Basis phenol hydrogenation

The adipic acid process is a relatively complex process and essentially contains two plants phenol hydrogenation and KA oil oxidation. We should therefore assume at least four shift positions for each plant, say nine total. For a Northeast Asia basis, we expect that the salary cost per shift position will be lower than the typical 50,000 per year that we would assume for a U.S. Gulf Coast plant. As a first approximation this is estimated as 30,000/y. The remaining salary and overhead costs are fixed following the assumptions given in Section 6.2.4. 

Titanium Silicates. A number of titanium siUcate minerals are known (160) examples are Hsted in Table 19. In most cases, it is convenient to classify these on the basis of the connectivity of the SiO building blocks, eg, isolated tetrahedra, chains, and rings, that are typical of siUcates in general. In some cases, the SiO units may be replaced, even if only to a limited extent by TiO. For example, up to 6% of the SiO in the garnet schorlomite can be replaced by TiO. In general, replacement of SiO by TiO bull ding blocks increases the refractive indices of these minerals. Ti has also replaced Si in the framework of various zeofltes. In addition, the catalytic activity of both titanium-substituted ZSM-5 (TS-1) and ZSM-11 (TS-2) has received attention (161), eg, the selective oxidation of phenol, with hydrogen peroxide, to hydroquinone and catechol over TS-1 has been operated at the 10,000 t/yr scale in Italy (162). 

Hydrogenation of carbonyls, or incipient carbonyls such as phenols (86), in lower alcohol solvents may result in the formation of ethers. The ether arises through formation of acetals or ketals with subsequent hydrogenolysis. The reaction has been made the basis of certain ether syntheses (45,97). Reaction of alcohols with carbonyls may be promoted by trace contamination, such as iron in platinum oxide (22,53), but it is also a property of the hydrogenation catalyst itself. So strong is the tendency of palladium-hydrogen to promote acetal formation that acetals may form even in basic media (61). 

Much rarer than the inclusion of phenols is complex formation between alcohols and pyridinomacrocycles. In some combinations (selected macro-cycles and alcohols) complexes could be isolated (Weber and Vogtle, 1980). TTie hydrogen bond formation between pyridines and alcohols is the basis for an application, the additions of alcohols to ketenes catalysed by concave pyridines [13] (Liining et al., 1991b Schyja, 1995). 

Note that any attempt to differentiate carboxylic acids from phenols on the basis of how broad their respective signals are is to be discouraged in the strongest possible terms Whilst carboxylic acids tend to be broader than phenols, it is by no means guaranteed that this is always the case. Steric and electronic factors and hydrogen bonding can reverse this in certain situations. 

Carbanionic metal alkyls and hydridic metal hydrides will react with alcohols or phenols to give alkoxides and phenoxides, typically in excellent yields. The reaction is also important as it forms the basis for the calorimetric measurement of a large number of metal-alkyl bond dissociation energies.93,94 This synthetic method tends to be very convenient due to the volatility of the generated alkane or hydrogen side products. Monoalkyl alkoxides of Be,95 Mg96 and Zn97 can be obtained in this way (equation 26). 

The ligands on the basis of spatially hindered phenols can exist in different redoxforms diamagnetic phenol, paramagnetic phenoxyl, phenolate, and quinolate. These forms are interrelated by reversible transitions, including electron, proton and hydrogen transport (5.11) ... 

The structure of the capsule, proposed initially on the basis of these NMR-data, was completely confirmed by the first single crystal X-ray structure (Figure 5.2) [34]. The two calix[4]arenes are connected via their wide rims by a seam of intermolecular hydrogen bonds alternatingly involving the urea residues of both calixarenes. The directionality of this hydrogen bonded belt is the reason for the inequivalence of the two aromatic protons of a given phenolic unit mentioned above. 

Table 5.3 shows the enthalpy and Gibbs free energy of formation of species at 289.13 K and 1 atm [3]. On this basis standard AH and AG[J can be determined, as shown in Table 5.4. The hydrogenation of phenol is highly exothermic, while the dehydrogenation of cyclohexanol is moderately endothermic. The conversion...

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