Fluid catalytic dehydration

Figure 3.35 shows a process flow diagram of Phillips MTBE/ETBE/TAME process. This process is often called the Phillips Etherification Process. The reaction section (1,2) which receives methanol and isobutene concentrate, contains an ion exchange resin. The isobutene concentrate may be mixed olefins from a Fluid Catalytic Cracking Unit (FCCU) or steam cracker or from the on-purpose dehydration of isobutene (Phillips STAR process). High purity MTBE (99 wt%) is removed as a bottoms product from the MTBE fractionator (3). AH of the unreacted methanol is taken overhead, sent to a methanol... 

Isobutene, the main feedstock, is obtained in the form of raffinate from steam crackers, which make up an estimated 40% of MTBE feedstock throughout the world. Isobutene in the form of butene-butane fractions from fluid catalytic crackers represents 28% of MTBE feedstocks isobutene from dehydrogenation of isobutane represents 12% of MTBE feedstocks and isobutene by dehydration of tert-butanol represents 36% of MTBE feedstocks. The Butamer process is often used for the primary butane isomerization, while the Catofln and Olefex processes are commonly used for the isobutane dehydrogenation. 

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... 

Fontes tt al. [224,225 addressed the acid—base effects of the zeolites on enzymes in nonaqueous media by looking at how these materials affected the catalytic activity of cross-linked subtilisin microcrystals in supercritical fluids (C02, ethane) and in polar and nonpolar organic solvents (acetonitrile, hexane) at controlled water activity (aw). They were interested in how immobilization of subtilisin on zeolite could affected its ionization state and hence their catalytic performances. Transesterification activity of substilisin supported on NaA zeolite is improved up to 10-fold and 100-fold when performed under low aw values in supercritical-C02 and supercritical-ethane respectively. The increase is also observed when increasing the amount of zeolite due not only to a dehydrating effect but also to a cation exchange process between the surface proton of the enzyme and the sodium ions of the zeolite. The resulting basic form of the enzyme enhances the catalytic activity. In organic solvent the activity was even more enhanced than in sc-hexane, 10-fold and 20-fold for acetonitrile and hexane, respectively, probably due to a difference in the solubility of the acid byproduct. 

Fluid-solid MSR have been extensively used particularly for gas-solid reactions such as catalytic partial oxidations, selective hydrogenations, dehydrogenations, dehydrations, and reforming processes [57, 58]. Similarly to the other reactions carried out in MSR, the main objective was to achieve better temperature control in order to prevent selectivity loss, catalyst deactivation, hot spot formation and, thus, allowing safe processing with high throughput. 

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