Isomerization Shell process

Cobalt carbonyls are the oldest catalysts for hydroformylation and they have been used in industry for many years. They are used either as unmodified carbonyls, or modified with alkylphosphines (Shell process). For propene hydroformylation, they have been replaced by rhodium (Union Carbide, Mitsubishi, Ruhrchemie-Rhone Poulenc). For higher alkenes, cobalt is still the catalyst of choice. Internal alkenes can be used as the substrate as cobalt has a propensity for causing isomerization under a pressure of CO and high preference for the formation of linear aldehydes. Recently a new process was introduced for the hydroformylation of ethene oxide using a cobalt catalyst modified with a diphosphine. In the following we will focus on relevant complexes that have been identified and recently reported reactions of interest. 

The operating conditions for the three processes are very similar— only temperatures are somewhat dissimilar. The Shell Development system, employing a modified Friedel-Crafts system, operates at a lower temperature—150°-210°F vs. 250°-400°F for the other two processes. However, the equilibrium effects of the temperature differences are minimized as shown by the similarity in n-C4 and n-C5 yields shown in Table VI. Unleaded octane numbers for C5/C6 isomerate, obtained from a pure C5/C6 straight-run fraction, could not be found in the literature for the Shell process. However, pilot unit operations charging laboratory blends of n-C5, n-C6, and C6 naphthenes have been reported (26, 45). In the Shell process the use of antimony trichloride and hydrogen has considerably reduced the amount of side reactions for a Friedel-Crafts system so that the yield for this process is quite close to the yield structure for the other two processes. 

Fiq. 12. Vapor-phase butane isomerization. Shell Isocel process. 

Fiq. 18. Liquid-phase butane isomerization. Shell antimony chloride process. 

Fig. 20. Process variables for butane isomerization. Shell liquid-phase process. Conditions (unless otherwise noted) temperature, 176°F. residence time, 13-15 minutes AlCU, 7.5 wt.% HCl, 4.0 wt.% catalyst-to-hydrocarbon ratio, 1/1.

Essential features of the Shell naphthene isomerization process (24) are outlined in Figure 26. Although the contactor principle employed in the other liquid-phase Shell processes is used, the catalyst is handled in the form of hydrocarbon complex. A carefully fractionated and dried concentrate of dimethylcyclopentanes is preheated to 200°F., and about 0.1% of anhydrous hydrogen chloride is added. The feed is joined by a stream of catalyst complex and charged to the reactor under a gauge... 

The three major commercial Hcensors of xylenes isomerization processes are Engelhard, UOP, and Mobil. Several other companies have developed and used their own catalysts. These companies include Mitsubishi Gas—Chemical, Toray, ICI, Amoco, and Shell. AH of these processes are discussed herein. 

Shell Higher Olefin Process) plant (16,17). C -C alcohols are also produced by this process. Ethylene is first oligomerized to linear, even carbon—number alpha olefins using a nickel complex catalyst. After separation of portions of the a-olefins for sale, others, particularly C g and higher, are catalyticaHy isomerized to internal olefins, which are then disproportionated over a catalyst to a broad mixture of linear internal olefins. The desired fraction is... 

Paraffin Isomerization. Another weU-estabhshed commercial process which employs zeoflte catalysts is the isomerization of normal paraffins into higher octane, branched isomers. The catalyst for the Hysomet process of the Shell Oil Co. is dual-functional, and consists of a highly acidic, latge-pote zeoflte loaded with a small amount of a noble-metal hydrogenation component. This catalyst possesses the same... 

Examples for necessary process improvements through catalyst research are the development of one-step processes for a number of bulk products like acetaldehyde and acetic acid (from ethane), phenol (from benzene), acrolein (from propane), or allyl alcohol (from acrolein). For example, allyl alcohol, a chemical which is used in the production of plasticizers, flame resistors and fungicides, can be manufactured via gas-phase acetoxylation of propene in the Hoechst [1] or Bayer process [2], isomerization of propene oxide (BASF-Wyandotte), or by technologies involving the alkaline hydrolysis of allyl chloride (Dow and Shell) thereby producing stoichiometric amounts of unavoidable by-products. However, if there is a catalyst... 

The earliest industrial zeolitic isomerization process was the Hysomer process, formerly offered for license by Shell. Currently UOP offers a zeolite- and Pt-con-taining catalyst HS-10 in the fixed-bed UOP TIP process [3]. A similar catalyst Hysopar was introduced by Sud-Chemie [22] in the CKS Isom process (Cepsa-Kellogg-Sud Chemie). Recently there were reports of IMP-02 and CI-50 commercial catalysts from China [23] and Russia [24]. 

The third liquid-phase butane-isomerization process, shown in Figure 5, was developed by Shell as an improvement over the original intermittent vapor-phase process. 

Pentane Isomerization. Pentane isomerization, although carried out on a much smaller scale, increased the critical supply of aviation gasolines toward the end of the war. Two pentane processes—one developed by Shell and one by Standard (Indiana) —were commercialized before the end of the war. The principal differences between the butane and pentane processes are the use in pentane isomerization of somewhat milder conditions and the use of an inhibitor to suppress side reactions, principally disproportionation. In general, the problems of the butane processes are inherent also in pentane isomerization, but the quality of the feed stocks is less important. Catalyst life is much... 

Naphthene Isomerization. In addition to the paraffin isomerization processes, naphthene isomerization also proved useful during the war in connection with the manufacture of toluene. In the Shell dehydrogenation process for the manufacture of toluene, good yields depend upon increasing the methylcyclohexane content of the feed by isomerization of dimethylcyclopentanes. This process was employed commercially at one refinery in the Midwest and one on the Pacific Coast. 

The naphthene isomerization process has been applied also to the conversion of meth-ylcyclopentane to cyclohexane for subsequent dehydrogenation to benzene. Shell s Wilmington, Calif., refinery has been operating commercial equipment on this basis since March 1950 (18). 

Alkenes. At present alkene isomerization is an important step in the production of detergent alkylates (Shell higher olefin process see Sections 12.3 and 13.1.3).264 265 Ethylene oligomerization in the presence of a nickel(O) catalyst yields terminal olefins with a broad distribution range. C4-C6 and C2o+ alkenes, which are not suitable for direct alkylate production, are isomerized and subsequently undergo metathesis. Isomerization is presumably carried out over a MgO catalyst. 

Salient features of the three commercialized processes are shown in Table VI. The Shell Development Co s liquid phase isomerization process uses an improved Friedel-Crafts catalyst system consisting of a solution of A1C13 in SbCl3 and uses HC1 as a promoter. This process was first evaluated in an existing isomerization unit in 1961 (26) giving it the... 

In the case of closed-shell organic molecules M can be an excited singlet or triplet state. M can react on its own in unimolecular reactions (dissociations, isomerizations) or it can react with another (ground state) molecule N in bimolecular processes (e.g. additions, substitutions, etc.). 

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