Catalysts early development

Houdry The first catalytic petroleum cracking process, based on an invention by E. J. Houdiy in 1927, which was developed and commercialized by the Houdry Process Corporation. The process was piloted by the Vacuum Oil Company, Paulsboro, NJ, in the early 1930s. The catalyst was contained in a fixed bed. The first successful catalyst was an aluminosilicate mineral. Subsequently, other related catalysts were developed by Houdry in the United States, by I. G. Farbenindustrie in Germany, and by Imperial Chemical Industries in England. After World War II, the clay-based catalysts were replaced by a variety of synthetic catalysts, many based on alumino-silicates. Later, these too were replaced by zeolites. U.S. Patents 1,837,963 1,957,648 1,957,649. 

Written by the author mainly from his private notes and with but little literature available, this paper represents the early development of multicomponent catalysts, a field in which he played a decisive role. A few insertions on theoretical points and several references have been added by the translator where it seemed indicated. The theoretical investigations and practical applications of multicomponent catalysts after about 1920 are not included in this paper. 

In 1944 a fluid catalyst pilot plant was erected and operated at the Olean laboratory. A schematic flow diagram of the unit is shown in Figure 1. The unit operated well from the beginning. The conversion of jeactants exceeded that achieved by the Germans even at space velocities 10 to 20 times those used in Europe. Also, iron catalysts were developed which gave oil yields comparable with those obtained by fixed-bed operations. Typical results from these early experiments are shown in Table I. A discussion of the conditions for the different runs is given in subsequent paragraphs. 

Isomerization catalysts were developed along two paths—by Friedel-Crafts halide systems or by dual site heterogeneous catalysts, originating with the commercial introduction of platinum-aluminas for catalytic reforming in the 1940,s. The Friedel-Crafts systems (aluminum chloride-hydrocarbon complexes) were used exclusively during the early stages of... 

From the Early Developments to Low-Pressure Homogeneous Catalysts. 197... 

The use of reactive distillation for reactions that rely on a solid catalyst was developed in the early 1970s [4], Heterogeneously catalyzed reactive distillation poses the additional problem of how to place the solid cata-... 

The stabihty and excellent conductivity of silver helped foster the early development of silver plating in the electrochemical industry (6). Although silver is perceived to be and designated a precious metal, it is actually more abundant and less costly than most other late transition metals (5). Silver metal and silver-based compounds are utilized as catalysts, additives, oxidants, and ligand-transfer reagents in various chemical transformations (7-11). 

As expected many new catalysts have been commercialized for light feed hydrodesulfurization. Nearly all catalyst manufacturers are active in this segment. At the end of the eighties Akzo Nobel introduced Ketjenfine 752 which until recently was the most active diesel HDS catalyst with sales of over 15.000 tons. A few catalyst manufacturers recently introduced catalysts with a performance in a range similar to that of Ketjenfine 752. Early this year Akzo Nobel introduced Ketjenfine 756. This catalyst was developed in cooperation with Exxon and successfully used as RT 601 in several units in Exxon refineries and DODD units. Ketjenfine 756 is most probably the highest activity commercially applied diesel HDS catalyst today. 

AECL is working with several Canadian PEM developers to apply its heterogeneous catalyst expertise (developed for processes to produce and purify heavy water) to PEM technology. Early work suggests that a significant reduction in platinum loading may be achievable. 

Finally, an important trade-off with obtaining high S/C ratios is that of time. In early development it is often more desirable to have reactions complete in a short and reproducible timeframe, rather than to optimize catalyst loading. For larger scale manufacture, especially for markets other than pharmaceuticals, obtaining the best S/C ratio will be of greater importance. 

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