Shell Higher Olefins Process SHOP

Shell Higher Olefins Process (SHOP). In the Shell ethylene oligomerization process (7), a nickel ligand catalyst is dissolved in a solvent such as 1,4-butanediol (Eig. 4). Ethylene is oligomerized on the catalyst to form a-olefins. Because a-olefins have low solubiUty in the solvent, they form a second Hquid phase. Once formed, olefins can have Htfle further reaction because most of them are no longer in contact with the catalyst. Three continuously stirred reactors operate at ca 120°C and ca 14 MPa (140 atm). Reactor conditions and catalyst addition rates allow Shell to vary the carbon distribution. 

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... 

Biphasic catalysis is not a new concept for oligomerization chemistry. On the contrary, the oligomerization of ethylene was the first commercialized example of a biphasic, catalytic reaction. The process is known under the name Shell Higher Olefins Process (SHOP) , and the first patents originate from as early as the late 1%0 s. 

In addition to the neutral nickel/phosphine complexes used in the Shell Higher Olefins Process (SHOP), cationic Ni-complexes such as [(mall)Ni(dppmo)][SbF6] (see Figure 5.2-7) have attracted some attention as highly selective and highly active catalysts for ethylene oligomerization to HAOs [106]. 

FIG. 3 Flow sheet of the manufacture of n-u-olefins and /z-y-olefins by the Shell higher olefin process (SHOP)... 

Apart from the UOP Pacol process, today s only other meaningful economic process is the Shell higher olefin process (SHOP) in which /z-olefins are produced by ethylene oligomerization. Until 1992 Hiils AG used its own technology to produce -60,000 t/year of /z-olefins by the chlorination of /z-paraffins (from Molex plant) and subsequent dehydrochlorination [13]. In the past, the wax cracking process (Shell, Chevron) played a certain role. In the Pacol and Hiils processes, olefins are obtained as diluted solutions in paraffin (Pacol to max. 20%, Hiils about 30%) without further processing these are then used for alkylation. In contrast, the SHOP process produces pure olefins. 

Catalysts based on nickel that dimerize or oligomerize a-olefins have been known for many years and are commercially valuable. The Shell higher olefin process (SHOP), for example, uses Ni(II) catalysts developed by Keim and coworkers such as 1.1 and 1.2 bearing P-O chelating ligands to oligomerize ethylene into higher olefins in the manufacture of surfactants, lubricants, and fine chemicals (Fig. 1) [9-11]. Late transition metals are more suited for the polymerization of... 

Sheet production, of methacrylic ester polymers, 16 282 Sheet silicon, 23 40—41 Shell a-olefin manufacture, 17 713—714. See also Shell higher olefins process (SHOP)... 

Shell entrained flow gasifier, 6 799-800 Shellfish poison, 5 822 Shell higher olefins process (SHOP), 17 122, 718-720, 725, 26 939... 

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... 

By far the largest application of metathesis is a principal step in the Shell higher olefin process (SHOP),24 140 141 with the aim of producing detergent-range olefins... 

Grubbs group [31, 32] developed another type of Ni-based catalyst. This neutral Ni-catalyst, based on salicylaldimine ligands, is active in ethene polymerisation without any co-activator and originated from the Shell higher olefin process (SHOP). Shortly thereafter another active neutral P,0-chelated nickel catalysts for polymerisation of ethene in emulsion was developed by Soula et al. [33, 34, 35]. The historical development of single site catalysts is represented in Fig. 1. 

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. 

Oligomerization of ethylene to higher even carbon number alpha olefins. This is the growth part of the Shell Higher Olefin Process (SHOP) Unit. 

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