Hydrogenation reactions using dense carbon dioxide

Recently, a combination of fluorous substituents and a sugar-derived structure allowed the preparation of the scC02-soluble copolymer 53 as a novel phase-transfer catalyst (Figure 4.8). ° Dendrimers with fluorous substituents were also prepared for the same use. ° They are soluble in dense carbon dioxide and can solubilize otherwise C02-insoluble compounds such as Pd-nanoparticles (Scheme 92). The resulting dendrimer-encapsulated Pd catalyzes the hydrogenation of styrene and the Heck reaction of phenyl iodide. 

Sihcon carbide is comparatively stable. The only violent reaction occurs when SiC is heated with a mixture of potassium dichromate and lead chromate. Chemical reactions do, however, take place between sihcon carbide and a variety of compounds at relatively high temperatures. Sodium sihcate attacks SiC above 1300°C, and SiC reacts with calcium and magnesium oxides above 1000°C and with copper oxide at 800°C to form the metal sihcide. Sihcon carbide decomposes in fused alkahes such as potassium chromate or sodium chromate and in fused borax or cryohte, and reacts with carbon dioxide, hydrogen, ak, and steam. Sihcon carbide, resistant to chlorine below 700°C, reacts to form carbon and sihcon tetrachloride at high temperature. SiC dissociates in molten kon and the sihcon reacts with oxides present in the melt, a reaction of use in the metallurgy of kon and steel (qv). The dense, self-bonded type of SiC has good resistance to aluminum up to about 800°C, to bismuth and zinc at 600°C, and to tin up to 400°C a new sihcon nitride-bonded type exhibits improved resistance to cryohte. 

Similar to the case of dehydrogenation or other hydrogen-generating reactions, the use of a dense membrane reactor to remove oxygen from an oxygen-generating reaction such as decomposition of carbon dioxide displaces the reaction equilibrium and increases the conversion from 1.2% (limited by the equilibrium) to 22% [Nigara and Cales, 1986]. This has been confumed by Itoh et al. [1993]. 

A commercial nickel catalyst was used for methane steam reforming performed at a 500 °C reaction temperature, a S/C ratio of 3.0 and atmospheric pressure, while the permeate side was evacuated. The performance of the vapour deposited platinum membrane was similar to the plated dense palladium membrane. In the permeate of the deposited ruthenium and palladium membranes, small amounts of carbon oxides and also methane were observed. While it was expected that all these species had passed through the membranes by diffusion, in addition some methane was converted into carbon dioxide over the noble metals of the membranes. Kikuchi et al. demonstrated by simulations that conversion and hydrogen permeation in a membrane reactor is higher, where the first portion of the catalyst bed is not coupled to the membrane. Such an arrangement as shown in Figure 7.16 would clearly save expensive membrane surface area. Experimental work by Itoh et al. performed for methanol steam reforming [521] confirmed the assumptions of Kikuchi et al. 

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