Oxygen bases

Chemical Properties. Although the chemical properties of the trivalent lanthanides are quite similar, some differences occur as a consequence of the lanthanide contraction (see Table 3). The chemical properties of yttrium are very similar too, on account of its external electronic stmcture and ionic radius. Yttrium and the lanthanides are typical hard acids, and bind preferably with hard bases such as oxygen-based ligands. Nevertheless they also bind with soft bases, typicaUy sulfur and nitrogen-based ligands in the absence of hard base ligands. 

With concentrated sulfuric acid, anthraquinone forms oxonium salts, thus falling into a class of compounds known as " oxygen bases" (15). In an aqueous solution, anthraquinone has an ionisation constant equal to 7 x 10 and a of 7.4 (16). 

There are 12 producers of ethylene oxide ia the United States. Table 9 shows the plant locations, estimated capacities, and types of processes employed. The total U.S. production capacity for 1992 was ca 3.4 x 10 metric tons. The percentages of total domestic production made by the air- and oxygen-based processes are ca 20 and 80%, respectively. The largest producer is Union Carbide Corp. with approximately one-third of the United States ethylene oxide capacity. About 94% of domestic ethylene oxide capacity is located on the Gulf Coast near secure and plentiful ethylene suppHes. Plans for additional U.S. production ia the 1990s have been announced by Union Carbide (incremental expansions), Eormosa Plastics (at Pt. Comfort, Texas), and Shell (at Geismar, Louisiana) (101). 

Figure 3 shows a simple schematic diagram of an oxygen-based process. Ethylene, oxygen, and the recycle gas stream are combined before entering the tubular reactors. The basic equipment for the reaction system is identical to that described for the air-based process, with one exception the purge reactor system is absent and a carbon dioxide removal unit is incorporated. The CO2 removal scheme illustrated is based on a patent by Shell Oil Co. (127), and minimises the loss of valuable ethylene in the process. 

Fig. 3. Oxygen-based direct oxidation process for ethylene oxide (96,102,103,109,117—119,127).

Process Technology Considerations. Innumerable complex and interacting factors ultimately determine the success or failure of a given ethylene oxide process. Those aspects of process technology that are common to both the air- and oxygen-based systems are reviewed below, along with some of the primary differences. 

Both air and oxygen processes can be designed to be comparable in the following areas product quaUty, process flexibiUty for operation at reduced rates, and on-stream rehabiUty (97,182). For both processes, an on-stream value of 8000 h/yr is typical (196). The rehabiUty of the oxygen-based system is closely linked to the rehabiUty of the air-separation plant, and in the air process, operation of the multistage air compressor and power recovery from the vent gas is cmcial (97). 

For the same production capacity, the oxygen-based process requires fewer reactors, all of which operate in parallel and are exposed to reaction gas of the same composition. However, the use of purge reactors in series for an air-based process in conjunction with the associated energy recovery system increases the overall complexity of the unit. Given the same degree of automation, the operation of an oxygen-based unit is simpler and easier if the air-separation plant is outside the battery limits of the ethylene oxide process (97). 

From the preceding discussion, it is clear that no meaningful generalizations can be made regarding the overall superiority of either the air- or oxygen-based process. 

Oxygen nucleophiles usually attack a ring carbon atom rather than the sulfur atom of a thiirane, and those cases in which desulfurization is observed on treatment of a thiirane with oxygen bases probably involve the extrusion of sulfur by mechanisms other than a nucleophilic attack on sulfur, e.g. thermal. Desulfurization of thiirane intermediate (43)... 

It was pointed out earlier that the low nucleophilicity of fluoride ion and its low concentration in HF solutions can create circumstances not commonly observed with the other halogen acids. Under such conditions rearrangement reactions either of a concerted nature or via a true carbonium ion may compete with nucleophilic attack by fluoride ion. To favor the latter the addition of oxygen bases, e.g., tetrahydrofuran, to the medium in the proper concentration can provide the required increase in fluoride ion concentration without harmful reduction in the acidity of the medium. 

Diffusion-limited rate control at high basicity may set in. This is more eommonly seen in a true Br nsted plot. If the rate-determining step is a proton transfer, and if this is diffusion controlled, then variation in base strength will not affect the rate of reaction. Thus, 3 may be zero at high basicity, whereas at low basicity a dependence on pK may be seen. ° Yang and Jencks ° show an example in the nucleophilic attack of aniline on methyl formate catalyzed by oxygen bases. 

Nakano, M. (1990). Determination of superoxide radical and singlet oxygen based on chemiluminescence of luciferin analog. Method. Enzymol. 186 585-591. 

Vanadium-based turnover rates for the oxidation of methanol matched those obtained previously using these same samples but a different reactor [12], The oxygen-based turnover rates agreed very well with those obtained by Oyama and Somorjai. 

Oxygen-based industrial process Micro reactor-based process (laser-LICA) Micro reactor-based process (etched) Micro reactor-based process (Aluchrom)... 

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