Isomerization fluid catalytic cracking

The modem gasolines are produced by blending products from cmde oil distillation, that is, fluid catalytic cracking, hydrocraking, reforming, coking, polymerization, isomerization, and alkylation.Two clear examples of the possible use of solid-acid catalysts in refining processes are the isomerization of lineal alkanes and the alkylation of isobutene with butanes. In both these cases, and due to the octane... 

A number of catalytic processes in current use make use of these strategies including reforming, isomerization, dimerization, alkylation and fluid catalytic cracking (FCC). The object of this paper is to discuss the catalytic strategies available to produce octane in the FCC unit. 

Cracking reactions are carried out in order to reduce the molecular size and to produce more valuable transport fuel fractions (gasoline and diesel). Fluid catalytic cracking is acid catalyzed (zeolites) and a complex network of carbe-nium ion reactions occur leading to size reduction and isomerization (see Chapter 4, Section 4.4). Hydrogenation also takes place in hydrocracking, as well as cracking. 

Microporous and, more recently, mesoporous solids comprise a class of materials with great relevance to catalysis (cf. Chapters 2 and 4). Because of the well-defined porous systems active sites can now be built in with molecular precision. The most important catalysts derived from these materials are the acid zeolites. The acid site is defined by the crystalline structure and exhibits great chemical and steric selectivities for catalytic conversions, such as fluid catalytic cracking and alkane isomerization (cf. Chapter 2). In Section 9.5 we discuss the synthesis of zeolites and, briefly, of mesoporous solids. 

An inspection of the industrial use of zeolites as catalysts shows, however, that only a rather limited number of zeolite topologies are currently used in major industrial processes. Among the more important ones are ultrastable Y (USY) (FAU), rare-earth-exchanged faujasite-type (X, Y) (FAU) andZSM-5-type (MFI) zeolites in fluid catalytic cracking (FCC) of oil fractions [4] noble-metal-loaded U SY for hydroisomerization and hydrocracking of naphtha feedstocks [5] mordenite (MOR) and zeolite Omega (MAZ) -based catalysts for C4-C6 alkane isomerization [6] zeolites ZSM-23 (MTT), ZSM-35 (FER), ZSM-5 for selective oil dewaxing [7] ZSM-5, silicalite (MFI), MCM-22 (MWW), Beta-type (BEA) zeolites for aromatics alkylation to yield ethylbenzene, p-xylene. 

Improvements in chemical processes are very often based on the discovery or development of new catalysts or adsorbents. One particularly exciting example in the field of zeolite catalysis is the replacement of the formerly used amorphous silica-aliunina catalysts in fluid catalytic cracking (FCC) of vacuiun gas oil by rare earth exchanged X-type zeoUtes [1]. This resulted in considerably improved yields of the desired gasoUne and, hence, a much more efficient utilization of the crude oil. Fiuther examples are the introduction of zeolite HZSM-5 as catalyst in the synthesis of ethylbenzene from benzene and ethylene [2], for xylene isomerization [3] and for the conversion of methanol to high-... 

Molecular mechanics has also been used to study skeletal isomerization of 1-butene to isobutene (80), olefin selectivity in fluid catalytic cracking using ZSM-5, zeolite Y, mordenite and P (81), carbon-sulfur bond cleavage over zeolite Y (82), and the location of naphthalene and 2-methylnaphthalene in HZSM-5 (83). In all cases, a methodology similar to those described earlier were adopted (75,77). 

MTBE is produced by reacting methanol with isobutene. Isobutene is contained in the C4 stream from steam crackers and from fluid catalytic cracking m the crude oil-refining process. However, isobutene has been in short supply in many locations. The use of raw materials other than isobutene for MTBE production has been actively sought. Figure 2 describes the reaction network for MTBE production. Isobutene can be made by dehydration of i-butyl alcohol, isomerization of -butenes [73], and isomerization and dehydrogenation of n-butane [74, 75]. t-Butanol can also react with methanol to form MTBE over acid alumina, silica, clay, or zeolite in one step [7678]. t-Butanol is readily available by oxidation of isobutane or, in the future, from syngas. The C4 fraction from the methanol-to-olefins process may be used for MTBE production, and the C5 fraction may be used to make TAME. It is also conceivable that these... 

The new Brownsville, Tex., plant for the manufacture of synthetic liquid fuels from natural gas makes use of this reaction to increase the octane number of its product by as much as 20 units. Synthetic naphtha produced over iron catalyst is highly olefinic and contains substantial amounts of straight-chain isomers with terminal double bonds (8). The shifting of these double bonds toward the center of the molecule may be accomplished by vapor-phase treatment employing synthetic cracking catalyst in the fluid state, under mild catalytic cracking conditions. Oxygenated compounds also present are converted under the isomerization conditions to hydrocarbons and water. 

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