either cobalt-based or iron-based catalysts. Cobalt is usually deposited on a refractory oxide support, such as alumina, silica, titania, or zirconia. Iron is typically not supported and may be prepared by precipitation. 

Cobalt- rather than iron-based FT catalysts have been examined, in order to minimize the competing water-gas shift reaction, which would result in a lowered carbon efficiency. Most cobalt FT catalysts have been prepared by coprecipitation of Co salts with various promoters onto a slurried oxide support to afford mixed phase systems (J ). Reduction to the active catalyst was controlled by addition of various promoters (e.g. MgO, Th02, AI2O3) (2). In part, these promoters are necessary to maintain good metal dispersion in the catalyst and resistance to sintering. Dispersion... 

We presented a facile route for the modification of zeolites and for the preparation of bifunctional catalysts possessing both acidic and hydrogenation functions via solid-solid reaction. Branched and higher hydrocarbons were obtained over such modified composite catalysts. Sodium migration from the surface of the iron-based catalyst to the zeolite during the solid-solid reaction accounts for the change of catalytic activity. XRD measurements exhibited evidence for Na migration. 

In the early research stages of ammonia synthesis catalyst, Mittasch et al. studied almost all metal elements and their bimetallic alloy in the Periodic Table. Several metals have no or less catal3dic functions themselves. However, the addition of some promoter could increase their activities. The addition of a secondary metal into Fe, Mo, W, Co, Ni, Pd, Pt, Os, Mn enhances their activities. The different ratio between two metals leads to a different activity. It can be concluded from these results that the addition of metals in Vlff or VI groups favors enhancing of iron-based catalyst activity. For example, Fe-Mo (1 1) catalyst has high activity. If the Mo content is less than 80%, the activity decreases after running for a long-time. These catalysts are prepared by calcinations of metal nitrates and ammonium molybdate... 

Ray et al. [93] treated organically modified MMT (OMMT) with a MAO solution after vacuum-drying at 100°C. The resulting MAO-treated clay was subsequently used for ethylene polymerization in the presence of 2,6-bis [l-(2,6-diisopropylphenylimino)ethyl]pyridine iron(ll) dichloride with additional MAO in a glass reactor. In addition, they compared the methods of nanocomposite preparation and observed that the nanocomposite produced by catalyst supported on MAO-pretreated OMMT was more efficiently exfoliated than the nanocomposite produced when only a mixture of catalyst and clay was used. This result led them to conclude that at least some of the active centers resided within the clay galleries. Similarly, Guo et al. [100] in a separate studies successfully used pyridine diimine-based iron(ll) catalysts for preparation of exfoliated PE/clay nanocomposites. 

Iron-based catalysts are used in both LTFT and HTFT process mode. Precipitated iron catalysts, used in fixed-bed or slurry reactors for the production of waxes, are prepared by precipitation and have a high surface area. A sihca support is commonly used with added alumina to prevent sintering. HTFT catalysts for fluidized bed apphcations must be more resistant to attrition. Fused iron catalysts, prepared by fusion, satisfy this requirement (Olah and Molnar, 2003). For both types of iron-based catalysts, the basicity of the surface is of vital importance. The probability of chain growth increases with alkali promotion in the order Li, Na, K, and Rb (Dry, 2002), as alkalis tend to increase the strength of CO chemisorption and enhance its decomposition to C and O atoms. Due to the high price o Rb, K is used in practice as a promoter for iron catalysts. Copper is also typically added to enhance the reduction of iron oxide to metallic iron during the catalyst pretreatment step (Adesina, 1996). Under steady state FT conditions, the Fe catalyst consists of a mixture of iron carbides and reoxidized Fe304 phase, active for the WGS reaction (Adesina, 1996 Davis, 2003). 

The selection of raw materials and the method of preparation of the catalyst base are important in determining the final quality of the catalyst. Impregnating almost any iron oxide with potassium hydroxide and drying it will yield a catalyst of some activity, but care must be exercised both in selecting the raw materials and in the method of preparation, if a superior catalyst is to be obtained. Generally, the purer the components the better the catalyst, but substantial quantities of impurities such as silicon dioxide, aluminum oxide, and carbon can be tolerated. Suitable raw materials are obtainable at low cost, and satisfactory methods of preparation are simple and inexpensive. 

Deactivation of the copper zeolites under de-NO, conditions was one of the major reasons why the catalyst was never used in a commercial application. Recent environmental legislation intensified the hunt for a water- and sulfur-stable active catalyst One of the most successful preparative methods was reported by HaU and Feng [42, 43]. They reported excellent de-NO, performance based on an iron exchanged ZSM-5 zeolite. The activity was reported to remain constant for extended times, even under high water and sulfur content conditions. The initial catalytic study initiated a whole raft of characterization studies by a number of groups. The interest was significantly increased when it became obvious that there are issues with catalyst preparation reprodudbihty [44, 45]. XAS was crucial in the discussion of the structure of active sites for de-NO, and the site responsible for the high... 

The early development of catalysts for ammonia synthesis was based on iron catalysts prepared by fusion of magnetite with small amounts of promoters. However, Ozaki et al. [52] showed several years ago that carbon-supported alkali metal-promoted ruthenium catalysts exhibited a 10-fold increase in catalytic activity over conventional iron catalysts under the same conditions. In this way, great effort has been devoted during recent years to the development of a commercially suitable ruthenium-based catalyst, for which carbon support seems to be most promising. The characteristics of the carbon surface, the type of carbon material, and the presence of promoters are the variables that have been studied most extensively. 

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