Industrial processes Shell higher olefin process

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... 

The Shell higher olefins process, or SHOP, is one of the most important large-scale processes in the chemical industry which uses homogeneous catalysis [79]. In this process, ethene is oligomerized to medium- and long-chain a-olefins. The products... 

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. 

The Ni complex incorporating mixed-donor P/O-ligands find industrial application in the Shell Higher Olefin Process (SHOP) to yield a-alkenes, while the complex (71) has been shown to be active in the polymerization of olefins and will also tolerate functionalized monomers such as methyl methacrylate. Grubbs and coworkers have adapted the standard SHOP catalyst to yield a highly active family of catalysts (eg. 72) for the polymerization of low-branched polyethylene. This is in contrast to the diimine catalysts (Section 5.2) which lead to a more highly branched polyethylene. 

Table 2.1 gives a comparative overview of the pro and cons of the various options in processes with multiphasic operations. On going from left to right in the table the industrial relevance of the processes decreases. The RCH/RP oxo process and the Shell Higher Olefin Process (SHOP) discussed later belong to the first class (aqueous biphase) and second class (organic biphase), respectively. 

For an industrial application see the Shell higher olefin process (SHOP) ... 

The nickel-catalyzed Shell higher olefin process (SHOP) is of major industrial importance [9,11]. Ethylene is converted to a-olefins with a statistical distribution in which the lower oligomers are favored (so-called Schulz Flory distribution). This is carried out at 80-120 °C and 70 140 bar in the presence of a nickel catalyst with phosphine ligands such as Ph2PCH2COOK. The product mixture is separated into C4 io, C12-18, and C20+ fractions by distillation. 

The liquid support may be water, supercritical fluids, ionic liquids, organic liquids or fluorous liquids [12]. The Shell higher olefin process (SHOP) and the Oxo synthesis (hydrofomylation) are examples of important industrial processes based on biphasic catalytic systems. 

The Shell higher olefin process (SHOP process) is an example for ethenolysis on an industrial scale. From the ethenolysis of an oleic double bond such as in tall oil fatty acid methyl ester using a Grubbs catalyst methyl-9-decenoate and 1-decene are formed (Figure 3B.15) key intermediates in the synthesis of flavors and fragrances, insect pheromones as environmentally friendly alternatives to pesticides, and prostaglandins on the one side and poly-a-olefins as lubricant base stock on the other. ... 

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]. 

This reaction was first used in petroleum reformation for the synthesis of higher olefins (Shell higher olefin process - SHOP), with nickel catalysts under high pressure and high temperatures. Nowadays, even polyenes with MW > 250,000 are produced industrially in this way. 

Dimerisation of olefins is a major industrial process, and is carried out on a multi million ton scale annually.111 One of the most important methods is represented by the Shell Higher Olefin Process (SHOP), which can even be run under biphasic conditions. In the oligomerisation of ethylene, the catalyst is generated in situ in 1,4-butanediol from a nickel salt, Na[BH4] and a chelating ligand. The olefins formed in the reaction are immiscible with the polar solvent and are isolated by phase separation and subsequent distillation.[2]... 

The reaction is applied in industrial processes (Phillips triolefin process. Shell higher olefin process) and has importance in ring opening-metathesis polymerization (ROMP) in polymer chemistry [1]. In the past, olefin metathesis was not commonly applied in organic synthesis [2] because of the reversibility of the reaction, leading to olefin mixtures. In contrast, industrial processes often handle product mixtures easily. In ROMP, highly strained cyclic olefins allow the equilibrium of the reaction to be shifted towards the product side. 

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