Shell higher olefin process hydroformylation

The 0x0 process is employed to produce higher alcohols from linear and branched higher olefins. Using a catalyst that is highly selective for hydroformylation of linear olefins at the terminal carbon atom. Shell converts olefins from the Shell higher olefin process (SHOP) to alcohols. This results in a product that is up to 75—85% linear when a linear feedstock is employed. Other 0x0 processes, such as those employed by ICI, Exxon, and BASE (all in Europe), produce oxo-alcohols from a-olefin feedstocks such alcohols have a linearity of about 60%. Enichem, on the other hand, produces... 

Shell higher olefin process (organic/organic) and the Ruhrchemie-Rhone Poulenc propene hydroformylation process (aqueous/organic). The diversity of the applications may confuse the newcomer but it is not easy to comprehend even by the more experienced. A guide to this field may help a lot, and this is why the book of Adams, Dyson and Tavener is most welcome. 

A very elegant solution to solve this problem is the introduction of either a permanent or a temporary phase boundary between the molecular catalyst and the product phase. The basic principle of multiphase catalysis has already found implementation on an industrial scale in the Shell higher olefin process (SHOP) and the Ruhrchemie/Rhdne-Poulenc propene hydroformylation process. Over the years, the idea of phase-separable catalysis has inspired many chemists to design new families of ligands and to develop new separation... 

As described in the introductory chapter, biphasic catalysis has been around for a long time, but despite a few notable successes such as the Shell Higher Olefin Process (SHOP) and the Rhone-Poulenc-Ruhrchemie hydroformylation process, very few biphasic processes have made it into the industrial arena. The limitations of the solvents used so far in biphasic (or multiphasic) catalysis appear to be overcome by ionic liquids, and even if the perfect ionic liquid is not yet available, then there seems to be almost no limit to the number of new ionic liquids that can be made. It has been estimated that up to 1018 different ionic liquids may exist[1 2] and with such a vast number to choose from it is essential that understanding increases in order to allow accurate predictions of their properties and functions, opening up the possibility of designer solvents. 

Two important industrial processes are based on biphasic systems the Shell higher olefin process (SHOP) [3] and the hydroformylation developed by Ruhrchemie/ Rhone Poulenc [4]. Prerequisite was the synthesis of water-soluble ligands, especially water-soluble phosphines. Scheme 1 shows a selection of optically active phosphines for asymmetric reactions under biphasic conditions. 

The most prominent example of equilibration between terminal and internal olefins is the Shell Higher Olefins Process (SHOP) for linear a-olefins (Gum and Freitas, 1979). Here the internal olefin, 2-decene, is converted to the corresponding terminal olefin which then is hydroformylated to the linear aldehyde... 

Hydroformylations catalyzed by ECo(CO) are typically run at high temperature (120-170 °C) and high pressure of a 1 1 mixture of CO E, (200-300 atm "synthesis gas"). These reactions are typically conducted with alkenes, sudi as propene, 1-octene, or a mixture of internal and alkenes generated as part of the Shell higher olefin process (SHOP). 

FIGURE 11.5 A schematic description of the Shell higher olefins process (SHOP). Keim s nickel catalyst gives 1-alkenes of various chain lengths. The subsequent steps allow the chain lengths to be manipulated to maximize the yield of C10-C14 products. Finally, SHOP alkenes are often hydroformylated, in which case the internal alkenes largely give the linear product, as discussed in Chapter 9. 

The required terminal olefins used as substrates for the hydroformylation, such as 1-pentene or 1-octene, are available in large scales and can be derived either from Sasol s Fischer-Tropsch process or from the shell higher olefins process (SHOP), respectively [43, 44]. Alternatively, trimerization or tetramerization of ethylene affords 1-hexene [45] or 1-octene [46]. Dimerization of butadiene in methanol in the presence of a Pd catalyst (telomerization) is another industrially used access for the manufacture of 1-octene [46]. 1-Octene can also be produced on a large scale from 1-heptene via hydroformylation, subsequent hydrogenation, and dehydration (Scheme 6.2) [44]. This three-step homologation route is also valuable for the production of those higher olefins that bear an odd number of C atoms. (X-Olefins can also be derived from internal olefins by cross-metathesis reaction with ethylene [47]. 

Phosphine-modified cobalt hydroformylation is only used commercially by Shell. It is tightly coupled to Shell s Higher Olefins Process (SHOP, see Metathesis Polymerization Processes by Homogeneous Catalysis) that produces a C4 through C20 mixture of linear, internal alkenes for hydroformylation to detergent-grade alcohols. 

FIG. 5 Hydroformylation of higher molecular weight olefins with a ligand-modified cobalt carbonyl catalyst [HCo(CO)3PR3] (Shell process). 

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